CN109516781A - A kind of quaternary system negative temperature coefficient thermistor material and preparation method thereof - Google Patents
A kind of quaternary system negative temperature coefficient thermistor material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to negative tempperature coefficient thermistor preparation technical field, a kind of quaternary system negative temperature coefficient thermistor material and preparation method thereof is refered in particular to.Using manganese sulfate, nickel sulfate, copper sulphate and cobaltous sulfate as initial feed, oxalic acid is as precipitating reagent, pass through pH value, ion concentration, temperature and the mixing time etc. in control precipitation reaction, precipitating particle is avoided agglomeration occur, organic impurities is removed by the filtration washing of deionized water and dehydrated alcohol, obtains finely dispersed nano particle.By pressure forming after pre-burning grain granulation, etc. static pressure, be placed in sintering in sintering furnace and negative temperature coefficient heat-sensitive resistance material be made.The features such as preparation process of the present invention is simple, repeatability is high, and consistency is good, energy consumption is low；The features such as ceramic thermal resistance of preparation has low resistance/high B-value performance characteristics, and stability is high, interchangeability is good, high sensitivity, temperature measurement, control and line build-out etc. suitable for equipment such as refrigerators.
Description
Technical field
The present invention relates to negative tempperature coefficient thermistor preparation technical fields, refer in particular to a kind of quaternary system negative temperature coefficient heat-sensitive
Resistance material and preparation method thereof.
Background technique
Negative temperature coefficient (NTC) thermistor is a kind of sensitive components that resistance value decline is increased with temperature, has temperature
The functions such as degree measurement, temperature control and temperature-compensating, are widely used in household electrical appliance, automotive electronics, power industry, communication, army
The fields such as thing science, aerospace.The NTC thermistor material of system containing galaxite has become the foundation stone of NTC material.Currently, point is brilliant
Stone series metal oxide be substantially locked as several transiting group metal elements oxides based on Mn, Co, Ni, Cu, Fe etc. and
A combination thereof.The performance of Cu-Mn, Co-Mn, Ni-Mn, Co-Cu, Co-Ni binary system of early stage is too sensitive to process conditions,
It is no longer taken seriously, instead the ternary and quaternary system less sensitive to preparation process, through ingredient, ball milling, form,
Thermal resistor is made in the traditional ceramics techniques such as sintering.This NTC thermistor prepared by spinel structure material has spirit
Sensitivity is high, respond the advantages that fast, small in size, the service life is long, at low cost and temperature range can be applied big.
About the thermistor material of spinel structure, current research is concentrated mainly on ternary system or quaternary series elements group
At by the resistivity of NTC heat-sensitive semiconductor ceramic material and relational expression ρ=ρ of temperature0Exp (B/T), (wherein B=Δ E/k)
It is found that the activation energy of material is higher, electricalresistivityρ is bigger, and under normal circumstances, resistivity and material constant B value are with uniformity, because
This low resistance, high B value NTC thermistor material be difficult to develop.Such as Chinese patent CN 104051093 A " low-resistance high B value
Negative tempperature coefficient thermistor " is to prepare Mn-Co-Cr-Ca system thermistor by using doctor-blade casting process；Chinese patent CN
108439970 A " NTC thermistor material and preparation method thereof and NTC themistor and preparation method thereof " are by adopting
Cu-Mn-Co-Ru system thermistor is prepared with solid phase method；106876069 A of Chinese patent CN " manganese cobalt nickel based negative temperature coefficient heat
The uniform co-precipitation preparation method of quick resistance material " is to prepare binary or ternary system thermo-sensitive material by using coprecipitation.So
And the preparation or complex process of these thermistors, it is at high cost or be exactly preparation process existing defects or be only
The thermistor for meeting industrial application requirement can not be prepared using binary or ternary series elements.
Summary of the invention
The purpose of the present invention is be difficult exploitation and traditional preparation side for the NTC thermistor material of low resistance, high B value
Method there are the problem of, it is desirable to provide a kind of NTC thermistor material of low resistance/high B-value, and be applied to household electrical appliance and industry
Instrument etc.；There is provided simultaneously a kind of sintering temperature is low, energy consumption less, the subzero temperature that consistency is high, surface metal electrode and porcelain body are combined
Spend coefficient resistance preparation method.
The present invention uses following specific technical solution:
A kind of preparation method of quaternary system negative temperature coefficient thermistor material, the specific steps are as follows:
1) prepare precursor powder: for the present invention using sulfate as raw material, oxalic acid is precipitating reagent, the composition of the sulfate according to
Weight percent calculates as follows: MnSO4·H2O:NiSO4·6H2O:CuSO4·5H2O:CoSO4·7H2O=35%~65%:
15%~25%:10%~20%:0%~40%.The additional amount of the oxalic acid excessive compared to quality needed for calculating 10~
15% in order to can be such that sulfate sufficiently reacts with oxalic acid.Load weighted sulfate is placed in No. 1 beaker, distilled water is added
It is placed on magnetic stirring apparatus and is stirred, be uniformly dissolved drug.Meanwhile load weighted oxalic acid being put in No. 2 beakers, it is added
Distilled water is placed in 60 DEG C of water-bath and stirs.After being all completely dissolved, sulfate liquor is slowly added into oxalic acid solution
In, and be 3~4 by pH value adjustment with ammonium hydroxide, continue 3~5h of stirring later, that is, can be taken off being aged.Digestion time is 24 hours,
Vacuum filters after the completion of ageing, washs, dry, obtains precursor powder.
2) prepare pre-burning particle: by precursor powder dry it is ground after, in 750 DEG C of 3~5h of pre-burning, it is (poly- that PVA is added later
Vinyl alcohol) solution, the mass concentration of PVA solution is 8~12%, and weight is the 5~10% of granulation powder quality.
3) prepare ceramic matrix: by powder tablet press machine pressure forming after granulation, briquetting pressure is 6~10MPa, is adopted later
Green compact are obtained with static pressure such as 300MPa.Green compact are placed in high temperature sintering furnace, temperature rises to 1100~1250 DEG C by room temperature, heating
Speed is 10~15 DEG C/min, is sintered 3~5 hours, then furnace cooling is cooled to room temperature, obtains thermal sensitive ceramics matrix；
4) it prepares surface electrode: surface electrode, the table being prepared using screen printing mode in thermal sensitive ceramics matrix surface
Face electrode is silver metal.Potsherd after silver-plated drying in 750 DEG C of heat preservation 20min, so that it is close to contact electrode and potsherd.
The beneficial effect that the present invention is compared with existing thermistor material and its technology of preparing is:
The present invention uses tetra- kinds of elements of Mn, Ni, Cu and Co.Resistance R and material coefficient B value is caused to decline according to Cu, Co is mentioned
The mechanism of action of high material coefficient B value develops the material mixture ratio of function admirable by adjusting different element ratios column, according to formula
Be made nanoscale precursor powder, through pre-burning, form and wait static pressure after obtain even particle size green compact, be not in globs of material
Poly-, there is no the grain structures excessively grown up.By experimental analysis it is found that aforesaid way preparation thermistor material have with
Lower advantage: firstly, prepared thermistor material has low resistance/high B-value, household electrical appliance and industrial instrument can be efficiently applied to
Device etc., by with the SEM of traditional preparation methods figure and density measurement Comparative result it is found that prepared thermistor ceramic crystalline grain
Grain is tiny and uniform, and bulk density is higher, and preparation process is simple, prepares that powder active is higher, and low-temperature solid phase reaction does not use
Solvent, sintering temperature is low, energy consumption is low；The present invention prepares the room temperature resistance R of thermistor25It is for 5~15 Ω, material constant B
2500~3500K.
Specific embodiment
This experiment uses the pure MnSO of nanoscale analysis4·H2O、NiSO4·6H2O、CuSO4·5H2O and CoSO4·7H2O is
Initial feed is made into mixed solution, C2H2O4·4H2O is precipitating reagent, under magnetic stirrer, slowly by sulfate liquor
It is added in oxalic acid solution.The pH value for controlling solution, is aged after fully reacting, is first filtered with deionized water, uses dehydrated alcohol later
Washing, drying obtain precursor powder.By the pre-burning of presoma powder, granulation, molding, etc. electrode, test are applied after static pressure, sintering.
Illustrate the present invention with specific implementation below.
Embodiment 1:
1) prepare precursor powder: using sulfate as raw material, oxalic acid is precipitating reagent for this experiment, with electronic balance precise,
Weight percentage of each component in sulfate are as follows:
MnSO4·H2O:NiSO4·6H2O:CuSO4·5H2O:CoSO4·7H2O=48:19:16:17；The additional amount phase of oxalic acid
It is more excessive by 12% than the quality needed for calculating.Load weighted sulfate is placed in No. 1 beaker and distilled water is added is placed in magnetic force and stirs
It mixes and is stirred on device, be uniformly dissolved sulfate.Meanwhile load weighted oxalic acid being put in No. 2 beakers, it is added a certain amount of
Distilled water is placed in 60 DEG C of water-bath and stirs to dissolve completely.After being all completely dissolved uniformly, sulfate is mixed molten
Liquid is slowly added into oxalic acid solution, and adjusts solution pH value to 4 with ammonium hydroxide, is continued to stir 3h later, that is, be can be taken off being aged, old
Changing the time is 24 hours.Vacuum is filtered, washs, is dried after the completion of ageing.
2) prepare pre-burning particle: by precursor powder dry it is ground after, in 750 DEG C of pre-burning 4h, PVA (poly- second is added later
Enol) solution, the concentration of PVA solution is 8%, and quality is the 6% of granulation powder quality.
3) ceramic matrix is prepared: by the powder pressure forming after granulation, briquetting pressure 8MPa, later using 300MPa etc.
Static pressure obtains green compact.Green compact are placed in muffle furnace, temperature rises to 1150 DEG C by room temperature, is sintered 5 hours, then furnace cooling drop
It warms to room temperature, obtains thermal sensitive ceramics matrix.
4) it electrode production process: in the coated silver electrode paste in thermal sensitive ceramics matrix top and bottom, then dries；In Muffle furnace
It is rapidly heated to 750 DEG C, keeps the temperature 20min afterwards, take out rapid cooling in air.
Embodiment 2, with embodiment 1, the difference is that weight percentage of each component are as follows: MnSO4·H2O:NiSO4·6H2O:
CuSO4·5H2O:CoSO4·7H2O=41:17:15:27；The additional amount of oxalic acid is compared to the quality excessive 12% needed for calculating.
The mixed solution of sulfate is slowly added into oxalic acid solution, and solution pH value is adjusted to 4 with ammonium hydroxide, continues to stir later
3h can be taken off being aged.Digestion time is 24 hours.Vacuum filters after the completion of ageing, washs, dry；The pre-burning 4 at 750 DEG C
After hour, PVA (polyvinyl alcohol) solution is added, the mass concentration of PVA solution is 8%, and quality is the 6% of granulation powder quality,
Powder tablet press machine pressure forming after being granulated, briquetting pressure 8MPa obtain green compact using static pressure such as 300MPa later.It will give birth to
Base is in 1150 DEG C of sintering 5h.
Sample number into spectrum 1,2 respectively corresponds the thermistor of embodiment 1, the preparation of 2 thermistor materials.Prepared temperature-sensitive pottery
Tile tests respectively after silver-plated and lead, 25 DEG C of resistance values, 50 DEG C of resistance values, B value, test result is as follows table:
As seen from the table, by comparison:
The resistance value of the thermistor ceramics prepared through the invention meets the requirement of low resistance/high B-value.
Thermistor resistance value prepared by embodiment 2 is slightly larger than embodiment 1；So in the present invention by adjusting different elements
Content can obtain low resistance/high B-value thermistor parameter.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
In the protection scope of art scheme.
Claims (6)
1. a kind of preparation method of quaternary system negative temperature coefficient thermistor material, which is characterized in that specific step is as follows:
1) precursor powder is prepared using sulfate as raw material, and oxalic acid is precipitating reagent, and the sulfate is MnSO4·H2O、NiSO4·
6H2O、CuSO4·5H2O and CoSO4·7H2O；Load weighted sulfate is placed in No. 1 beaker and distilled water is added is placed in magnetic force and stirs
It mixes and is stirred on device, be uniformly dissolved drug；Meanwhile load weighted oxalic acid being put in No. 2 beakers, distilled water is added, and
It is placed in water-bath and stirs；After being all completely dissolved, sulfate liquor is slowly added into oxalic acid solution, and is adjusted with ammonium hydroxide
PH value takes out ageing after continuing stirring, and vacuum filters after the completion of ageing, washs, dry, obtains precursor powder；
2) it prepares pre-burning particle: precursor powder being dried into ground rear pre-burning, polyvinyl alcohol (PVA) solution is added after pre-burning and makes
Grain；
3) prepare ceramic matrix: by powder tablet press machine pressure forming after granulation, the static pressure such as use obtain green compact later, by green compact
It is placed in high temperature sintering furnace, temperature rises to 1100~1250 DEG C by room temperature, is sintered 3~5 hours, then furnace cooling is cooled to room
Temperature obtains thermal sensitive ceramics matrix；
4) it prepares surface electrode: surface electrode, the surface electricity being prepared using screen printing mode in thermal sensitive ceramics matrix surface
Extremely silver metal；Potsherd is kept the temperature after silver-plated drying, so that it is close to contact electrode and potsherd.
2. a kind of preparation method of quaternary system negative temperature coefficient thermistor material as described in claim 1, which is characterized in that
In step 1), the composition of the sulfate is calculated as follows in percentage by weight: MnSO4·H2O:NiSO4·6H2O:CuSO4·
5H2O:CoSO4·7H2O=35%~65%:15%~25%:10%~20%:0%~40%, by adjusting different elements
Content can obtain the thermistor of low resistance/high B-value；The additional amount of the oxalic acid is excessive compared to the quality needed for calculating
10~15% in order to can be such that sulfate sufficiently reacts with oxalic acid.
3. a kind of preparation method of quaternary system negative temperature coefficient thermistor material as described in claim 1, which is characterized in that
In step 1), the bath temperature is 60 DEG C；The pH value adjustment is 3~4；The time for continuing stirring is 3~5h；Digestion time
It is 24 hours.
4. a kind of preparation method of quaternary system negative temperature coefficient thermistor material as described in claim 1, which is characterized in that
In step 2), calcined temperature is 750 DEG C, and burn-in time is 3~5h；The mass concentration of PVA solution is 8~12%, and weight is to make
The 5~10% of grain powder quality.
5. a kind of preparation method of quaternary system negative temperature coefficient thermistor material as described in claim 1, which is characterized in that
In step 3), briquetting pressure is 6~10MPa, hydrostatic pressure 300MPa；1100~1250 DEG C of heating speed is risen to by room temperature
Degree is 10~15 DEG C/min.
6. a kind of preparation method of quaternary system negative temperature coefficient thermistor material as described in claim 1, which is characterized in that
In step 4), holding temperature is 750 DEG C, soaking time 20min.
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| CN115073140A (en) * | 2022-06-08 | 2022-09-20 | 盐城工学院 | Preparation method of copper-containing negative temperature coefficient thermal sensitive ceramic material |
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