CN110054493A - A kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material and preparation method - Google Patents
A kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material and preparation method Download PDFInfo
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Abstract
The invention belongs to negative tempperature coefficient thermistor technical field more particularly to a kind of Lanthanum Chromite based perovskite phases and Spinel NTC thermal sensitive ceramic material and preparation method.The layer structure that the NTC thermal sensitive ceramic material is mutually formed by Lanthanum Chromite based perovskite is connected in series with the layer structure that Spinel is formed, and Lanthanum Chromite based perovskite phase and Spinel interface are the transition zone that the two-phase powder is uniformly mixed to form, the Lanthanum Chromite based perovskite is mutually LaCr1‑ xMxO3(M refers to transition metal or alkali earth metal), the Spinel are AB2O4.It connects with Spinel stratiform NTC thermal sensitive ceramic material the present invention is based on Lanthanum Chromite based perovskite phase, the resistance value and calculated value of measurement are almost the same；Meanwhile by control two phase material it is compound than and doping can effectively controlled material resistance value B value variation it is small；Chromium lanthanum based perovskite phase LaCr1‑xMnxO3Introducing improve the stability of material.
Description
Technical field
The invention belongs to negative tempperature coefficient thermistor technical field more particularly to a kind of Lanthanum Chromite based perovskite phases and point
Spar phase NTC thermal sensitive ceramic material and preparation method.
Background technique
It is only intended to increase understanding of the overall background of the invention for information disclosed in background of invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Negative temperature coefficient (NTC) thermistor, because it is high with temperature measurement accuracy, interchangeability is good, high reliablity, at low cost etc.
Advantage in temperature measurement, control, compensation and inhibits the various aspects such as surge current to be widely used, it is considered to be to have
The electronic component of tremendous expansion potentiality has good application prospect.NTC thermal sensitive ceramic material is generally with spinel structure
Its B value is also high when the resistivity of principal crystalline phase, this kind of material is high, and vice versa；The polynary system ceramics of spinel structure composition simultaneously
The stability of material is poor, and sintered ceramics are in nonequilibrium condition, and material electric property is caused to change, this two o'clock constrains
The application of spinelle NTC temperature-sensitive element solves the problems, such as that this key is to explore new NTC thermal sensitive ceramic material.Previous research
It is mainly improved from the composition of material system, for example mixes Cu in spinel, resistance value can be greatly lowered, but same
When will cause the decline of B value and stability；Highly conductor phase is for another example introduced in spinel and carries out conventional composite, i.e. powder is equal
Forming and sintering after even mixing can substantially reduce its resistivity, but B value also can be reduced and then simultaneously.
It is considered herein that: multiplicity, the connection type of composite material are adjustable and change, and reaching homogenous material cannot obtain
Excellent performance, also homogenous material can be generated due to product effect and completely new performance that technology is unable to get；The law of resistance
The resistance R of conductor is directly proportional to its length L, electricalresistivityρ in (R=ρ L/S), is inversely proportional with its cross-sectional area S, therefore, cross section
In the case that product is constant, thickness reduction will be such that its resistance value is greatly lowered；Perovskite Phase ceramics Lanthanum Chromite (LaCrO3) because of tool
Have giant magnetoresistance (GMR) effect, sensing and a catalytic performance, and solid oxide fuel cell connecting material, high temperature exothermic material,
Catalyst etc. is widely used, and is up-and-coming ceramic material, but its application as NTC thermistor
Wait to develop.
Summary of the invention
For the one-way and limitation and preparation method etc. of above-mentioned spinel structure NTC thermo-sensitive material electrical property regulation
There are the problem of, the present invention is intended to provide a kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material and preparation
Method.The present invention can guarantee that material resistance value is height-adjustable while it is small to keep its B value to change, this is used for different necks to preparation
Domain, low resistance, the NTC thermistor of high B value of especially inhibition surge current are of great significance.
An object of the present disclosure is to provide a kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Second purpose of the invention, is to provide the Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material
Preparation method.
Third purpose of the present invention, provide the Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material and its
The application of preparation method.
For achieving the above object, the invention discloses following technical proposals:
Firstly, the present invention discloses a kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, by chromic acid
The layer structure that the layer structure that lanthanum based perovskite is mutually formed is formed with Spinel is connected in series, and Lanthanum Chromite based perovskite phase
It is the transition zone that the two-phase powder is uniformly mixed to form with Spinel interface, the Lanthanum Chromite based perovskite is mutually LaCr1- xMnxO3, and 0≤x≤0.8；The Spinel is AB2O4。
Optionally, described A, B refer to one of transient metal Mn, Co, Ni etc..
LaCrO3With good high-temperature stability and electric conductivity, Modulatory character of the electric conductivity by Doped ions and environment
Height, and there is NTC characteristic in certain temperature range.The advantage and the law of resistance of bonded composite of the present invention, pass through doping
Means have devised completely new NTC material complex form: stratiform series connection；Adjustable to obtain resistance value height, the variation of B value is small, surely
The qualitative high and excellent NTC thermal sensitive ceramics of consistency.Layered series connection refers between Lanthanum Chromite based perovskite and Spinel
Organic connection is realized by transition zone, forms the cascaded structure of stratiform, and this structure helps to significantly improve thermistor material
The performance of material.
Further, the Lanthanum Chromite based perovskite, transition zone, Spinel volume ratio be (0.1-0.89): 0.01:
(0.89-0.1)。
Further, in the transition zone, LaCr1-xMnxO3And AB2O4Volume ratio be 1:1.
Preferably, the oxide molecule formula of the Spinel is NiMn2O4。
Secondly, the present invention discloses the preparation side of the Lanthanum Chromite based perovskite phase Yu Spinel NTC thermal sensitive ceramic material
Method includes the following steps:
(1) prepared by slurry:
By LaCr1-xMnxO3Middle atom molar ratio weighs the oxide of each metallic element, and wet-milling obtains C slurry, spare；
By AB2O4Middle atom molar ratio weighs the oxide of each metallic element, and wet-milling obtains D slurry, spare；
(2) C slurry, D slurry are separately dried, are then ground respectively, obtain C powder, D powder, it is spare；
(3) C powder, D powder are calcined respectively, respectively obtains Perovskite Phase (LaCr1-xMnxO3) powder, Spinel
(AB2O4) powder；In addition, by LaCr1-xMnxO3And AB2O4It is mixed to get mixed powder；
(4) by the LaCr in step (3)1-xMnxO3Powder, LaCr1-xMnxO3And AB2O4Mixed powder, AB2O4Powder is pressed
Block materials are made according to said sequence, wherein the mixed powder is transition zone；
(5) block materials in step (4) are first warming up to 400-500 DEG C of heat preservation 5-7h, then heat to 1250-1300
DEG C heat preservation 10-20min, be cooled to 1050-1100 DEG C of heat preservation 10-15h after the completion, finally cool to the furnace room temperature to get.
In step (1), the wet-milling is using agate ball as ball-milling medium, using dehydrated alcohol as decentralized medium；Agate ball: former
Material: dehydrated alcohol mass ratio is 2.5:1:1；Preferably, wet-milling is along counterclockwise alternately, along interval time counterclockwise
30min；The wet-milling time is 24-36h.
In step (2), the drying temperature is 80-90 DEG C, and drying time is for 24 hours；Milling time is 2h.
In step (3), while guaranteeing powder crystallinity again will not crystal grain it is excessive, therefore by the calcining of C powder, D powder
Temperature is selected as 850-950 DEG C；Calcination time is 2-4h.
In step (3), the LaCr1-xMnxO3Powder, AB2O4Powder, LaCr1-xMnxO3And AB2O4Mixed powder it is logical
The mode for crossing binder granulation obtains, in order to obtain epigranular, the powder body material of good fluidity.
It further, further include by LaCr before the granulation1-xMnxO3Powder, AB2O4The step of powder is ground, in order to
Obtain even-grained powder.
Preferably, the LaCr1-xMnxO3D50It is 0.117-1.421 μm；The AB2O4D50For 0.108-1.213 μ
m.The D50Refer to that cumulative particle sizes volume percentile reaches partial size corresponding when 50%.
Optionally, the binder of the granulation is PVA；The additional amount of PVA is the 2.0- of granulation powder weight
3.0%.
In step (3), in the mixed powder, LaCr1-xMnxO3And AB2O4Volume ratio be 1:1.
In step (4), using the method suppressed under stress by LaCr1-xMnxO3Powder, LaCr1-xMnxO3With
AB2O4Mixed powder, AB2O4Block materials are made in powder；Method particularly includes: it is pressed into Φ 10mm's under the pressure of 10MPa
Disk, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min.
In step (5), the heating rate for being warming up to 400-500 DEG C is 1-5 DEG C/min；It is described to be warming up to 1250-
1300 DEG C of heating rate is 10-15 DEG C/min；It is described be cooled to 1050-1100 DEG C used in the time be set as 1-3min.This
This two-step sintering method that invention uses facilitates while inhibiting crystal boundary migration, and grain boundary decision is kept to be in active state.
Finally, the present invention discloses the Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material and its preparation
Method is inhibiting the application in surge current and observing and controlling temperature field.The present invention is based on Lanthanum Chromite based perovskites and spinelle to pass through layer
The negative temperature coefficient thermal-sensitive ceramic material of shape series system design can be in the case where keeping the variation of material B value small, and resistance value is high
It spends adjustable, makes material that there is different parameter combinations, stability also significantly improves, and meets and multi-field (inhibits surge current, wide temperature
Area's thermometric etc.) requirement to NTC thermistor.
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) the present invention is based on the negative temperature systems that Lanthanum Chromite based perovskite phase and Spinel are designed by stratiform series system
Number thermal sensitive ceramic material is combined by the series connection of two major phase material stratiforms, and resistance change meets resistance series connection changing rule,
That is RString=R1+R2, the resistance value and calculated value of measurement be almost the same, it was demonstrated that mentality of designing of the present invention is in practical applications
Reasonability and feasibility.
(2) the advantages of present invention is according to the law of resistance and composite material, devises completely new NTC material complex form-layer
Shape series connection is compound, and Lanthanum Chromite based perovskite can provide good electric conductivity and stability mutually for composite material, and Spinel
Good NTC effect is provided for composite material；The mixed uniformly transition of transition zone that two-phase powder at two-phase interface is formed
Layer then ensure that the matching of thermal expansion coefficient in high-temperature sintering process, and such complex form energy Effective Regulation resistance value while protects
The B value variation for holding material is small, to provide new material bodies to prepare the multi-field NTC thermistor combined with different parameters
It is and instructs thinking.
(3) the Perovskite Phase LaCrO that the present invention uses3Itself has very high electrochemical stability and electric conductivity；And mistake
The doping of metallic element Mn is crossed not only due to its variable valency (Mn2+、Mn3+、Mn4+、Mn5+Etc. multivalent state) improve the electricity of material
Performance adjustability, while also increase the forbidden bandwidth of basis material, further improves the stability of the material system, also into
One step improves base material LaCrO3NTC effect；Because the connection of transition zone has good phase stability at two-phase interface,
Two phase material is effectively prevented because the difference of shrinking percentage in sintering process is deformed crack in interface, therefore the stratiform is connected
NTC thermal sensitive ceramic material has high resistance adjustability and stability.
(4) present invention prepares NTC thermal sensitive ceramic material using two-step sintering method, that is, is warming up to after maximum sintering temperature quickly
Lower temperature is cooled to, and carries out long-time heat preservation under the lower temperature, by this sintering schedule, avoids high temperature sintering
Issuable crystal grain is grown up in the process, thus keep grain boundary decision to be in active state while inhibiting crystal boundary migration, it is real
The purpose that sintering is completed under the premise of crystal grain is not grown up is showed；In addition from the angle of environmental protection, which can also effectively be saved
Energy.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is the R of NTC thermal sensitive ceramic material prepared by embodiment 1-3 and comparative example 1-225℃And theoretical calculation and measurement are tied
Fruit comparison diagram.
The resistance-temperature characteristic curve (- 20-150 for the NTC thermal sensitive ceramic material that Fig. 2 is embodiment 3-6 and prepared by comparative example 1
℃)。
Fig. 3 is the SEM picture of the section two-phase interface junction of NTC thermal sensitive ceramic material prepared by embodiment 1.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As previously mentioned, so far, guarantee B value while without energy Effective Regulation resistance value and vary less and stablize
The good method of property.Therefore, exploring new method and material system keeps material resistance height-adjustable while keeping its B value constant,
And then prepare being even more important for the NTC material change that resistance height is adjustable, stability is high.For this purpose, the present invention proposes a kind of chromic acid
Lanthanum based perovskite phase and Spinel NTC thermal sensitive ceramic material and preparation method；Now in conjunction with the drawings and specific embodiments to this
Invention is further illustrated.
Embodiment 1
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase (LaCr0.9Mn0.1O3)
With Spinel (NiMn2O4) in atom molar ratio, weigh each oxide respectively and be placed in agate jar, using agate ball as ball
Grinding media, dehydrated alcohol are decentralized medium, and wet-milling for 24 hours, controls each material mass ratio in ball grinder are as follows: agate ball: raw material: anhydrous
Ethyl alcohol=2.5:1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively
Material；
(2) two kinds of slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively；
(3) C powder is calcined into 2h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCr0.9Mn0.1O3) powder；By D
Powder calcines 4h at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(4) by LaCr0.9Mn0.1O3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains
LaCr0.9Mn0.1O3And NiMn2O4Powder granularity (D50) it is respectively 1.421 μm and 1.213 μm, then again using PVA as binder pair
The powder is granulated, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to mobility
Good, good moldability LaCr0.9Mn0.1O3Powder, NiMn2O4Powder and LaCr0.9Mn0.1O3And NiMn2O4Mixed powder, institute
The additional amount for stating PVA is the 2.5% of granulation powder weight, LaCr in the mixed powder0.9Mn0.1O3And NiMn2O4Volume
Than for 1:1；
(5) LaCr that will be granulated described in step (4)0.9Mn0.1O3Powder, mixed powder, NiMn2O4Powder is successively
Sequence is laid in a mold, forms LaCr0.9Mn0.1O3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder
(transition zone) is located at LaCr0.9Mn0.1O3Powder layer and NiMn2O4Between powder layer, the LaCr0.9Mn0.1O3Powder, mixed powder
Body, NiMn2O4The volume ratio of powder is sequentially 0.1:0.01:0.89, with the pressure of 10MPa by pressed by powder after laying
At the disk of Φ 10mm, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get at
The good block materials of type；
(6) block materials obtained in step (5) are first warming up to 450 DEG C of heat preservation 6h with the rate of 1 DEG C/min；Then with
The rate of 10 DEG C/min rises to 1250 DEG C of heat preservation 20min, is cooled to 1050 DEG C of heat preservations 15h, Zhi Housui in 3min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Embodiment 2
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, with embodiment 1, area
It is not: in step (5), the LaCr0.9Mn0.1O3Powder, mixed powder, NiMn2O4The volume ratio of powder is sequentially 0.3:
0.01:0.69。
Embodiment 3
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, with embodiment 1, area
It is not: in step (5), the LaCr0.9Mn0.1O3Powder, mixed powder, NiMn2O4The volume ratio of powder is sequentially 0.5:
0.01:0.49。
Embodiment 4
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, with embodiment 1, area
It is not: in step (5), the LaCr0.9Mn0.1O3Powder, mixed powder, NiMn2O4The volume ratio of powder is sequentially
0.89:0.01:0.1。
Embodiment 5
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase LaCrO3And spinelle
Phase NiMn2O4Middle atom molar ratio weighs each oxide respectively and is placed in agate jar, using agate ball as ball-milling medium, anhydrous
Ethyl alcohol is decentralized medium, and wet-milling 36h controls each material mass ratio in ball grinder are as follows: agate ball: raw material: dehydrated alcohol=2.5:
1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively；
(2) two kinds of component slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively
Body；
(3) C powder is calcined into 2h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCrO3) powder；By D powder in
4h is calcined at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(4) by LaCrO3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains LaCrO3With
NiMn2O4Powder granularity (D50) it is respectively 0.127 μm and 0.138 μm, then the powder is made using PVA as binder again
Grain, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to good fluidity, good moldability
LaCrO3Powder, NiMn2O4Powder and LaCrO3And NiMn2O4Mixed powder, the additional amount of the PVA is granulation powder
The 3% of weight, LaCrO in the mixed powder3And NiMn2O4Volume ratio be 1:1；
(5) LaCrO that will be granulated described in step (4)3Powder, mixed powder, NiMn2O4Powder is sequentially laid with
In a mold, LaCrO is formed3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder (transition zone) is located at
LaCrO3Powder layer and NiMn2O4Between powder layer, the LaCrO3Powder, mixed powder, NiMn2O4The volume ratio of powder is successively
Sequence is 0.5:0.01:0.49, after laying with the pressure of 10MPa by pressed by powder at the disk of Φ 10mm, the dwell time is
5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get forming good block materials；
(6) block materials obtained in step (5) are first warming up to 500 DEG C of heat preservation 5h with the rate of 3 DEG C/min；Then with
The rate of 15 DEG C/min rises to 1280 DEG C of heat preservation 15min, is cooled to 1090 DEG C of heat preservations 13h, Zhi Housui in 2min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Embodiment 6
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase LaCr0.7Mn0.3O3With
Spinel NiMn2O4Middle atom molar ratio weighs each oxide respectively and is placed in agate jar, is situated between by ball milling of agate ball
Matter, dehydrated alcohol are decentralized medium, and wet-milling 36h controls each material mass ratio in ball grinder are as follows: agate ball: raw material: dehydrated alcohol
=2.5:1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively；
(2) two kinds of component slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively
Body；
(3) C powder is calcined into 2h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCr0.7Mn0.3O3) powder；By D
Powder calcines 4h at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(4) by LaCr0.7Mn0.3O3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains
LaCr0.7Mn0.3O3And NiMn2O4Powder granularity (D50) it is respectively 0.117 μm and 0.108 μm, then again using PVA as binder pair
The powder is granulated, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to mobility
Good, good moldability LaCr0.7Mn0.3O3Powder, NiMn2O4Powder and LaCr0.7Mn0.3O3And NiMn2O4Mixed powder, institute
The additional amount for stating PVA is the 2% of granulation powder weight, LaCr in the mixed powder0.7Mn0.3O3And NiMn2O4Volume ratio
For 1:1；
(5) LaCr that will be granulated described in step (4)0.7Mn0.3O3Powder, mixed powder, NiMn2O4Powder is successively
Sequence is laid in a mold, forms LaCr0.7Mn0.3O3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder
(transition zone) is located at LaCr0.9Mn0.1O3Powder layer and NiMn2O4Between powder layer, the LaCr0.7Mn0.3O3Powder, mixed powder
Body, NiMn2O4The volume ratio of powder is sequentially 0.5:0.01:0.49, with the pressure of 10MPa by pressed by powder after laying
At the disk of Φ 10mm, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get at
The good block materials of type；
(6) block materials obtained in step (5) are first warming up to 400 DEG C of heat preservation 7h with the rate of 3 DEG C/min；Then with
The rate of 13 DEG C/min rises to 1280 DEG C of heat preservation 15min, is cooled to 1090 DEG C of heat preservations 13h, Zhi Housui in 1min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Embodiment 7
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase LaCr0.5Mn0.5O3With
Spinel NiMn2O4Middle atom molar ratio weighs each oxide respectively and is placed in agate jar, is situated between by ball milling of agate ball
Matter, dehydrated alcohol are decentralized medium, and wet-milling for 24 hours, controls each material mass ratio in ball grinder are as follows: agate ball: raw material: dehydrated alcohol
=2.5:1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively；
(2) two kinds of component slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively
Body；
(3) C powder is calcined into 2h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCr0.5Mn0.5O3) powder；By D
Powder calcines 3h at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(4) by LaCr0.5Mn0.5O3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains
LaCr0.5Mn0.5O3And NiMn2O4Powder granularity (D50) it is respectively 1.235 μm and 1.102 μm, then again using PVA as binder pair
The powder is granulated, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to mobility
Good, good moldability LaCr0.5Mn0.5O3Powder, NiMn2O4Powder and LaCr0.5Mn0.5O3And NiMn2O4Mixed powder, institute
The additional amount for stating PVA is the 2.5% of granulation powder weight, LaCr in the mixed powder0.5Mn0.5O3And NiMn2O4Volume
Than for 1:1；
(5) LaCr that will be granulated described in step (4)0.5Mn0.5O3Powder, mixed powder, NiMn2O4Powder is successively
Sequence is laid in a mold, forms LaCr0.5Mn0.5O3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder
(transition zone) is located at LaCr0.9Mn0.1O3Powder layer and NiMn2O4Between powder layer, the LaCr0.5Mn0.5O3Powder, mixed powder
Body, NiMn2O4The volume ratio of powder is sequentially 0.5:0.01:0.49, with the pressure of 10MPa by pressed by powder after laying
At the disk of Φ 10mm, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get at
The good block materials of type；
(6) block materials obtained in step (5) are first warming up to 400 DEG C of heat preservation 7h with the rate of 2 DEG C/min；Then with
The rate of 15 DEG C/min rises to 1300 DEG C of heat preservation 10min, is cooled to 1100 DEG C of heat preservations 10h, Zhi Housui in 3min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Embodiment 8
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase LaCr0.3Mn0.7O3With
Spinel NiMn2O4Middle atom molar ratio weighs each oxide respectively and is placed in agate jar, is situated between by ball milling of agate ball
Matter, dehydrated alcohol are decentralized medium, and wet-milling for 24 hours, controls each material mass ratio in ball grinder are as follows: agate ball: raw material: dehydrated alcohol
=2.5:1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively；
(2) two kinds of component slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively
Body；
(1) C powder is calcined into 2h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCr0.3Mn0.7O3) powder；By D
Powder calcines 3h at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(2) by LaCr0.3Mn0.7O3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains
LaCr0.3Mn0.7O3And NiMn2O4Powder granularity (D50) it is respectively 1.114 μm and 0.954 μm, then again using PVA as binder pair
The powder is granulated, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to mobility
Good, good moldability LaCr0.3Mn0.7O3Powder, NiMn2O4Powder and LaCr0.3Mn0.7O3And NiMn2O4Mixed powder, institute
The additional amount for stating PVA is the 2.5% of granulation powder weight, LaCr in the mixed powder0.3Mn0.7O3And NiMn2O4Volume
Than for 1:1；
(3) LaCr that will be granulated described in step (2)0.3Mn0.7O3Powder, mixed powder, NiMn2O4Powder is successively
Sequence is laid in a mold, forms LaCr0.3Mn0.7O3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder
(transition zone) is located at LaCr0.9Mn0.1O3Powder layer and NiMn2O4Between powder layer, the LaCr0.3Mn0.7O3Powder, mixed powder
Body, NiMn2O4The volume ratio of powder is sequentially 0.5:0.01:0.49, with the pressure of 10MPa by pressed by powder after laying
At the disk of Φ 10mm, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get at
The good block materials of type；
(4) block materials obtained in step (3) are first warming up to 450 DEG C of heat preservation 6h with the rate of 1 DEG C/min；Then with
The rate of 13 DEG C/min rises to 1300 DEG C of heat preservation 10min, is cooled to 1100 DEG C of heat preservations 10h, Zhi Housui in 2min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Embodiment 9
A kind of preparation method of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, includes the following steps:
(1) to analyze pure Ni2O3、MnO2、La2O3、Cr2O3For raw material, by Lanthanum Chromite based perovskite phase LaCr0.2Mn0.8O3With
Spinel NiMn2O4Middle atom molar ratio weighs each oxide respectively and is placed in agate jar, is situated between by ball milling of agate ball
Matter, dehydrated alcohol are decentralized medium, and wet-milling for 24 hours, controls each material mass ratio in ball grinder are as follows: agate ball: raw material: dehydrated alcohol
=2.5:1:1, ball milling are along counterclockwise alternately, suitable interval time 30min counterclockwise obtains C and D slurry respectively；
(2) two kinds of component slurries in step (1) are separately dried for 24 hours in 80 DEG C, then grind 2h, obtain C and D powder respectively
Body；
(1) C powder is calcined into 3h at 950 DEG C, obtains Lanthanum Chromite based perovskite phase (LaCr0.2Mn0.8O3) powder；By D
Powder calcines 4h at 850 DEG C, obtains Spinel (NiMn2O4) powder；
(2) by LaCr0.2Mn0.8O3Powder, NiMn2O4Powder, which is respectively placed in agate mortar, respectively grinds 5h, obtains
LaCr0.2Mn0.8O3And NiMn2O4Powder granularity (D50) it is respectively 1.114 μm and 0.954 μm, then again using PVA as binder pair
The powder is granulated, meanwhile, it is granulated by mixture of the binder to described two powders of PVA；Up to mobility
Good, good moldability LaCr0.2Mn0.8O3Powder, NiMn2O4Powder and LaCr0.2Mn0.8O3And NiMn2O4Mixed powder, institute
The additional amount for stating PVA is the 2.5% of granulation powder weight, LaCr in the mixed powder0.3Mn0.7O3And NiMn2O4Volume
Than for 1:1；
(3) LaCr that will be granulated described in step (2)0.2Mn0.8O3Powder, mixed powder, NiMn2O4Powder is successively
Sequence is laid in a mold, forms LaCr0.2Mn0.8O3Powder layer, mixed powder layer, NiMn2O4Powder layer, and the mixed powder
(transition zone) is located at LaCr0.2Mn0.8O3Powder layer and NiMn2O4Between powder layer, the LaCr0.2Mn0.8O3Powder, mixed powder
Body, NiMn2O4The volume ratio of powder is sequentially 0.5:0.01:0.49, with the pressure of 10MPa by pressed by powder after laying
At the disk of Φ 10mm, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get at
The good block materials of type；
(4) block materials obtained in step (3) are first warming up to 500 DEG C of heat preservation 5h with the rate of 1 DEG C/min；Then with
The rate of 10 DEG C/min rises to 1300 DEG C of heat preservation 10min, is cooled to 1100 DEG C of heat preservations 10h, Zhi Housui in 3min again after the completion
Furnace is cooling to get Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material.
Comparative example 1
A kind of Spinel (NiMn2O4) NTC thermal sensitive ceramic material, include the following steps:
(1) to analyze pure Ni2O3、MnO2For raw material, by NiMn2O4Middle atom molar ratio, weighs Ni2O3、MnO2It is placed in agate
It is decentralized medium by ball-milling medium, dehydrated alcohol of agate ball in ball grinder, wet-milling 36h controls each material mass in ball grinder
Than are as follows: agate ball: material: dehydrated alcohol=2.5:1:1, ball milling are along counterclockwise alternately, along interval time counterclockwise
30min obtains D slurry；
(2) the D slurry in step (1) is dried for 24 hours in 80 DEG C, then grinds 2h and obtains D powder；
(3) the D powder in step (2) is obtained into Spinel (NiMn in 850 DEG C of calcining 4h2O4) powder；Then at agate
5h is ground in mortar, obtained NiMn2O4Powder granularity (D50) it is 0.121 μm, it using PVA is again then binder to NiMn2O4Powder
Body is granulated, and the additional amount of PVA is NiMn2O4The 2.5% of powder weight is to get good fluidity, the NiMn of good moldability2O4
Powder；
(4) obtained NiMn will be granulated in step (3)2O4Powder is pressed into the disk of Φ 10mm under the pressure of 10MPa,
Dwell time is 5min, then by the disk under the pressure of 350MPa isostatic cool pressing 10min to get forming good block material
Material；
(5) block materials obtained in step (4) are first warming up to 450 DEG C with the rate of 1 DEG C/min, keep the temperature after 6h again with
The rate of 10 DEG C/min rises to 1250 DEG C, be then cooled to rapidly in 2min again after 1050 DEG C of heat preservation 13h furnace cooling to get
Spinel NiMn2O4NTC thermal sensitive ceramic material.
Comparative example 2
A kind of Lanthanum Chromite based perovskite phase (LaCr0.9Mn0.1O3) NTC thermal sensitive ceramic material, include the following steps:
(1) to analyze pure La2O3、Cr2O3、MnO2For raw material, by LaCr0.9Mn0.1O3Middle atom molar ratio, weighs La2O3、
Cr2O3、MnO2It is placed in agate jar, is decentralized medium, wet-milling 36h, control by ball-milling medium, dehydrated alcohol of agate ball
Each material mass ratio in ball grinder are as follows: agate ball: material: dehydrated alcohol=2.5:1:1, ball milling be along counterclockwise alternately into
Row obtains C slurry along interval time 30min counterclockwise；
(2) the C slurry in step (1) is dried for 24 hours in 80 DEG C, then grinds 2h and obtains C powder；
(3) the D powder in step (2) is obtained into Perovskite Phase (LaCr in 950 DEG C of calcining 2h0.9Mn0.1O3) powder；Again
5h is ground in agate mortar, obtained LaCr0.9Mn0.1O3Powder granularity (D50) be 0.175 μm, then again with PVA be bonding
Agent is to LaCr0.9Mn0.1O3Powder is granulated, and the additional amount of PVA is LaCr0.9Mn0.1O3The 2.0% of powder weight is to get flowing
Good, good moldability the LaCr of property0.9Mn0.1O3Powder；
(4) obtained LaCr will be granulated in step (3)0.9Mn0.1O3Powder is first pressed into Φ 10mm under the pressure of 10MPa
Disk, dwell time 5min, then by the disk under the pressure of 360MPa isostatic cool pressing 10min to get form it is good
Block materials；
(5) block materials obtained in step (4) are first warming up to 450 DEG C with the rate of 1 DEG C/min, keep the temperature after 6h again with
The rate of 10 DEG C/min rises to 1300 DEG C, be then cooled to rapidly in 3min again after 1100 DEG C of heat preservation 15h furnace cooling to get
Perovskite Phase LaCr0.9Mn0.1O3Ceramic material.
Comparative example 3
A kind of preparation method of no transition zone Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, with real
Apply example 1, difference is: in step (4), the granulation process does not include the mixture pelleting of two kinds of powders；Suddenly it in (5), does not wrap
Correlation procedure containing intermediate layer, the LaCr0.9Mn0.1O3Powder, NiMn2O4The volume ratio of powder is 0.1:0.9.
Performance test:
Fig. 1 is R in embodiment 1-3 and comparative example 1-225℃And theoretical calculation and measurement result comparison diagram, it can be seen by Fig. 1
Theoretical calculation and actual measured results are almost the same out, and the goodness of fit is high, this has been well demonstrated that proposed by the present invention based on chromic acid
Lanthanum based perovskite phase and Spinel are strong by the feasibility for the negative temperature coefficient thermal-sensitive ceramic material that stratiform series system designs,
New approaches are provided for design New NTC thermal sensitive ceramic material.
Fig. 2 is Ln ρ-of the NTC thermal sensitive ceramic material within the scope of -20-150 DEG C in embodiment 3,6-8 and comparative example 1
1000/T curve, it can be seen that stratiform NTC thermal sensitive ceramic material NTC effect in the temperature range is obvious, linear relationship
It is good；And the introducing of transition metal element Mn but also makes matrix material not only because its variable valency effectively reduces the resistivity of material
The forbidden bandwidth of material increases, and improves the stability of the material system, improves the NTC effect of base material Lanthanum Chromite.
Fig. 3 is the section interface of Lanthanum Chromite based perovskite phase prepared by embodiment 1 and Spinel NTC thermal sensitive ceramic material
The SEM picture of junction, it can be seen that split-phase is obvious (in Fig. 3 shown in white dashed line) at the layer structure interface cohesion, almost
Pore-free exists, and illustrates that the lamellar composite NTC thermal sensitive ceramics consistency of this method preparation is high, microstructure is complete, further demonstrate,proves
The presence of bright transition zone has become organic whole, this is the premise to its electrical property Effective Regulation.
Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, comparative example prepared by above-described embodiment 1-9
The single-phase spinelle and Lanthanum Chromite based perovskite ceramic material and comparative example 3 of 1-2 preparation prepare without transition zone Lanthanum Chromite base calcium
Titanium ore phase and Spinel NTC thermal sensitive ceramic material carry out electrical property and ageing properties are tested, using Agilent 34401A number
Multimeter four-wire system technology measures its resistance value, and calculates the R in its B value and baking oven at 150 DEG C when aging 1000h25℃Change rate
ΔR/R0=(R-R0)/R0.As a result as shown in table 1 below.
Table 1
| R25℃/Ω | B25/50/K | ΔR/R0/ % | |
| Embodiment 1 | 17268.9 | 4327 | 0.77 |
| Embodiment 2 | 13589.3 | 4208 | 0.62 |
| Embodiment 3 | 9837.2 | 4216 | 0.59 |
| Embodiment 4 | 510.8 | 4160 | 0.50 |
| Embodiment 5 | 10997.7 | 4238 | 0.79 |
| Embodiment 6 | 5324.6 | 4151 | 0.54 |
| Embodiment 7 | 3048.2 | 4298 | 0.47 |
| Embodiment 8 | 1205.3 | 4319 | 0.45 |
| Embodiment 9 | 995.3 | 4288 | 0.46 |
| Comparative example 1 | 19019.5 | 4008 | 1.21 |
| Comparative example 2 | 490.6 | 2972 | 0.41 |
| Comparative example 3 | 17926.3 | 3962 | 1.02 |
With LaCr it can be seen from the data of 1 embodiment 1-9 of table0.9Mn0.1O3The increase of amount, stratiform series connection NTC heat
The resistance R of sensitive ceramic material25℃It is reduced rapidly, and and LaCr0.9Mn0.1O3Content there are linear relationships；Stratiform series connection NTC heat
The resistance R of sensitive ceramic material25℃It is reduced with the increase of Mn doping；Meanwhile material constant B is varied less, Jin Jin
Between 4151-4327K.It follows that by the multiplicity of control two-phase and the doping of Mn small feelings can be changed guaranteeing B value
Under condition, the resistance value of a wide range of controlled material makes it have different parameter combinations, can be used in broader field, such as inhibits wave
It gushes electric current (high B, low-resistance), wide warm area thermometric (low B, high resistant) etc..It is compared with comparative example 1, B changes very after stratiform series connection is compound
It is small, and R25℃It is substantially reduced, stability also significantly improves；It is compared with comparative example 2, B is significantly improved after stratiform series connection is compound.With it is right
Ratio 3 compares, and resistance change rate is below the Lanthanum Chromite base of no transition zone after the thermal sensitive ceramic material aging of embodiment 1-9 preparation
Perovskite Phase and Spinel NTC thermal sensitive ceramic material, illustrate that the presence of transition zone improves the stability of the system.Therefore,
Connecting compound NTC thermal sensitive ceramic material according to this stratiform that the law of resistance and the theory of composite material design can be in holding material
B value variation it is small in the case where, resistance value height it is adjustable, stability also significantly improves, can meet more areas (inhibit surge current,
Wide warm area thermometric etc.) requirement to NTC thermistor.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of Lanthanum Chromite based perovskite phase and Spinel NTC thermal sensitive ceramic material, it is characterised in that: by Lanthanum Chromite base calcium titanium
The layer structure that the layer structure that mine is mutually formed is formed with Spinel is connected in series, and Lanthanum Chromite based perovskite phase and spinelle
The transition zone being uniformly mixed to form at phase interface for the two-phase powder, the Lanthanum Chromite based perovskite is mutually LaCr1-xMnxO3, institute
Stating Spinel is AB2O4；Wherein, 0≤x≤0.8.
2. NTC thermal sensitive ceramic material as described in claim 1, it is characterised in that: the Lanthanum Chromite based perovskite, transition zone,
The volume ratio of Spinel is (0.01-0.98): 0.01:(0.98-0.01)；
Preferably, in the transition zone, LaCr1-xMxO3And AB2O4Volume ratio be 1:1.
3. NTC thermal sensitive ceramic material as claimed in claim 1 or 2, it is characterised in that: described A, B refer to transition metal element Mn,
One of Co, Ni.
4. NTC thermal sensitive ceramic material as claimed in claim 3, it is characterised in that: the oxide molecule formula of the Spinel
For NiMn2O4。
5. the system of Lanthanum Chromite based perovskite phase according to any one of claims 1-4 and Spinel NTC thermal sensitive ceramic material
Preparation Method includes the following steps:
(1) prepared by slurry:
By LaCr1-xMnxO3Middle atom molar ratio weighs the oxide of each metallic element, and wet-milling obtains C slurry, spare；
By AB2O4Middle atom molar ratio weighs the oxide of each metallic element, and wet-milling obtains D slurry, spare；
(2) C slurry, D slurry are separately dried, are then ground respectively, obtain C powder, D powder, it is spare；
(3) C powder, D powder are calcined respectively, respectively obtains LaCr1-xMnxO3Powder, AB2O4Powder；In addition, by LaCr1- xMnxO3And AB2O4It is mixed to get mixed powder；
(4) by the LaCr in step (3)1-xMnxO3Powder, LaCr1-xMnxO3And AB2O4Mixed powder, AB2O4Powder is according to upper
It states sequence and block materials is made, wherein the mixed powder is transition zone；
(5) block materials in step (4) are first warming up to 400-500 DEG C of heat preservation 5-7h, then heat to 1250-1300 DEG C of guarantor
Warm 10-20min is cooled to 1050-1100 DEG C of heat preservation 10-15h after the completion, finally cool to the furnace room temperature to get.
6. preparation method as claimed in claim 5, it is characterised in that: in step (1), the wet-milling is situated between by ball milling of agate ball
Matter, using dehydrated alcohol as decentralized medium；Agate ball: raw material: dehydrated alcohol mass ratio is 2.5:1:1；Preferably, wet-milling is along inverse
Clockwise alternately, along interval time 30min counterclockwise；The wet-milling time is 24-36h；
Alternatively, the drying temperature is 80-90 DEG C, and drying time is for 24 hours in step (2)；Milling time is 2h.
7. preparation method as claimed in claim 5, it is characterised in that: in step (3), C powder, D powder calcination temperature be
850-950℃；Calcination time is 2-4h；
Alternatively, in step (3), the LaCr1-xMnxO3Powder, AB2O4Powder, LaCr1-xMnxO3And AB2O4Mixed powder it is equal
It is obtained by way of binder granulation；It preferably, further include by LaCr before the granulation1-xMnxO3Powder, AB2O4Powder is ground
The step of mill；Preferably, the binder of the granulation is PVA；The additional amount of PVA is the 2.0- of granulation powder weight
3.0%.
8. preparation method as claimed in claim 5, it is characterised in that: in step (3), in the mixed powder, LaCr1- xMnxO3And AB2O4Volume ratio be 1:1.
9. such as the described in any item preparation methods of claim 5-8, it is characterised in that: in step (4), using under stress
The method of compacting is by LaCr1-xMnxO3Powder, LaCr1-xMnxO3And AB2O4Mixed powder, AB2O4Block materials are made in powder；
Method particularly includes: be pressed into the disk of Φ 10mm under the pressure of 10MPa, dwell time 5min, then by the disk in
Isostatic cool pressing 10min under the pressure of 360MPa；
Alternatively, the heating rate for being warming up to 450 DEG C is 1-5 DEG C/min in step (5)；It is described to be warming up to 1250-1300 DEG C
Heating rate be 10-15 DEG C/min；It is described be cooled to 1050-1100 DEG C used in the time be set as 1-3min.
10. Lanthanum Chromite based perovskite phase according to any one of claims 1-4 and Spinel NTC thermal sensitive ceramic material and/
Or if the described in any item preparation methods of claim 5-9 are in the application for inhibiting surge current and observing and controlling middle benefit gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942285A (en) * | 2019-04-09 | 2019-06-28 | 济南大学 | A kind of in-situ preparation lamellar composite negative temperature coefficient thermal-sensitive ceramic material and preparation method and application |
| CN111634950A (en) * | 2020-06-28 | 2020-09-08 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
| CN115894026A (en) * | 2022-11-29 | 2023-04-04 | 唐山恭成科技有限公司 | NTC thermistor material with low resistivity and high B value and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124014A (en) * | 2014-01-09 | 2014-10-29 | 华东理工大学 | Double-layer NTC (Negative Temperature Coefficient) thermistor and preparation method thereof |
| EP3012350A1 (en) * | 2014-10-21 | 2016-04-27 | United Technologies Corporation | Cold spray manufacturing of maxmet composites |
| CN107056273A (en) * | 2017-05-25 | 2017-08-18 | 中国科学院新疆理化技术研究所 | A kind of double-deck negative tempperature coefficient thermistor and preparation method thereof |
| CN108439982A (en) * | 2018-05-14 | 2018-08-24 | 济南大学 | A kind of axial composite-rotor negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof |
| CN108585794A (en) * | 2018-05-14 | 2018-09-28 | 济南大学 | A kind of chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material |
-
2019
- 2019-03-26 CN CN201910233870.6A patent/CN110054493A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124014A (en) * | 2014-01-09 | 2014-10-29 | 华东理工大学 | Double-layer NTC (Negative Temperature Coefficient) thermistor and preparation method thereof |
| EP3012350A1 (en) * | 2014-10-21 | 2016-04-27 | United Technologies Corporation | Cold spray manufacturing of maxmet composites |
| CN107056273A (en) * | 2017-05-25 | 2017-08-18 | 中国科学院新疆理化技术研究所 | A kind of double-deck negative tempperature coefficient thermistor and preparation method thereof |
| CN108439982A (en) * | 2018-05-14 | 2018-08-24 | 济南大学 | A kind of axial composite-rotor negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof |
| CN108585794A (en) * | 2018-05-14 | 2018-09-28 | 济南大学 | A kind of chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material |
Non-Patent Citations (2)
| Title |
|---|
| WENWEN KONG ET AL.: "Improvement of electrical properties of single-phase film thermistors by a Ni0.75Mn2.25O4/LaMnO3 bilayer structure", 《J MATER SCI: MATER ELECTRON》 * |
| YONG-LI ZHAO ET AL.: "LaMnO3–Ni0.75Mn2.25O4 Supported Bilayer NTC Thermistors", 《J. AM. CERAM. SOC.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942285A (en) * | 2019-04-09 | 2019-06-28 | 济南大学 | A kind of in-situ preparation lamellar composite negative temperature coefficient thermal-sensitive ceramic material and preparation method and application |
| CN111634950A (en) * | 2020-06-28 | 2020-09-08 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
| CN111634950B (en) * | 2020-06-28 | 2021-10-22 | 北京理工大学重庆创新中心 | Preparation method of perovskite type high-emissivity spherical agglomerated powder |
| CN115894026A (en) * | 2022-11-29 | 2023-04-04 | 唐山恭成科技有限公司 | NTC thermistor material with low resistivity and high B value and preparation method thereof |
| CN115894026B (en) * | 2022-11-29 | 2023-08-08 | 唐山恭成科技有限公司 | NTC thermistor material with low resistivity and high B value and preparation method thereof |
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