BaTiO
3The preparation technology of base lamination sheet type PTC themistor
Technical field
The invention belongs to the electrode component preparing technical field, be specifically related to a kind of preparation technology of BaTiO3 base lamination sheet type PTC themistor.
Background technology
In recent years, along with the development of mechanics of communication and surface mounting technology, the various electronic components of an urgent demand develop to small size, low power consumption and chip type direction.For PTC themistor, except that requiring miniaturization, lower room temperature resistance and bigger lift-drag ratio to be arranged also.But because the resistivity of ptc material is higher, the normal temperature resistance of conventional bulk formula PTC components and parts can not be too low, is difficult to further resistance lowering.And lamination sheet type PTC temperature-sensitive element can be realized resistance lowering by Multi-layer Parallel, and can obviously improve the resistance-warm lagging characteristics of thermistor, and proof voltage, anti-rush of current.The version of the similar multilayer chip capacitor of laminated ptc element (MLCC) is equivalent to superimposed being together in parallel of a plurality of PTC elements, burns till the back and forms an integral body, can satisfy miniaturization, low-resistance requirement.To the laminated ptc element generally, the temperature gradient of thickness direction relaxes greatly, can not produce the heat damage situation.Simultaneously, electrode is sealed in the porcelain body, has avoided oxidation, comes off, scolding tin etch and the external world cause drawbacks such as damage, thereby improved the reliability of components and parts.
Compare with multilayer chip capacitor, multilayer sheet type PTC structurally has extremely strong inheritance, can directly use for reference the preparation technology of existing multilayer chip capacitor.But because BaTiO
3Be PTC semiconductor material sintering temperature height and the problems such as ohmic contact that have metal electrode, must seek and to be total to the Ohm contact electrode that burns with it that its preparation technology's difficulty is bigger, depends on high reliability electrode formation technology and low temperature co-fired technology.Introduced a kind of method for making of lamination PTC themistor in Japanese patent laid-open 3-145920, though realized resistance lowering, lift-drag ratio is too little only to be 10
2, have void layer owing on the structure in addition, and the area of electrode is bigger on the PTC monolithic, easy short circuit when being used in the overcurrent protection occasion, reliability is low.Preparing the lamination sheet type PTC themistor also can take high temperature to burn till low temperature adhesion---burn earlier the method for afterwards folding.The drawback of this method is, because the PTC effect is to utilize the grain boundary effect of polycrystalline ceramics, the thickness of chip PTC can not be too thin, so the mechanical strength of the PTC potsherd after burning till is lower, is being difficult to form excellent contact between assurance electrode and the potsherd under the not high situation of evenness.
Summary of the invention
The object of the present invention is to provide a kind of comparatively easy BaTiO
3The preparation technology of base lamination sheet type PTC themistor, the room temperature resistance of prepared PTC thermistor is little, lift-drag ratio is big, the reliability height.
A kind of BaTiO of the present invention
3The preparation technology of base lamination sheet type PTC themistor may further comprise the steps successively:
(1) adopt film rolling forming process to prepare chip PTC green compact: to choose mass percent concentration and be 15 ~ 20% polyvinyl alcohol water solution and make adhesive, wherein add and account for the glycerine of polyvinyl alcohol water solution 4~6wt% as plasticizer, the amount that adhesive adds accounts for 32 ~ 37wt% of powder, and making its thickness is 0.2 ~ 0.4mm;
(2) electrode in the sputter: the designing mask plate, adopt ion sputtering method sputter nickel on above-mentioned green compact to form interior electrode;
(3) burn altogether: containing partial pressure of oxygen 10
-9~10
-12The H of Mpa
2-N
2Mix in the reducing atmosphere, high temperature sintering, and take the mode of hot pressing that the tight contact of each monolithic is combined into one, reoxidize processing in the temperature-fall period, to obtain good PTC effect;
(4) form the termination electrode: burning infiltration bottom and top layer electrode and electroplate solder layer successively constitute three layers of termination electrode, with the protective effect of raising to electrode.
This patent have the PTC green compact of Ni electrode to be superimposed together simultaneously a plurality of sputters sintering forms, it has following advantage:
(1) adopting the rolling formation method to prepare chip PTC green compact, is solvent with water, and environmental pollution is little, and labour intensity is low, easy operating and with low cost.
(2) the base sheet that makes of rolling formation has certain uniformity, density and fineness, and the pliability of film base is better, has the favorable manufacturability energy.
(3) utilize the mask plate of certain size, a plurality of laminations of sputter simultaneously PTC green compact, its consistency height, flexible operation is simple, is easy to realization, has improved operating efficiency.
(4) method of employing sputtering unit sputter lamination internal electrode, the thickness and the adhesive force of control electrode are beneficial to the performance and the reliability that improve device easily.
(5) adopt hot pressing sintering method, in sintering process, be easy to form good Ohmic contact.
(6) adopt elder generation that base substrate and interior electrode are burnt in reducing atmosphere altogether, under lower temperature, make the sintering processing of porcelain body grain boundary oxidation then, efficiently solve the problem of oxidation of metal electrode, and formed good PTC effect as oxidation processes.
(7) can come the regulating element characteristic by the number of plies of change lamination raw cook and the thickness of raw cook, method is flexible and easy.
Description of drawings
Fig. 1 is sputter schematic diagram among the present invention;
Fig. 2 is the oblique view of laminated layer sequence among the present invention;
Fig. 3 is the laminated body cutaway view after burning altogether among the present invention;
Fig. 4 is the cutaway view of lamination sheet type PTC themistor among the present invention.
[symbol description among the figure]
1: mask plate 2: the sputter hole
3: the PTC ceramic green 4 of rolling formation: the PTC ceramic green in the sputter behind the electrode
5: the die-cut size 6 of lamination monolithic, 6a~d: interior electrode
7, ceramic laminated (is example with 5 layers) 8a of 7a~e:PTC, 8b: external electrode
Embodiment
The present invention is further detailed explanation by way of example below.
[example 1]
(1) batching and pre-burning
The component of PTC specimen material is: (Ba
0.8Sr
0.2) Ti
1.01O
3+ 1.5mol%SiO
2+ 0.5mol%Al
2O
3+ 0.3mol%Y
2O
3+ 0.1mol%Mn (NO
3)
2Batching back ball milling mixes according to the above ratio, places 1155 ℃ of pre-burnings 2 hours.
(2) rolling formation
60 mesh sieves are also crossed in the PTC powder ball mill grinding of pre-burning.Get the 50g powder, adding the 17g mass percent concentration is that 18% polyvinyl alcohol (PVA) aqueous solution is made adhesive, and add 6ml glycerine and make plasticizer, mixing one-tenth plasticity material group, place between roll forming machine two roll mandrels and roll refining repeatedly, take off after the uniformity, density, fineness and the pliability of waiting to reach certain, the thickness of film is 0.3mm, and is die-cut into 55 * 40mm.
(3) electrode in the sputter
(thickness is 1mm, and the planar dimension in each sputter hole is 10 * 7mm) closely to cover (as shown in Figure 1) on the film base, makes its three directions on each monolithic stay the limit, prevents electric pole short circuit with mask plate.Place sputtering unit together and regulate the sputter that its each running parameter carries out interior electrode, the thickness of the nickel electrode layer of acquisition is about 2 μ m.And, being of a size of 15 * 10 * 0.3mm by being die-cut into a plurality of lamination monolithics among Fig. 1 shown in the dotted line, corresponding sputter hole is measure-alike on the two dimensional surface size of its interior electrode and the mask plate, still is 10 * 7mm.
(4) burn altogether behind the lamination
Each lamination monolithic is superimposed together according to shown in Figure 2, and adopts the mode of hot pressing to make it to be combined into one, place reducing atmosphere (H at its thickness direction
2-N
2Mist and H
2/ N
2=3%) in the stove, in 1330 ℃ and 10
-9Burnt till under the partial pressure of oxygen of Mpa 1 hour, and reduced to 1100 ℃ with the rate of temperature fall of 250 ℃/h then, and oxidation 30 minutes in air, outage thereafter naturally cools to room temperature.The final laminated body that forms as shown in Figure 3.
(5) apply external electrode
By print primer silver electrode shown in Figure 4 and burning infiltration, print the surface silver coating electrode then thereon on the laminated body after burning till, electroplate solder layer after the burning infiltration, constitute three layers of termination electrode.
The number of plies of this laminated ptc element is 3, and final size is 11 * 8 * 0.7mm, and its room temperature resistance is 3.3 Ω, and lift-drag ratio is 8.4 * 10
4, temperature coefficient of resistance is 24%/℃.
[example 2]
Adopt the method identical to make the PTC green compact with example 1, section and carry out lamination after the sputter nickel electrode in sputtering unit, hot pressing is burnt till and is reoxidized and handles the back and make the termination electrode in the reducing atmosphere stove.Relevant parameter is as follows respectively: the mass percent concentration of the PVA aqueous solution of choosing in the rolling formation is 15% (wherein having added the glycerine that accounts for PVA aqueous solution 4wt%), and the amount of its adding accounts for the 37wt% of powder, and the thickness of preparation is 0.2mm; H
2-N
2H in the mist
2/ N
2=4%, at 1325 ℃ and 10
-10Burnt till under the partial pressure of oxygen of Mpa 1.5 hours, and reduced to 1000 ℃ with the rate of temperature fall of 280 ℃/h then, and oxidation 45 minutes in air, outage thereafter naturally cools to room temperature.
The number of plies of this laminated ptc element is 5, and final size is 11 * 8 * 0.9mm, and its room temperature resistance is 2.0 Ω, and lift-drag ratio is 8.9 * 10
4, temperature coefficient of resistance is 25%/℃.
[example 3]
Adopt the method identical to make the PTC green compact with example 1, section and carry out lamination after the sputter nickel electrode in sputtering unit, hot pressing is burnt till and is reoxidized and handles the back and make the termination electrode in the reducing atmosphere stove.Relevant parameter is as follows respectively: the mass percent concentration of the PVA aqueous solution of choosing in the rolling formation is 16% (wherein having added the glycerine that accounts for PVA aqueous solution 5wt%), and the amount of its adding accounts for the 34wt% of powder, and the thickness of preparation is 0.4mm; H
2-N
2H in the mist
2/ N
2=5%, at 1320 ℃ and 10
-11Burnt till under the partial pressure of oxygen of Mpa 2 hours, and reduced to 900 ℃ with the rate of temperature fall of 300 ℃/h then, and oxidation 60 minutes in air, outage thereafter naturally cools to room temperature.
The number of plies of this laminated ptc element is 9, and final size is 11 * 8 * 2.9mm, and its room temperature resistance is 1.2 Ω, and lift-drag ratio is 1.2 * 10
5, temperature coefficient of resistance is 18%/℃.
[example 4]
Adopt the method identical to make the PTC green compact with example 1, section and carry out lamination after the sputter nickel electrode in sputtering unit, hot pressing is burnt till and is reoxidized and handles the back and make the termination electrode in the reducing atmosphere stove.Relevant parameter is as follows respectively: the mass percent concentration of the PVA aqueous solution of choosing in the rolling formation is 20% (wherein having added the glycerine that accounts for PVA aqueous solution 5wt%), and the amount of its adding accounts for the 32wt% of powder, and the thickness of preparation is 0.2mm; H
2-N
2H in the mist
2/ N
2=3%, at 1328 ℃ and 10
-12Burnt till under the partial pressure of oxygen of Mpa 1 hour, and reduced to 1000 ℃ with the rate of temperature fall of 250 ℃/h then, and be 10 containing partial pressure of oxygen
-4Handled 30 minutes in the atmosphere of Mpa, outage thereafter naturally cools to room temperature.
The number of plies of this laminated ptc element is 5, and final size is 11 * 8 * 0.9mm, and its room temperature resistance is 1.8 Ω, and lift-drag ratio is 7.4 * 10
4, temperature coefficient of resistance is 19%/℃.
[example 5]
Adopt the method identical to make the PTC green compact with example 1, section and carry out lamination after the sputter nickel electrode in sputtering unit, hot pressing is burnt till and is reoxidized and handles the back and make the termination electrode in the reducing atmosphere stove.Relevant parameter is as follows respectively: the mass percent concentration of the PVA aqueous solution of choosing in the rolling formation is 15% (wherein having added the glycerine that accounts for PVA aqueous solution 6wt%), and the amount of its adding accounts for the 36wt% of powder, and the thickness of preparation is 0.3mm; H
2-N
2H in the mist
2/ N
2=4%, at 1320 ℃ and 10
-10Burnt till under the partial pressure of oxygen of Mpa 1.5 hours, and reduced to 900 ℃ with the rate of temperature fall of 270 ℃/h then, and be 10 containing partial pressure of oxygen
-5Handled 45 minutes in the atmosphere of Mpa, outage thereafter naturally cools to room temperature.
The number of plies of this laminated ptc element is 7, and final size is 11 * 8 * 1.6mm, and its room temperature resistance is 1.5 Ω, and lift-drag ratio is 1.3 * 10
5, temperature coefficient of resistance is 21%/℃.
[example 6]
Adopt the method identical to make the PTC green compact with example 1, section and carry out lamination after the sputter nickel electrode in sputtering unit, hot pressing is burnt till and is reoxidized and handles the back and make the termination electrode in the reducing atmosphere stove.Relevant parameter is as follows respectively: the mass percent concentration of the PVA aqueous solution of choosing in the rolling formation is 19% (wherein having added the glycerine that accounts for PVA aqueous solution 4wt%), and the amount of its adding accounts for the 33wt% of powder, and the thickness of preparation is 0.4mm, H
2-N
2H in the mist
2/ N
2=5%, at 1330 ℃ and 10
-11Burnt till under the partial pressure of oxygen of Mpa 2 hours, and reduced to 800 ℃ with the rate of temperature fall of 300 ℃/h then, and be 10 containing partial pressure of oxygen
-5Handled 60 minutes in the atmosphere of Mpa, outage thereafter naturally cools to room temperature.
The number of plies of this laminated ptc element is 11, and final size is 11 * 8 * 3.7mm, and its room temperature resistance is 0.9 Ω, and lift-drag ratio is 2.2 * 10
5, temperature coefficient of resistance is 26%/℃.