CN1279553C - TiO2 non-linear pressure-sensitive ceramic resistor and its preparation method - Google Patents
TiO2 non-linear pressure-sensitive ceramic resistor and its preparation method Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 238000005476 soldering Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 abstract description 7
- 229910052745 lead Inorganic materials 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract 3
- 230000007547 defect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
The present invention discloses a TiO2 non-linear voltage sensitive ceramic resistor with dual functions of voltage sensitivity and capacitance and a preparation method thereof, which belongs to the technical field of information electronic components. The TiO2 non-linear voltage sensitive ceramic resistor with dual functions of voltage sensitivity and capacitance is prepared in such a manner that a layer of electrodes are coated on the surface of a circular or annular ceramic substrate, and the chemical structural formula of the ceramic substrate: AxByCz. TiO2 or AxByCzDf. TiO2. The prepared TiO2 non-linear voltage sensitive ceramic resistor without Bi and Pb in the ceramic substrate overcomes the defect that the existing adulterant contains Bi oxides and Pb oxides; the thermal shock resistance of a voltage sensitive resistor is increased, the electronic property of a voltage sensitive resistor can be improved by selecting proper molar ratio, and the quantity and the type pf a semiconductive agent, and the practical requirement of the electrical property is met; when the TiO2 non-linear voltage sensitive ceramic resistor with dual functions of voltage sensitivity and capacitance is applied to a direct current micromotor, the electromagnetic noise can be effectively eliminated, and the service life of the direct current micromotor can be prolonged.
Description
Technical field
The invention belongs to information electronic devices and components field, particularly have the bifunctional a kind of TiO that does not contain Bi and Pb of pressure-sensitive-electric capacity
2Non-linear pressure-sensitive ceramic resistor device and preparation method thereof.
Background technology
Varistor be its resistance with alive variation and a kind of resistive element of non-linear change, i.e. the resistor that its resistance reduces rapidly when applying magnitude of voltage and surpass a certain threshold voltage.Be a kind of self-resistance to the applied voltage sensitivity, and can use repeatedly and the electronic component that can not damage.
Traditional ZnO is a varistor, and non-linear pressure-sensitive character is good, as the mesohigh varistor, has overvoltage protection, and critical functions such as absorption of high energy surge and high voltage stabilizing are widely used in electric power system, electronic circuit and the household electrical appliance.But it is not obtaining important breakthrough as yet aspect low-voltage device, thereby is restricted in the application in low-voltage field, because the dielectric coefficient of ZnO monocrystalline is little, only is 8.5 particularly, thereby ZnO is that varistor also lacks electric capacity (big capacity) effect simultaneously.
Along with multi-functional, developing rapidly of the electronic equipment of high reliability, miniaturization, particularly along with the application of semiconductor product in electronic equipment that with large scale integrated circuit (LSIC) is the center is increasingly extensive, the operating voltage of these devices is lower, and the ability of bearing the overvoltage impact is very weak.Noise, surge current and the static electricity on human body who invades equipment in power line that slave unit is outer and the external environment condition often makes these electronic equipment generation misoperations or wrecks.Usually can adopt varistor to prevent that accident from taking place, have shortcomings such as capacitance is little, de-noising ability, can not satisfy instructions for use but ZnO is a varistor.
Particularly be widely used in the DC micromotor in the electronic equipment, it is the main driver part in acoustic image system, computer and the communication equipment, but the potential pulse of the very wideband section that produces between commutator and brush, promptly the electromagnetic noise of commutator has caused serious disturbance to environment and system itself.Electromagnetic compatibility (EMC) has become the problem of very paying close attention in the world, comprises that the many countries of China have stipulated clearly that all electrical micro-machine must authenticate by EMC.Though eliminate the varistor that this noise does not need to have very high non linear coefficient, but because the wide frequency range of noise, and general varistor can only absorb the noise of a certain frequency range, therefore, absorb the noise of wide frequency range, usually just need be at the two ends of varistor jumbo capacitor in parallel.SrTiO
3Be that varistor has higher non-linearity coefficient and big capacitance, be easy to low pressureization, can satisfy instructions for use preferably, but this material will be in reducing atmosphere high temperature sintering, also need to carry out high-temperature thermal oxidation then and handle, the manufacturing process complexity, production cost is higher.
TiO
2Be electric capacity one varistor, the novel varistor that grows up after the eighties in 20th century, its circuit function is equivalent to the combination in parallel of a capacitor and a varistor.Because its pressure sensitive voltage V
1mALower (being lower than 6V) that can do, the relative dielectric constant of non linear coefficient α higher (can be higher than 9) and superelevation is (10
4～10
5Therefore the order of magnitude), can make things convenient for and absorb noise of motor effectively, realize the miniaturization of device and circuit and prevent the misoperation of equipment.As report in the U.S. Pat 4306214, be used in TiO at present
2The alloy that is piezo-resistance contains Bi and Pb more, but Bi and Pb are volatile when sintering, not only makes properties of sample be difficult to control, and can pollute environment.And with respect to SrTiO
3Be varistor, TiO
2Based material can be in atmosphere once-firing, thereby its production technology is simple, cost is low, realize product low pressureization easily, has vast market prospect.The objective of the invention is to make and do not contain Bi and Pb and satisfy the practical TiO that requires of electrical property
2It is pressure-sensitive-electric capacity double-function device.This pottery is made annular voltage-sensitive resistor especially and is used for direct current micromotor, can not only effectively eliminate electromagnetic noise, and can also prolong electrical machinery life.
Summary of the invention
The objective of the invention is to propose a kind of TiO
2Non-linear pressure-sensitive ceramic resistor device, the chemical constitution formula of the ceramic substrate of described non-linear pressure-sensitive ceramic resistor device are A
xB
yTiO
2, comprise first composition of forming by the oxide of Ti; At least a second composition A that forms by the oxide of Nb and Ce; Form the 3rd composition B by the Si oxide of y=0.1mol%, be used for effectively improving electrology characteristic, such as non linear coefficient α; It is characterized in that: described x is the oxide CeO to the Nb of the described second composition A and Ce
2And NbO
5/2The molal quantity that calculates is 1.2mol%≤x≤5.2mol%.
Described ceramic substrate applies continuous electrode on the surface, or applies 2 or 4-8 noncontinuous electrode.
The preparation method of described non-linear pressure-sensitive ceramic resistor device is:
1) span by x, y takes by weighing required raw material in the ceramic substrate, according to a conventional method material powder is carried out mixing and ball milling technology, and the granularity that makes various powder stocks is less than 2 microns;
2) mixed-powder of ball milling is sieved,, prilling powder is sieved, make granulation and the powder compacting that sieves ball milling and the manual granulation of powder or the mist projection granulating that sieve;
3) in type idiosome is accompanied burning-off to remove organic bond and made it through 600 ℃～1120 ℃ have certain intensity;
4) idiosome that will accompany burning-off to remove organic bond carries out sintering in air, and temperature is between 1050 ℃-1450 ℃, and sintering time is between 0.5-10 hour; Oxygen partial pressure is strong for being not less than 0.2 atmospheric pressure during sintering;
5) heat treated once more step is carried out in 600 ℃ of-1200 ℃ of air atmospheres; Electric performance stablity, particularly soldering reliability when being used to improve the user and using;
6) ceramics two sides burning infiltration Ag or Cu electrode, sintering temperature is 500-800 ℃, is incubated 15-20 minute.
The invention has the beneficial effects as follows that 1. have not only improved the resistance to sudden heating of varistor, by reducing the SiO that is used as sintering aid as far as possible
2Amount, suppressed because the generation heat cracks that the caused localized heat of abominable welding condition impacts, and total amount compensates owing to reduce SiO by regulating
2The deterioration of the caused sintering degree of amount.2. by suitably selecting the amount and the type of molar ratio and semiconducting agent, can improve the electric property of varistor.3. make the TiO that does not contain Bi and Pb
2Be pressure-sensitive-electric capacity varistor, solved in the past and contained the shortcoming of Bi and Pb oxide in the alloy, and satisfied the practical requirement of electrical property.Be used for direct current micromotor and can not only effectively eliminate electromagnetic noise, and can also prolong electrical machinery life.
Description of drawings
Fig. 1 (a) is annular non-linear pressure-sensitive ceramic resistor device structural representation, and Fig. 1 (b) is the A-A cutaway view of Fig. 1 (a);
Fig. 2 (a) is circular non-linear pressure-sensitive ceramic resistor device structural representation, and Fig. 2 (b) is the B-B cutaway view of Fig. 2 (a).
Embodiment
The present invention is pressure-sensitive for having-the bifunctional a kind of TiO of containing of electric capacity
2Non-linear pressure-sensitive ceramic resistor device and preparation method thereof.Annular and circular non-linear pressure-sensitive ceramic resistor device structural representation shown in Fig. 1 (a) and (b) Fig. 2 (a) and (b).The ceramic substrate 1 of this non-linear pressure-sensitive ceramic resistor device is disk shape or ring-type, and applies the continuous electrode 2 of one deck on two surfaces up and down of disk shape ceramic substrate 1; On at least one surface of ring-shaped pottery substrate 1, apply one deck continuous or 2-8 discontinuous electrode 2.Above-mentioned continuous electrode and noncontinuous electrode are mainly by comprising Ag or Cu and the organic substance grout material is formed.Its electrode slurry is an a kind of and two or more mixture in terpinol, ethyl cellulose, cyclohexanone, the aviation gasoline with the organic substance slurry.Described non-linear pressure-sensitive ceramic resistor device also can be square.
The chemical constitution formula of the ceramic substrate of described non-linear pressure-sensitive ceramic resistor device is A
xB
yTiO
2, comprise first composition of forming by the oxide of Ti; At least a second composition A that forms by the oxide of Nb and Ce; Form the 3rd composition B by the Si oxide of y=0.1mol%, be used for effectively improving electrology characteristic, such as non linear coefficient α; It is characterized in that: described x is the oxide CeO to the Nb of the described second composition A and Ce
2And NbO
5/2The molal quantity that calculates is 1.2mol%≤x≤5.2mol%.
The preparation method of described non-linear pressure-sensitive ceramic resistor device is:
1) span by x, y takes by weighing required raw material in the ceramic substrate, according to a conventional method material powder is carried out mixing and ball milling technology, and the granularity that makes various powder stocks is less than 2 microns;
2) mixed-powder of ball milling is sieved,, prilling powder is sieved, make granulation and the powder compacting that sieves ball milling and the manual granulation of powder or the mist projection granulating that sieve;
3) in type idiosome is accompanied burning-off to remove organic bond and made it through 600 ℃～1120 ℃ have certain intensity;
4) idiosome that will accompany burning-off to remove organic bond carries out sintering in air, and temperature is between 1050 ℃-1450 ℃, and sintering time is between 0.5-10 hour; Oxygen partial pressure is strong for being not less than 0.2 atmospheric pressure during sintering.
5) heat treatment is carried out in 600 ℃ of-1200 ℃ of air atmospheres once more, and described heat treated once more step is in order to improve the electric performance stablity, particularly soldering reliability of user when using.
6) ceramics two sides burning infiltration Ag or Cu electrode, sintering temperature is 500-800 ℃, is incubated 15-20 minute.
The electrical property measurement of the pressure-sensitive-difunctional nonlinear resistor of electric capacity of final circle is to be measured by the pressure-sensitive tester of circle.The electrical property measurement of the pressure-sensitive-difunctional nonlinear resistor of electric capacity of final annular is to be measured by the pressure-sensitive tester of annular.
The present invention is further specified for embodiment below in conjunction with accompanying drawing.
Adopt the pure TiO of industrial reagent
2, additive Nb
2O
5, CeO
2And sintering aid SiO
2, press table 1 and form wet-mixed, 250 rev/mins of planetary mills, ball milling 5 hours, oven dry, granulation, 150MPa is dry-pressing formed to be diameter 10mm, the disk shape idiosome of thickness 1.2mm accompanies burning-off to remove organic bond and makes it through 600 ℃～1120 ℃ to have certain intensity.1350 ℃ of sintering in the air are incubated 4 hours, once-firing, and sample is folded to burn 2～3 layers, uses burnt TiO
2Powder is done bedding and padding.Ceramics two sides burning infiltration Ag electrode, 580 ℃ of silver ink firings are incubated 15 minutes.Sample is measured V with piezo-resistance dc parameter measuring instrument
1mA, measure capacitor C and loss tg δ with the LCR digital electric bridge.
The content of fix N b and Si is constant, and the content that changes Ce is from 0～5.0mol%, and the electrical property of sample is as shown in table 1.
Table 1
| Sample number | Form content (mol%) | Electrical property | |||||||
| TiO 2 | Nb 2O 5 | SiO 2 | CeO 2 | V 1mA (V/mm) | α | C(nF) 1kHz | ε r× 10 4 | tgδ | |
| 1-1 | 99.70 | 0.20 | 0.10 | 0.00 | 42.82 | 3.31 | 20.00 | 3.66 | 0.64 |
| 1-2 | 99.60 | 0.20 | 0.10 | 0.10 | 41.96 | 6.10 | 27.14 | 4.97 | 0.11 |
| 1-3 | 98.70 | 0.20 | 0.10 | 1.00 | 23.52 | 4.55 | 43.06 | 7.88 | 0.23 |
| 1-4 | 98.20 | 0.20 | 0.10 | 1.50 | 20.00 | 5.05 | 66.47 | 12.16 | 0.22 |
| 1-5 | 97.70 | 0.20 | 0.10 | 200 | 15.84 | 4.62 | 86.70 | 15.86 | 0.32 |
| 1-6 | 97.20 | 0.20 | 0.10 | 2.50 | 17.74 | 3.81 | 64.20 | 11.75 | 0.32 |
| 1-7 | 96.70 | 0.20 | 0.10 | 3.00 | 20.92 | 4.03 | 61.34 | 11.23 | 0.35 |
| 1-8 | 95.70 | 0.20 | 0.10 | 4.00 | 27.16 | 4.34 | 48.98 | 8.96 | 0.34 |
| 1-9 | 94.70 | 0.20 | 0.10 | 5.00 | 32.80 | 4.22 | 41.57 | 7.60 | 0.39 |
In sintering temperature one regularly, with CeO
2The increase of content, V
1mAVoltage reduces, and is minimum during to 0.4mol%, slowly rises again afterwards; The α value changes mild 0.1 the highest afterwards; The variation of capacitor C and voltage are corresponding; The relative dielectric constant of sample is bigger, and Changing Pattern conforms to electric capacity; Loss tg δ also be 0.1 o'clock minimum, change little afterwards.The pressure sensitive voltage V of sample 1-2～1-9
1mA, nonlinear characteristic and be situated between relatively constant and loss all meet the requirements.
What embodiment 2 will carry out is that sample 1-5 has changed the sample that sintering schedule obtained in the comparing embodiment 1.
Fix other parameter,, carry out all process steps as embodiment 1 as the reagent proportioning, different is the variation of sintering schedule as shown in table 2, comprises sintering temperature and temperature retention time, under the sintering temperature of 1300 ℃～1400 ℃ * 2h～4h, the sample of system, its measurement is similar to the measurement in the example 1.The results are shown in table 2.
It is not linear relation to the influence of sample comprehensive electrochemical properties that this example demonstrates sintering temperature and temperature retention time.The voltage V of sample 2-3
1mA, nonlinear characteristic and be situated between relatively constant and loss be in best balance.So the composition of this sample and calcining system are best in the present invention.
Table 2
| Sample number | Sintering condition in the air | Electrical property | ||||
| Sintering temperature (℃) | Temperature retention time (hour) | V 1mA (V/mm) | α | C(nF) 1kHz | tgδ | |
| 2-1 | 1300 | 4 | 22.04 | 3.85 | 68.85 | 0.51 |
| 2-2 | 1330 | 2 | 15.82 | 4.32 | 77.92 | 0.43 |
| 2-3 | 1330 | 4 | 12.42 | 5.31 | 89.91 | 0.34 |
| 1-5 | 1350 | 4 | 15.84 | 4.62 | 86.70 | 0.32 |
| 2-4 | 1380 | 4 | 13.00 | 4.19 | 79.96 | 0.35 |
| 2-5 | 1400 | 4 | 23.50 | 4.54 | 61.27 | 0.37 |
Embodiment 3
What embodiment 3 will carry out is the sample that changes the content of semiconducting agent Nb.
Adopt fully the technological parameter identical with embodiment 1, the content of fixation of C e and Si is constant, and the content of change Nb is from 0～5.0mol%, and the electrical property of sample is as shown in table 3.
Table 3
| Sample number | Form content (mol%) | Electrical property | |||||||
| TiO 2 | Nb 2O 5 | SiO 2 | CeO 2 | V 1mA (V/mm) | α | C(nF) 1kHz | ε r× 10 4 | tgδ | |
| 3-1 | 99.70 | 0.00 | 0.10 | 0.20 | ＞1000 | ＜1 | 0.74 | 0.14 | 0.17 |
| 3-2 | 99.60 | 0.10 | 0.10 | 0.20 | 110.38 | 6.02 | 14.97 | 2.74 | 0.04 |
| 3-3 | 98.70 | 1.00 | 0.10 | 0.20 | 41.18 | 3.97 | 24.46 | 4.48 | 0.40 |
| 3-4 | 98.20 | 1.50 | 0.10 | 0.20 | 21.18 | 4.81 | 66.76 | 12.22 | 0.45 |
| 3-5 | 97.70 | 2.00 | 0.10 | 0.20 | 18.56 | 4.62 | 72.86 | 13.33 | 0.37 |
| 3-6 | 97.20 | 2.50 | 0.10 | 0.20 | 12.46 | 5.11 | 96.22 | 17.61 | 0.54 |
| 3-7 | 96.70 | 3.00 | 0.10 | 0.20 | 7.22 | 5.76 | 71.30 | 13.05 | 0.52 |
| 3-8 | 95.70 | 4.00 | 0.10 | 0.20 | 8.84 | 3.82 | 38.46 | 7.04 | 0.41 |
| 3-9 | 94.70 | 5.00 | 0.10 | 0.20 | 16.66 | 3.51 | 47.98 | 8.78 | 0.55 |
The amount of semiconducting agent influences the electrology characteristic of varistor pottery.In sample 3-1, there is not the semiconducting agent, pressure sensitive voltage V
1mAVery big, non linear coefficient is very little, and capacitance is very little, does not meet the requirement of pressure-sensitive-difunctional nonlinear resistor of electric capacity.The nonlinear characteristic of Nb content sample 3-2～3-9 in 0.1～5.0mol% scope, pressure sensitive voltage V
1mAAnd be situated between relatively constant and loss all meet the requirements.Consider low-voltage V
1mA, than the demand of high nonlinear coefficient and big electric capacity, sample 3-7 is the more preferred sample of the present invention.
Embodiment 4
What embodiment 4 will carry out is that the 3-6 sample has changed the sample that sintering schedule obtained in the comparing embodiment 3.
Fix other parameter,, carry out all process steps as embodiment 1 as the reagent proportioning, different is the variation of sintering schedule as shown in table 4, comprises sintering temperature and temperature retention time, under the sintering temperature of 1280 ℃～1350 ℃ * 4h, the sample of system, its measurement is similar to the measurement in the example 1.The results are shown in table 4.
Table 4
| Sample number | Sintering condition in the air | Electrical property | ||||
| Sintering temperature (℃) | Temperature retention time (hour) | V 1mA (V/mm) | α | C(nF) 1kHz | tgδ | |
| 4-1 | 1280 | 4 | 23.83 | 3.41 | 55.68 | 0.45 |
| 4-2 | 1300 | 4 | 15.72 | 4.98 | 68.04 | 0.58 |
| 4-3 | 1330 | 4 | 12.16 | 4.90 | 80.20 | 0.35 |
| 3-6 | 1350 | 4 | 12.46 | 5.11 | 96.22 | 0.54 |
Under the certain situation of temperature retention time, along with sintering temperature raises, the voltage V of sample
1mAReduce, non linear coefficient increases, and capacitance increases, and comprehensive electrochemical properties is tending towards optimizing.1350 ℃ * 4h is a calcining system of comparatively optimizing of the present invention for the sample of 3-6 composition.
Embodiment 5, annular sample
Adopt fully the technological parameter identical with embodiment 1, the prescription identical with sample 1-5 formed (being numbered 5-1), the granulation material is pressed into overall diameter 12mm, in directly through 8.0mm, the annular idiosome of thickness 1.1mm accompanies burning-off to remove organic bond through 600 ℃～1000 ℃, sintering 2～4h in the air in 1250 ℃～1350 ℃ scopes, for improving the consistency of voltage, adopt the method for burying burning, with formulation material or pure TiO
2Powder covers sintering fully with sample, and afterwards through cleaning, drying, at three Ag electrodes of the upper surface of ring-shaped pottery body printing 120 degree five equilibriums, 580 ℃ of silver ink firings are incubated 15 minutes.Sample is measured V with the ring varistor measuring instrument
0.1mAAnd V
1mA, calculate the table 5 that the results are shown in of non linear coefficient α.
Table 5
| Sample number | Technology | V 0.1mA(V/mm) | V 1mA(V/mm) | α |
| 5-1 | Bury burning with formulation material in the crucible | 12.2 | 37.0 | 2.7 |
| 13.7 | 38.0 | |||
| 12.7 | 37.4 | |||
| Bury burning with formulation material on the backing plate | 14.7 | 40.0 | 2.3 | |
| 14.6 | 41.0 | |||
| 14.3 | 39.0 | |||
| Do not bury burning | 12.5 | 34.5 | 2.3 | |
| 12.0 | 34.5 | |||
| 12.0 | 31.5 | |||
| Use pure TiO on the backing plate 2Bury burning | 13.2 | 37.4 | 2.21 | |
| 14 | 36.3 | |||
| 14.8 | 37.1 |
No matter this example is to use pure TiO if showing
2Still formulation material buries burying firing technique and all can not solving higher, the non-linear relatively poor problem of annular voltage-sensitive resistor voltage of imitation frosted glass.
Embodiment 6
Embodiment 6 is the improvement to embodiment 5, increases the investigation (numbering 6-2) to sample 1-6 simultaneously, adopts the technology of abrasive disc can reduce pressure sensitive voltage, improves non-linear.Prescription composition and technology are identical with example 5, and the ring-shaped pottery sheet behind the sintering grinds off surface 0.1mm at least with wafer lapping machine, and printed silver electrode behind the cleaning, drying is measured identical with example 5.The results are shown in table 6.
Table 6
| Sample number | Technology | V 0.1mA(V/mm) | V 1mA(V/mm) | α |
| 6-1 | 1350 ℃ * 4 do not grind | 15.5 | 34.0 | 2.93 |
| 13.9 | 29.0 | 3.13 | ||
| 14.6 | 31.0 | 3.06 | ||
| Mean value | 14.7 | 31.3 | 3.04 | |
| 1350 ℃ * 4 grind | 5.5 | 10.9 | 3.37 | |
| 5.2 | 10.7 | 3.19 | ||
| 5.5 | 11.2 | 3.24 | ||
| Mean value | 5.6 | 10.9 | 3.27 | |
| 6-2 | 1350 ℃ * 2 do not grind | 14.1 | 37.0 | 2.39 |
| 14.0 | 36.0 | 2.44 | ||
| 15.0 | 39.0 | 2.40 | ||
| Mean value | 14.3 | 37.3 | 2.41 | |
| 1350 ℃ * 2 grind | 4.7 | 9.7 | 3.18 | |
| 4.8 | 10.0 | 3.14 | ||
| 5.6 | 10.0 | 3.97 | ||
| Mean value | 5.03 | 10.0 | 3.43 |
This example shows that annular sample is carried out the abrasive disc PROCESS FOR TREATMENT can effectively reduce about 3 times of voltages.
Embodiment 7
Embodiment 7 is the further improvement to 1-5 prescription among the embodiment 5 to embodiment 6, except the upper surface printing Ag of ring-shaped pottery matrix electrode, also print a continuous annular electrode at the back side of ceramic matrix, can improve the consistency of pressure sensitive voltage, reduce voltage, improve non-linear.
Table 7
| Sample number | Sintering process | Electrode | V 0.1mA(V/mm) | V 1mA(V/mm) | α |
| 7-1 | 1350℃×4 | No back electrode | 5.7 | 17.6 | 2.04 |
| 5.7 | 17.0 | ||||
| 5.5 | 16.6 | ||||
| 7-2 | 1350℃×4 | Back electrode is arranged | 5.2 | 10.7 | 3.19 |
| 5.7 | 11.1 | ||||
| 5.6 | 11.6 | ||||
| 7-3 | 1350℃×2 | No back electrode | 6.2 | 20.5 | 1.93 |
| 7.6 | 26.5 | ||||
| 7.5 | 25.0 | ||||
| 7-4 | 1350℃×2 | Back electrode is arranged | 6.5 | 13.5 | 3.15 |
| 5.9 | 12.1 | ||||
| 6.6 | 12.9 |
Embodiment 8
Embodiment 8 is on embodiment 5 to embodiment 7 technology bases, and (numbering is respectively 8-1～8-5) to the annular voltage-sensitive resistor preparation technology's of 1-3～1-7 prescription further improvement.In 600 ℃ of-1200 ℃ of air or other suitable atmosphere the ring-shaped pottery body is heat-treated, time 0.5-10 hour, printing Ag electrode was measured electrical property behind the burning Ag.Adopt the constant temperature flatiron, under 350 ℃, 3 seconds time, sample is carried out the soldering reliability test.The results are shown in table 8.
Shown in the table 8, show this routine change in voltage Δ V
10mAWith non linear coefficient changes delta α all within industry product technology parameter and standard scope, illustrate atmosphere heat treatment technology can guarantee to weld before and after the stability of electrical property.Avoid simultaneously or ceramics face checking problem when having reduced welding, improved solderability.
The electrical property measurement of the pressure-sensitive-difunctional nonlinear resistor of electric capacity of final circle is to be measured by the pressure-sensitive tester of circle.The electrical property measurement of the pressure-sensitive-difunctional nonlinear resistor of electric capacity of final annular is to be measured by the pressure-sensitive tester of annular.
The comparison of performance change before and after table 8 welding
| Sample number | Before the welding | After the welding | Rate of change % | ||||||
| V 1mA | V 10mA | α | V 1mA | V 10mA | α | ΔV 10mA | Δα | The postwelding ceramics is apparent | |
| 8-1 | 10.52 | 23.29 | 2.9 0 | 9.95 | 22.67 | 2.8 | -2.66 | -3.44 | There is not be full of cracks |
| 10.74 | 23.53 | 10.21 | 22.90 | ||||||
| 11.08 | 23.51 | 10.25 | 22.95 | ||||||
| 8-2 | 10.76 | 24.45 | 2.8 0 | 9.95 | 23.65 | 2.66 | -3.27 | -5.00 | There is not be full of cracks |
| 11.03 | 24.32 | 10.31 | 23.55 | ||||||
| 11.52 | 24.97 | 10.37 | 23.64 | ||||||
| 8-3 | 10.56 | 24.16 | 2.7 8 | 9.65 | 23.03 | 2.64 | -4.68 | -5.04 | There is not be full of cracks |
| 10.81 | 24.71 | 9.86 | 23.63 | ||||||
| 11.10 | 25.42 | 10.26 | 24.37 | ||||||
| 8-4 | 10.98 | 24.71 | 2.8 4 | 9.57 | 22.90 | 2.64 | -7.32 | -7.04 | There is not be full of cracks |
| 10.84 | 24.45 | 9.66 | 23.03 | ||||||
| 10.81 | 24.19 | 8.71 | 21.57 | ||||||
| 8-5 | 11.58 | 25.23 | 2.9 6 | 10.89 | 24.32 | 2.87 | -3.6 | -3.04 | There is not be full of cracks |
| 11.08 | 24.68 | 10.49 | 23.80 | ||||||
| 11.38 | 24.97 | 10.54 | 23.93 | ||||||
| Mean value | 10.99 | 24.44 | 2.8 6 | 10.04 | 23.33 | 2.72 | -4.31 | -4.71 | There is not be full of cracks |
Claims (3)
1. TiO
2Non-linear pressure-sensitive ceramic resistor device, the chemical constitution formula of the ceramic substrate of described non-linear pressure-sensitive ceramic resistor device are A
xB
yTiO
2, comprise first composition of forming by the oxide of Ti; At least a second composition A that forms by the oxide of Nb and Ce; Form the 3rd composition B by the Si oxide of y=0.1mol%, be used for effectively improving electrology characteristic, such as non linear coefficient α; It is characterized in that: described x is the oxide CeO to the Nb of the described second composition A and Ce
2And NbO
5/2The molal quantity that calculates be 1.2mol%＜or=x＜or=5.2mol%.
2. according to the described TiO of claim 1
2Non-linear pressure-sensitive ceramic resistor device is characterized in that: described ceramic substrate applies continuous electrode on the surface, or applies 2 or 4-8 noncontinuous electrode.
3. the described TiO of claim 1
2The preparation method of non-linear pressure-sensitive ceramic resistor device is characterized in that: the preparation method of described non-linear pressure-sensitive ceramic resistor device is:
1) span by x, y takes by weighing required above-mentioned oxide raw material in the ceramic substrate, according to a conventional method raw material is carried out mixing and ball milling, and the particle size that makes various raw materials is less than 2 microns;
2) the mixed material powder of ball milling is sieved, to ball milling and the material powder manual granulation or the mist projection granulating that sieve, sieve, making granulating and forming is idiosome;
3) in type idiosome is accompanied burning-off to remove organic bond and made it through 600 ℃～1120 ℃ have certain intensity;
4) idiosome that will accompany burning-off to remove organic bond carries out sintering in air, and temperature is between 1050 ℃-1450 ℃, and sintering time is between 0.5-10 hour; Oxygen partial pressure is strong for being not less than 0.2 atmospheric pressure during sintering;
5) heat treated once more step is carried out in 600 ℃ of-1200 ℃ of air atmospheres; Electric performance stablity, particularly soldering reliability when being used to improve the user and using;
6) ceramics two sides burning infiltration Ag or Cu electrode, sintering temperature is 500-800 ℃, is incubated 15-20 minute.
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| CN100404460C (en) * | 2006-02-20 | 2008-07-23 | 清华大学 | Method for synthesizing pressure-sensitive ceramic material of giant dielectric, nonlinear type and rich in TiO2 |
| CN102533183A (en) * | 2010-12-09 | 2012-07-04 | 湖北航天化学技术研究所 | Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof |
| CN102584210A (en) * | 2012-02-07 | 2012-07-18 | 上海海事大学 | Preparation method for high-voltage TiO2 ring varistor |
| CN104051100B (en) * | 2014-06-23 | 2017-05-03 | 中国地质大学（北京） | Titanium oxide multilayer thin film varistor and preparation method for same |
| CN111524703A (en) * | 2020-06-03 | 2020-08-11 | 陕西华星电子开发有限公司 | Annular semiconductor ceramic capacitor and manufacturing method thereof |
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