CN106348733A - High-precision NTC (negative temperature coefficient) material and manufacturing method thereof - Google Patents
High-precision NTC (negative temperature coefficient) material and manufacturing method thereof Download PDFInfo
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- CN106348733A CN106348733A CN201610721279.1A CN201610721279A CN106348733A CN 106348733 A CN106348733 A CN 106348733A CN 201610721279 A CN201610721279 A CN 201610721279A CN 106348733 A CN106348733 A CN 106348733A
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B35/632—Organic additives
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- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
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Abstract
The invention discloses a high-precision NTC (negative temperature coefficient) material and a manufacturing method thereof. The NTC material is prepared by carrying out ceramic sintering on the materials mainly composed of transition metal oxides, wherein the materials comprise a metal oxide mixture, acrylic monomers, a coupling agent, an initiator and a dispersing agent. The manufacturing method comprises the following steps: mixing and grinding all the components expect the initiator, and adding the initiator into the obtained powder to initiate the reaction so as to obtain the jelly substance, thereby avoiding the stratification of the material and finally obtaining the high-uniformity material.
Description
Technical field
The invention belongs to field of electronic ceramic materials is and in particular to arrive negative temperature coefficient (ntc) Material Field, particularly one
Plant high accuracy ntc material and preparation method thereof.
Background technology
Negative temperature coefficient heat-sensitive resistance material is the material that resistance rises with temperature and reduces, due to ntc critesistor material
This performance of material, makes it be widely used in the aspects such as temperature survey, temperature control and temperature-compensating.
Ntc material is the ceramic material that a kind of material blends by predominantly transition metal oxide pass through that sintering is made
Material, at present, the conventional complete manufacturing process steps of ntc thermistor material are: 1, dispensing, by various conventional metal oxides powder
Material (copper oxide, manganese oxide, nickel oxide, ferrum oxide, aluminium oxide, cobalt oxide etc.) is pressed required ratio and is mixed；2nd, ball milling, by prepare
Powder adds water and abrasive media is put into and carried out ball milling in ball mill, makes powder fineness reach the fineness of submicron particles；3rd, dry
Pre-molding, the powder after ball milling is dried, is pressed into the shape of setting with forcing press in a mold in advance；4th, isostatic pressed compacting, will
The pre-molding ingot wrapping is put into sizing in isostatic pressed cavity；5th, high temperature sintering, the molding suppressing ingot is put into high temperature and stands
It is sintered so as to ceramic in formula sintering furnace.Sintering process is controlled to: -800 DEG C of room temperature (1 DEG C/min of heating rate, insulation
120 minutes) -1100 to 1300 DEG C of (0.5 DEG C/min of heating rate is incubated 180 minutes)-room temperatures (natural cooling)；6th, cut, use
Cutting mechanics cut to the ceramic core sheet stock block sintering, and cut into the thermistor chip eggshell china piece of set thickness.
After obtaining chip eggshell china piece, then carry out electrode preparation, scribing, encapsulation, may be manufactured without the ntc of same purposes, outward appearance, model, specification
Thermal resistor.
But in the preparation technology of traditional ntc thermistor material, in the drying course particularly after levigate,
Because the proportion difference of raw materials leads to material to occur differential settlement so that material is layered, lead to manufacture
The uniformity of product do not reach design requirement, the concordance of product is not therefore reached yet and is required with it.
Content of the invention
For solving in the preparation technology of traditional ntc thermistor material, particularly in drying course, due to used
The proportion difference of raw material leads to differential settlement thus causing layering so that the uniformity of the product manufacturing reaches not
To design requirement, the concordance of product does not therefore reach the problem requiring with it yet, and the present invention develops a kind of new ntc temperature-sensitive
The manufacturing process of resistance material.In the technique of the present invention, by adding polymerized monomer in the raw material grinding, lead to after grinding
Crossing and process so that the product obtaining after grinding is in g., jelly-like, solving the problems, such as that grinding-material is layered, thus improve manufactured goods
Concordance.
Specifically, present invention employs technical scheme below:
A kind of high accuracy ntc material, is made up through oversintering ceramic of the dispensing based on transition metal oxide, and its feature exists
In described dispensing includes metal oxide mixture, acrylic monomer, coupling agent, initiator and dispersant, wherein with metal
Oxide mixture is 100 weight portion meters, and the weight portion of acrylic monomer, coupling agent, initiator and dispersant is respectively
1.0-3.0、0-0.3、0.1-0.2、1.0-2.0.
Preferably, described metal oxide mixture includes 0-17.5 part sio by weight2, 0-2.5 part cuo, 30-
70 parts of mn3o4, 5-25 part nio, 5-35 part fe2o3, 0.5-4.5 part al2o3, 10-50 part co3o4.
In above material, described acrylic monomer is selected from one or more of following mixture: acrylic acid,
Methacrylic acid, acrylate, methacrylate, acrylamide, Methacrylamide and acrylamide and metering system
The n- methylated derivative of amide, the preferably mixture of two kinds of wherein at least, more preferably acrylamide or methacryl
Amine and its n- methylated derivative, such as n, n- DMAA.
Preferably, described coupling agent is silane coupling agent, and coupling agent can be added as needed on or without such as
Can be without this kind of silane coupling agent in the case that final ceramic material does not need doped silicon.
Preferably, described initiator is selected from one or more of following mixture: hydrogen peroxide, potassium peroxydisulfate,
Sodium peroxydisulfate, Ammonium persulfate..Initiator is preferably water miscible, is more preferably selected from hydrogen peroxide or Ammonium persulfate., most preferably
It is Ammonium persulfate..
Preferably, described dispersant is oligomer dispersant, acylate dispersant, inorganic acid salt dispersant and polyphosphoric acid
The mixture of one or more of dipersant.Preferred dispersant is oligomer dispersant or acylate dispersant,
More preferably oligomer dispersant and acylate dispersant are the ammonium salts of oligomer and organic acid, such as ammonium polyacrylate and Fructus Citri Limoniae
Sour ammonium.
The invention also discloses a kind of method manufacturing high accuracy ntc material is it is characterised in that methods described includes: 1)
Acrylic monomer, coupling agent, dispersant are mixed together, add a small amount of ammonia, together with metal oxide mixture powder
Enter grinding machine, add water and abrasive media carries out mixed grinding, until obtaining the fineness of submicron particles；2), after discharging, addition is drawn
Send out agent and stir, until obtaining gelatinous mixture；3) spawn achieved above is dried and be pressed into setting shape；
4) and then by being pressed into the material setting shape it is sintered, obtain ceramic material.
Preferably, also included to obtain the process of gelatinous mixture chopping, to increase surface before step 3) drying
Long-pending.
Preferably, the process of sintering includes: to 800 DEG C and is incubated 120 points with the ramp of 1 DEG C/min by room temperature first
Clock, then to 1100-1300 DEG C and is incubated 180 minutes with the ramp of 0.5 DEG C/min again, subsequently naturally cools to room temperature,
Obtain ceramic material.
Beneficial effect: the manufacture method of the high accuracy ntc material of the present invention efficiently avoid the feelings of mixed material lamination
Condition, improves the concordance of final products.
Specific embodiment
A kind of situation being difficult to avoid that during traditional ntc material manufacture is the layering of material.In the fabrication process,
Particularly in drying course, material can settle because of standing.Because the proportion of material therefor is different, therefore infall process be subject to than
Ghost image rings, and leads to differential settlement.For example in drying course, make ground slurry dry become the type of being suitable for compression into for
The dry powder of sintering, generally requires drying 12-24 hour at 80 DEG C.The so long time be enough to lead to material to make a difference finally
The differential settlement of performance.Ntc chip is of different sizes as needed, in the fabrication process, the differential settlement of material
Cause the inconsistent of product with layering, the microstructure of material internal is substantially inconsistent, the performance of impact product.In larger chi
In very little product, interiors of products microstructural inconsistent lead to properties of product decline, qualification rate reduce, quality reduce, lead to
Many product hierarchies decline.And in the product of reduced size, the change of microstructure smaller scale integrally will be made to product
One-tenth has a strong impact on, and leads to qualification rate to reduce, even results in a lot of products and directly discard, percent defective improves.Therefore solve product
Consistency problem it is critical only that the differential settlement and layering avoiding material.
The present invention develops a kind of new technique and solves the problems referred to above.The manufacturing process of the present invention include dispensing, ball milling,
Dry the steps such as precompressed, isostatic pressed compacting, high temperature sintering, cutting.
It will be appreciated that the present invention relates to some technical terms, the definition of this grade term refer to definition general in the industry.But
It is that, for ease of description, the present invention also specifically provides the definition of some terms, general definition in the field of business and description of the invention
In the case of the definition that provided is afoul, the definition provided in this specification is defined.
In dispensing, acrylic monomer, coupling agent, dispersant etc. are configured to after polymerized emulsion, and for manufacturing ntc
The metal oxide mixture of ceramic material is mixed together grinding, until being ground to the granularity of needs.Although it is it will be appreciated that big herein
Some areas are all to be illustrated with ball milling for the description ground, it is to be appreciated that all can grind material of the present invention
The method being ground to desired particle size may be used to the present invention, such as Vertical Mill, roller mill, rod milling, post mill, pipe mill and autogenous tumbling mill etc.,
Therefore adopt the scheme of corresponding Ginding process also within the scope of the present invention.Ground slurry adds initiator in stirring
In the case of make its mix homogeneously, then make its gelatine, form g., jelly-like gel, the wherein process of gelatine can be entered naturally
OK, obtain and carry out for improving under conditions of gelatine speed heats up in an oven, for example, be warming up to 60-80 DEG C of guarantor in an oven
Temperature, for example, be incubated 30 minutes, or can also improve the addition of initiator, and the addition of such as initiator increases to 3-4 times,
And carry out gelatine under conditions of heating up.Wherein in dispensing, if being counted with metal oxide mixture for 100 weight portions,
The weight portion of acrylic monomer, coupling agent, initiator and dispersant is respectively 1.0-3.0,0-0.3,0.1-0.4,1.0-
2.0.
Metal oxide mixture used by the present invention is the metal oxide mixture for manufacturing ntc material, wherein
Described metal-oxide includes being normally defined the oxide of the element of metal, also optionally includes being typically considered to semiconductor element
The oxide of the silicon of element, i.e. silicon oxide.The part of the main body for manufacturing the metal oxide mixture of ntc material is transition
Metal-oxide, optionally can also comprise silicon oxide, copper oxide etc..In one embodiment, manufacture the metal oxygen of ntc material
The various materials of compound are calculated as 0-17.5 part sio by weight2, 0-2.5 part cuo, 30-70 part mn3o4, 5-25 part nio, 5-35
Part fe2o3, 0.5-4.5 part al2o3, 10-50 part co3o4.
Acrylic monomer refers to contain the acrylic acid derivative of the unsaturated double-bond that can be used for being polymerized in molecule, including
Acrylic acid and its methylated derivative, acrylate and its methylated derivative, acrylamide and its methylated derivative.At this
In invention, conventional acrylic monomer can use.In the present invention, acrylic monomer be preferably selected from following in
One or more of mixture: acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, metering system
The n- methylated derivative of amide and acrylamide and Methacrylamide, the preferably mixture of two kinds of wherein at least, more
Preferably acrylamide or Methacrylamide and its n- methylated derivative, such as n, n- DMAA.For example at this
In one preferred embodiment of invention, monomer used is acrylamide and n, the mixture of n- DMAA, its use
Amount ratio is about 1:0.05-0.2, such as 10:1 by weight.
Coupling agent can also be added in dispensing.Preferably, described coupling agent is silane coupling agent, and coupling agent can
To be added as needed on or without such as can be without this kind of silicon in the case that final ceramic material does not need doped silicon
Alkanes coupling agent.
Initiator preferably water-soluble peroxide initiator, the therefore initiator used by the present invention are preferably selected from following
One or more of mixture: hydrogen peroxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate..Initiator is more preferably selected from
Hydrogen peroxide or Ammonium persulfate., most preferably Ammonium persulfate..
Dispersant is used for making metal-oxide and monomer and other composition dispersed in emulsion, forms stable dividing
Prose style free from parallelism system.Preferably, described dispersant is oligomer dispersant, acylate dispersant, inorganic acid salt dispersant and polyphosphoric acid
The mixture of one or more of dipersant.Preferred dispersant be oligomer dispersant or acylate dispersant or
Its mixture, preferred dispersant does not contain other metal ions, it is therefore preferable that oligomer dispersant and acylate dispersion
Agent is the ammonium salt of oligomer and organic acid, such as ammonium polyacrylate and ammonium citrate.
In above dispensing, selected material does not preferably contain any other metal ion, and salt therefore used is preferably
Ammonium salt, so during high temperature sintering, all by calcination totally, the final material obtaining is not mixed for all organic materials and salt
Miscellaneous other materials, the high-performance of ntc material is unaffected.
In the method for the manufacture high accuracy ntc material of the present invention, first by acrylic monomer, coupling agent, dispersant
It is mixed together in proportion, add a small amount of ammonia, adjust to ph9-10, enter grinding machine together with metal oxide mixture powder,
Add water and abrasive media carries out mixed grinding, until obtaining the fineness of submicron particles.After discharging, add initiator and stir all
Even, heat up in case of need, until obtaining gelatinous mixture.Spawn achieved above is dried and is pressed into
Set shape, preferably first gel piece is shredded before baking, for example, cut into lamellar with perching knife, to increase surface area.It is pressed in advance
The powder setting shape enters isostatic pressing machine cavity, is pressed into reservation shape wherein, then will be pressed into the material setting shape
Material is sintered, and obtains ceramic material.The ceramic material block obtaining can use cutting mechanics to be cut, and obtains setting thickness
The heat sensitive electronic chip eggshell china piece of degree.Carry out electrode preparation, scribing, encapsulation more afterwards, make different purposes, outward appearance, model, rule
The ntc thermal resistor of lattice.
Embodiment:
Below in conjunction with specific embodiment, the present invention to be described in further detail.
In following examples, the typical process flow of employing is as follows:
1st, ball milling: each component chemical element is poured in nylon ball grinder by formula proportion counterweight 400g.Addition pure water:
500ml, the ethanol 100ml of 95% content, planet ball put into by the material preparing.Grinding machine grind, ground after, pour in plate, put into
12 hour ~ 15 hours are dried in 130 DEG C of baking ovens.Cross 40 mesh sieve after drying and carry out pre-burning, calcined temperature is 850 DEG C ± 20
℃.Insulation closed stove after two hours, takes out, pour into and carry out secondary grinding in nylon tank after natural cooling.Add during secondary grinding
Pure water 500ml, the ethanol 100ml of 95% content.After two milleds, pour in plate, place into drying in oven, drying temperature
170 DEG C, 18 ~ 20 hours during baking.
2nd, pulverize: 120 mesh sieve crossed by the powder that two mills have been dried.
3rd, pre-molding: by the powder crushing briquetting molding on a hydraulic press.Pressure: 7mpa, pressurize: 2 minutes, directly
Footpath: 50, thickness: 30.
4th, isostatic pressed: carry out isostatic pressed with preservative film after the spindle of pre-molding is wrapped.Pressure: 350mpa, pressurize: 5
Minute.
5th, high temperature sintering: the good spindle of isostatic pressed is put in circle alms bowl in stove and carries out high temperature sintering, its sintering curre is as follows:
C1=30 DEG C, t1=700 divides；C2=110 DEG C, t2=90 divides；C3=110 DEG C, t3=1100 divides；C4=750 DEG C, t4=120 divides；
C5=750 DEG C, t5=650 divides；C6=1180 DEG C, t6=300 divides；C7=1180 DEG C, t7=800 divides；C8=1000 DEG C, t8=500 divides；c9
=800 DEG C, t9=700 divides；C10=200 DEG C, t10=-121 divides.Maximum temperature: 1180 DEG C, total time: 5390 minutes, burned from
So it is cooled to room temperature to can be taken off.
6th, score piece: will be cut into slices on mould bases on burned ceramic spindle, slice thickness is 0.25.
7th, Tu Yin: the disk cutting is made a good job of with ultrasonic cleansing after bake and carries out applying silver-colored beans, and use oven for drying.
8th, burn electrode: silver-colored beans disk will be coated and put into burning electrode in tunnel kiln.
9th, scribing: the disk of burned electrode is carried out scribing, scribing a size of 0.5 × 0.5.
10th, measure: the little chip pulling is made the glass envelope product of our needs, then measures, and calculate its b value with
R value has reached the qualification rate of the product of desired value.
For the dispensing that with the addition of polymerization system, during a ball milling, add the composition in addition to initiator in polymerization system,
After the stock discharge of milled is in plate, add initiator, stirring while adding, until aqueous solution becomes gel, mixing time is big
It is about 10 minutes.It is then placed in 80 DEG C of baking ovens to dry 30 minutes, that is, be condensed into g., jelly-like material.The gel material perching knife being formed
Cut into lamellar to increase surface area, after putting into oven for drying, treat pre-burning.
Table 1 below and table 2 provide the proportioning of composition used in embodiment.For embodiments of the invention, embodiment and right
The typical process flow of ratio is identical, and difference is that embodiment with the addition of the polymerization system shown in table 2 and increased as above one
The step of the interpolation polymerization system described in paragraph.I.e. the dispensing in table 1 do not add the system in table 2 for comparative example, added in table 2
Dispensing the corresponding embodiment for the present invention.
Table 1. chip basic element proportioning and detection performance, wherein each Ingredient Amount is in parts by weight.
| Numbering | mn3o4 | fe2o3 | nio | co3o4 | zno | zro2 | sio2 | b25/50 | r25 |
| 1 | 32.92 | 7.37 | 15 | 36.50 | 3.74 | 3.26 | 3750k | 15kω | |
| 2 | 42.57 | 10 | 45.68 | 1.20 | 4150k | 150kω | |||
| 3 | 84.70 | 10.30 | 2.58 | 3950 k | 10kω |
Added in table 2. embodiment polymerization system composition, wherein consumption be by metal oxide mixture be 100 weights
The parts by weight of amount part meter.
| Embodiment is numbered | Acrylamide | N, n- DMAA | despex a40 | Water | Ammonium persulfate. 10% | Yields (embodiment vs comparative example) |
| 1 | 1.0 | 0.1 | 0.6 | The 75% of grain weight | 10ml/kg | 67.7%vs39.8% |
| 2 | 2.0 | 0.2 | 1.0 | The 75% of grain weight | 10ml/kg | 77%vs45.7% |
| 3 | 2.5 | 0.25 | 2.0 | The 75% of grain weight | 20ml/kg | 68.5%vs51.6% |
The preparation of polymerization system: monomer and dispersant are mixed in water, then adds ammonia on a small quantity, stirring while adding,
Until ph value reaches 9-10.Above dispensing is put into ball mill grinding and is mixed after being mixed with metal oxide mixture, slurry
10% ammonium persulfate solution is added, stirring while adding, until aqueous solution becomes gel, mixing time is about 10 minutes after discharging.
It is then placed in 80 DEG C of baking ovens to dry 30 minutes, that is, be condensed into g., jelly-like material.The gel material perching knife being formed cuts into lamellar
To increase surface area, after putting into oven for drying, treat pre-burning.
It can be seen from the results that adopting the solution of the present invention, compared with comparative example, yields greatly improves.
Above in conjunction with specific embodiment, embodiments of the present invention are described in detail, but on the invention is not restricted to
State embodiment, in the ken that art those of ordinary skill possesses, can also be without departing from the present invention
Make a variety of changes on the premise of objective.
Claims (10)
1. a kind of high accuracy ntc material, is made up through oversintering ceramic of the dispensing based on transition metal oxide, its feature
It is, described dispensing includes metal oxide mixture, acrylic monomer, coupling agent, initiator and dispersant, wherein with gold
Genus oxide mixture is 100 weight portion meters, and the weight portion of acrylic monomer, coupling agent, initiator and dispersant is respectively
1.0-3.0、0-0.3、0.1-0.2、0.6-2.0.
2. high accuracy ntc material as claimed in claim 1 it is characterised in that described metal oxide mixture by weight
Meter includes 0-17.5 part sio2, 0-2.5 part cuo, 30-70 part mn3o4, 5-25 part nio, 5-35 part fe2o3, 0.5-4.5 part
al2o3, 10-50 part co3o4.
3. high accuracy ntc material as claimed in claim 1 is it is characterised in that described acrylic monomer is in following
One or more of mixture: acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methyl-prop
The n- methylated derivative of acrylamide and acrylamide and Methacrylamide.
4. high accuracy ntc material as claimed in claim 3 it is characterised in that described acrylic monomer be acrylamide with
The combination of n, n- DMAA.
5. high accuracy ntc material as claimed in claim 1 is it is characterised in that described coupling agent is silane coupling agent.
6. high accuracy ntc material as claimed in claim 1 is it is characterised in that described initiator is selected from one of following
Or multiple mixture: hydrogen peroxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate..
7. high accuracy ntc material as claimed in claim 1 is it is characterised in that described dispersant is oligomer dispersant, organic
The mixture of one or more of hydrochlorate dispersant, inorganic acid salt dispersant and polyphosphate dispersant.
8. a kind of method manufacturing high accuracy ntc material is it is characterised in that methods described includes: 1) by acrylic monomer, idol
Connection agent, dispersant are mixed together, and add a small amount of ammonia, enter grinding machine, add water and grind together with metal oxide mixture powder
Grinding media carries out mixed grinding, until obtaining the fineness of submicron particles；2) after discharging, add initiator and stir, until obtaining
Obtain gelatinous mixture；3) spawn achieved above is dried and be pressed into setting shape；4) and then will be pressed into and set
The material of setting shape is sintered, and obtains ceramic material.
9. the method manufacturing high accuracy ntc material as claimed in claim 8 is it is characterised in that went back before step 3) is dried
Including will obtain gelatinous mixture chopping process.
10. the method manufacturing high accuracy ntc material as claimed in claim 8 is it is characterised in that the process of sintering includes: first
First to 800 DEG C and it is incubated 120 minutes with the ramp of 1 DEG C/min by room temperature, then again with the ramp of 0.5 DEG C/min extremely
1100-1300 DEG C and be incubated 180 minutes, subsequently naturally cool to room temperature, obtain ceramic material.
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| CN114852990A (en) * | 2022-05-31 | 2022-08-05 | 武汉中原长江科技发展有限公司 | Preparation method of metal oxide material and lithium-metal oxide battery prepared by using same |
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