CN114394819B - High-reliability chip NTC thermistor material and preparation method and application thereof - Google Patents
High-reliability chip NTC thermistor material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-reliability chip NTC thermistor material and a preparation method and application thereof. The thermistor material is made of Mn 3 O 4 、Co 3 O 4 、Ni 2 O 3 As main formula material, znO and La are used 2 O 3 As a doping material; the material is prepared by ball milling, drying, presintering, ball milling and sanding the main formula material and the doping material. The chip NTC thermistor material comprises the following components in percentage by weight: 40 to 60% of Mn 3 O 4 20 to 40 percent of Co 3 O 4 5 to 15% of Ni 2 O 3 2 to 8 percent of ZnO and 0.5 to 1.5 percent of La 2 O 3 . The invention adopts manganous-manganic oxide to replace manganese dioxide, and compared with the prior formula, the invention has better consistency of resistance values and higher stability. According to the invention, by adding a small amount of zinc oxide and lanthanum oxide, the stability of the material is further improved, and the aging performance of the product is improved.
Description
Technical Field
The invention relates to the technical field of electronic devices, in particular to a high-reliability chip NTC thermistor material and a preparation method and application thereof.
Background
The NTC heat-sensitive material is a heat-sensitive material with a negative temperature coefficient, and the resistance value generally decreases exponentially along with the temperature rise. The common thermal sensitive ceramic material is made of Mn, fe, co, ni and other materialsThe transition metal oxide is doped with partial rare earth metal oxide as a raw material and is prepared by the traditional semiconductor ceramic process. NTC heat-sensitive materials with different resistivities and B values can be obtained by selecting different system materials, adjusting formula example proportions and preparation processes (sintering atmosphere, pre-sintering temperature, heat preservation time and the like), so that thermistor devices meeting different requirements are obtained. With the increasing requirements of practical application on thermosensitive materials and devices, the hot spots of the current research in the NTC industry in China are mainly the controllability of the electrical properties of ceramics, the optimization process of the aging performance of the materials, the multi-layer chip production process of the NTC thermosensitive ceramics and the like. The normal temperature NTC heat-sensitive ceramic material is mainly divided into manganese-containing series and non-manganese-containing series. Because the manganese-containing thermal sensitive material is generally stable in chemistry, the prepared NTC thermal sensitive ceramic can be directly used in the air, so that the normal-temperature NTC thermistor which is actually produced at present is mainly manganese-containing thermal sensitive ceramic. The manganese-based heat-sensitive ceramics can be produced from manganese oxide, manganese dioxide, trimanganese tetroxide, etc., but MnO, mnO 2 In the pre-sintering process and the sintering process, valence state change can occur, and the crystal structure is changed due to the fact that the crystal structure is not a spinel structure, so that the consistency of the NTC thermistor obtained by using manganese oxide and manganese dioxide as manganese sources is poor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-reliability chip NTC thermistor material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-reliability chip NTC thermosensitive resistor is prepared from Mn 3 O 4 、Co 3 O 4 、Ni 2 O 3 As main formula material, znO and La are used 2 O 3 As a doping material; the material is prepared by ball milling, drying, presintering, ball milling and sanding the main formula material and the doping material.
The design principle of the technical scheme of the invention is as follows: due to Mn 3 O 4 Is itself of spinel structure and has valence states of +2 and +3, so that Mn is used 3 O 4 In place of MnO 2 Or MnO is used as a manganese source and other elements are doped, so that the ceramic powder with a spinel structure can be easily synthesized, and the consistency of the ceramic powder is greatly improved. Because zinc ions are ions with unchanged valence and have higher stability, the existence of zinc improves the oxidation resistance of the ceramic on one hand and can limit the mutual movement of other cations at different positions of spinel on the other hand, and therefore, the stability of the resistance value of the resistor can be greatly improved by adding zinc oxide as a doping element in the formula. Lanthanum oxide has very high enthalpy value, and can be well fused with spinel phase to form good solid solution, which is beneficial to improving the stability of the thermosensitive material.
Further, the high-reliability chip NTC thermistor material comprises the following components in percentage by weight: 40 to 60 percent of Mn 3 O 4 20 to 40 percent of Co 3 O 4 5 to 15% of Ni 2 O 3 2 to 8 percent of ZnO and 0.5 to 1.5 percent of La 2 O 3 。
Further, the high-reliability chip NTC thermistor material comprises the following components in percentage by weight: 45 to 55 percent of Mn 3 O 4 25 to 35 percent of Co 3 O 4 10 to 15% of Ni 2 O 3 2 to 8 percent of ZnO and 0.5 to 1.5 percent of La 2 O 3 。
In a second aspect, the invention further provides a preparation method of the above high-reliability chip NTC thermistor material, comprising the following steps:
(1) Weighing Mn according to the formula 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Then adding the mixture into a ball mill, adding water into the ball mill, and carrying out ball milling;
(2) After the ball mill is cooled, transferring the slurry subjected to ball milling to a tray, placing the tray in an oven for drying, crushing the dried slurry, and placing the crushed dried slurry in a muffle furnace for presintering;
(3) Ball-milling the presintered powder and then sanding to obtain the powder with the specific surface area of 10 +/-2 m 2 The ceramic powder is high-reliability chip NTC thermistor material.
Further, in the step (1), the mass ratio of the mixed powder to the added water is 1.5-1.8; the ball milling speed is 30-50 rpm/min, and the ball milling time is 20-30 h.
Further, in the step (2), the drying temperature is 250 +/-10 ℃, the presintering temperature is 900 +/-50 ℃, and the presintering time is 2 hours. The inventor finds out through research that in order to improve the consistency of the high-resistance ceramic powder pre-synthesis process, increase the activity of finished powder and improve the distribution of particle size, the optimal pre-sintering temperature range is designed: 900 +/-10 ℃.
Further, in the step (3), the ball milling speed is 30 revolutions per minute, and the ball milling time is 4 hours; the sanding speed is 1200 r/min, and the sanding time is 8 hours. The inventor finds out through research that the uniformity of powder is improved through a graded milling process, and the specific surface area standard range of the material is finally determined: 10 +/-2 m 2 /g。
In a third aspect, the invention also provides the use of the high-reliability chip NTC thermistor material in an electronic component.
Further, the high-reliability chip NTC thermistor material is mixed with a solvent to prepare slurry, and the high-reliability chip NTC thermistor is obtained through tape casting, isostatic pressing, cutting and sintering. Tape casting refers to doctor blade molding and has the main advantage of a good method for preparing large-area, thin and flat ceramics. These are difficult to do with other methods. Such as in a dry-pressing process, a large number of through-going holes are created due to uneven mold filling. Therefore, the NTC thermistor is prepared by adopting a tape casting process.
Further, when the high-reliability chip NTC thermistor is prepared by sintering, the sintering temperature is 1200 +/-50 ℃, and the temperature is kept for 8-10 h. The inventor finds out through research that the sintering time has an influence on the NTC thermal sensitive ceramic microstructure, if the sintering time is short, the prepared ceramic body still has more air holes, and the ceramic body which is kept at 1200 +/-10 ℃ for 10 hours basically has no air holes, so that the consistency is better.
Compared with the prior art, the invention has the following beneficial effects: the invention adopts manganous-manganic oxide to replace manganese dioxide, and compared with the prior formula, the invention has better consistency of resistance values and higher stability. The manganous-manganic oxide is in a spinel structure and has valence states of +2 and +3, so the manganous oxide is used for replacing manganese dioxide or manganese oxide as a manganese source, and other elements are doped, so the spinel-structured porcelain powder can be easily synthesized, and the consistency of the porcelain powder is greatly improved. By adding a small amount of zinc oxide and lanthanum oxide, the stability of the material is further improved, and the aging performance of the product is improved. The zinc ion is an ion with a constant valence and has high stability, and the existence of zinc improves the oxidation resistance of the ceramic on one hand and can limit the mutual movement of other cations at different positions of spinel on the other hand, so that the stability of the resistance value of the resistor can be greatly improved by adding zinc oxide as a doping element in the formula. Lanthanum oxide has very high enthalpy value, and can be well fused with spinel phase to form good solid solution, which is beneficial to improving the stability of the thermosensitive material.
Drawings
Fig. 1 is a diagram of a chip NTC thermistor product manufactured in example 1 of the present invention;
FIG. 2 is a structural diagram of NTC thermal sensitive ceramic fiber with different holding times at 1190 ℃ in the embodiment 1 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In an embodiment of the high-reliability chip NTC thermistor material of the present invention, the material of this embodiment includes the following components by weight: 42.4% Mn 3 O 4 39.7% of Co 3 O 4 9.6% of Ni 2 O 3 7.8 percent of ZnO and 0.5 percent of La 2 O 3 。
The preparation method comprises the following steps:
(1) Weighing Mn according to the formula ratio 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing the ingredientsMixing, putting the weighed mixed powder and water into a ball milling tank according to the weight ratio of 1.5, and carrying out ball milling for 24 hours at the speed of 30 revolutions per minute;
(2) After the ball mill is cooled, transferring the slurry after ball milling to a tray and placing the tray in a drying oven at 250 ℃ for drying;
(3) The method comprises the following steps of crushing a drying material, placing the crushed drying material in a muffle furnace for presintering, crushing the drying material, placing the crushed drying material in the muffle furnace for presintering, and designing an optimal presintering temperature range for improving the consistency of a high-resistance porcelain powder presynthesizing process, increasing the activity of finished powder and improving the distribution of particle size: 900 +/-10 ℃;
(4) The secondary batching changes the ball-milling technology into rolling ball-milling earlier and then sanding, through the process of grinding in grades, improves the powder homogeneity, and the specific surface area standard range of final definite material: 10 +/-2 m 2 /g；
Preparing a chip NTC thermistor: the high-reliability chip NTC thermistor material and a casting agent carrier are mixed to prepare slurry, and then the chip NTC thermistor is obtained through the casting process, the isostatic pressing process, the high-precision cutting process, the sintering process and other technologies. The effect of the sintering time on the NTC thermal sensitive ceramic microstructure was investigated as shown in fig. 2. As can be seen from the figure, the porcelain body which is insulated at 1190 ℃ for 5h still has more air holes, while the porcelain body which is insulated at 1190 ℃ for 10h basically has no air holes, and the consistency is better.
And (3) testing the performance of the chip NTC thermistor: the resistance value is 10.04K omega, the B value is 3500, the performance requirement of 0805-10K omega products is met, the resistance value is tested in a constant-temperature oil tank at 25 ℃, the hit rate of 10 +/-5 percent is improved from 70 percent to 90 percent, the aging is carried out for 1000 hours at 150 ℃, and the resistance change rate is less than 1 percent.
Example 2
In an embodiment of the high-reliability chip NTC thermistor material of the present invention, the material in this embodiment includes the following components by weight: 45.3% Mn 3 O 4 37.7% of Co 3 O 4 8.7% of Ni 2 O 3 7.5 percent of ZnO and 0.8 percent of La 2 O 3 。
The preparation method comprises the following steps:
(1) Weighing Mn according to the formula ratio 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing the materials, putting the weighed mixed powder and water into a ball milling tank according to the weight ratio of 1.5, and carrying out ball milling for 24 hours at the speed of 30 revolutions per minute;
(2) After the ball mill is cooled, transferring the ball-milled slurry to a tray and placing the tray in a 250 ℃ oven for drying;
(3) Placing the crushed dried material into a muffle furnace for presintering, placing the crushed dried material into the muffle furnace for presintering, and designing an optimal presintering temperature range for improving the consistency of the high-resistance porcelain powder presynthesizing process, increasing the activity of finished powder and improving the distribution of particle size: 900 +/-10 ℃;
(4) The secondary batching changes the ball-milling technology into rolling ball-milling earlier and then sanding, through the process of grinding in grades, improves the powder homogeneity, and the specific surface area standard range of final definite material: 10 +/-2 m 2 /g；
Preparing a chip NTC thermistor: the high-reliability chip NTC thermistor material and a casting agent carrier are mixed to prepare slurry, and then the chip NTC thermistor is obtained through the casting process, the isostatic pressing process, the high-precision cutting process, the sintering process and other technologies. The effect of the sintering time on the NTC thermal sensitive ceramic microstructure was investigated as shown in fig. 2. As can be seen from the figure, the porcelain body which is insulated for 5h at 1190 ℃ still has more air holes, while the porcelain body which is insulated for 10h at 1190 ℃ has no air holes basically, and the consistency is better.
And (3) testing the performance of the chip NTC thermistor: the resistance value is 10.04K omega, the B value is 3500, the performance requirement of 0805-10K omega products is met, the resistance value is tested in a constant-temperature oil tank at 25 ℃, the hit rate of 10 +/-5 percent is improved from 70 percent to 90 percent, the aging is carried out for 1000 hours at 150 ℃, and the resistance change rate is less than 1 percent. Aging for 1000h
Example 3
In an embodiment of the high-reliability chip NTC thermistor material of the present invention, the material of this embodiment includes the following components by weight: 50.5% Mn 3 O 4 35.2% ofCo 3 O 4 8.2% of Ni 2 O 3 5.1% of ZnO,1.0% of La 2 O 3 。
The preparation method comprises the following steps:
(1) Weighing Mn according to the formula ratio 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing the materials, putting the weighed mixed powder and water into a ball milling tank according to the weight ratio of 1.5, and carrying out ball milling for 24 hours at the speed of 30 revolutions per minute;
(2) After the ball mill is cooled, transferring the slurry after ball milling to a tray and placing the tray in a drying oven at 250 ℃ for drying;
(3) The method comprises the following steps of crushing a drying material, placing the crushed drying material in a muffle furnace for presintering, crushing the drying material, placing the crushed drying material in the muffle furnace for presintering, and designing an optimal presintering temperature range for improving the consistency of a high-resistance porcelain powder presynthesizing process, increasing the activity of finished powder and improving the distribution of particle size: 900 plus or minus 10 ℃;
(4) The secondary batching changes the ball-milling technology into rolling ball-milling earlier and then sanding, through the process of grinding in grades, improves the powder homogeneity, and the specific surface area standard range of final definite material: 10 +/-2 m 2 /g；
Preparing a chip NTC thermistor: mixing the high-reliability chip NTC thermistor material with a casting agent carrier to prepare slurry, and then obtaining the chip NTC thermistor by the technologies of a casting process, an isostatic pressing process, a high-precision cutting process, a sintering process and the like. The effect of the sintering time on the NTC thermal sensitive ceramic microstructure was investigated as shown in fig. 2. As can be seen from the figure, the porcelain body which is insulated for 5h at 1190 ℃ still has more air holes, while the porcelain body which is insulated for 10h at 1190 ℃ has no air holes basically, and the consistency is better.
And (3) testing the performance of the chip NTC thermistor: the resistance value is 10.0K omega, the B value is 3500, the performance requirement of 0805-10K omega products is met, the resistance value is tested in a constant-temperature oil tank at 25 ℃, the hit rate of 10 +/-5 percent is improved from 70 percent to 90 percent, the aging is carried out for 1000 hours at 150 ℃, and the resistance change rate is less than 1 percent. Aging for 1000h
Example 4
In an embodiment of the high-reliability chip NTC thermistor material of the present invention, the material of this embodiment includes the following components by weight: 55.8% Mn 3 O 4 28.6% of Co 3 O 4 11.8% of Ni 2 O 3 2.3% of ZnO,1.5% of La 2 O 3 。
The preparation method comprises the following steps:
(1) Weighing Mn according to the formula ratio 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing the materials, putting the weighed mixed powder and water into a ball milling tank according to the weight ratio of 1.5, and carrying out ball milling for 24 hours at the speed of 30 revolutions per minute;
(2) After the ball mill is cooled, transferring the slurry after ball milling to a tray and placing the tray in a drying oven at 250 ℃ for drying;
(3) Placing the crushed dried material into a muffle furnace for presintering, placing the crushed dried material into the muffle furnace for presintering, and designing an optimal presintering temperature range for improving the consistency of the high-resistance porcelain powder presynthesizing process, increasing the activity of finished powder and improving the distribution of particle size: 900 +/-10 ℃;
(4) The secondary batching changes the ball-milling technology into rolling ball-milling earlier and then sanding, through the process of grinding in grades, improves the powder homogeneity, and the specific surface area standard range of final definite material: 10 +/-2 m 2 /g；
Preparing a chip NTC thermistor: mixing the high-reliability chip NTC thermistor material with a casting agent carrier to prepare slurry, and then obtaining the chip NTC thermistor by the technologies of a casting process, an isostatic pressing process, a high-precision cutting process, a sintering process and the like. The effect of the sintering time on the microstructure of the NTC thermal sensitive ceramic was investigated, as shown in fig. 2. As can be seen from the figure, the porcelain body which is insulated for 5h at 1190 ℃ still has more air holes, while the porcelain body which is insulated for 10h at 1190 ℃ has no air holes basically, and the consistency is better.
And (3) testing the performance of the chip NTC thermistor: the resistance value is 10.0K omega, the B value is 3500, the performance requirement of 0805-10K omega products is met, the resistance value is tested in a constant-temperature oil tank at 25 ℃, the hit rate of 10 +/-5 percent is improved from 70 percent to 90 percent, the aging is carried out for 1000 hours at 150 ℃, and the resistance change rate is less than 1 percent. Aging for 1000h
Example 5
In an embodiment of the high-reliability chip NTC thermistor material of the present invention, the material of this embodiment includes the following components by weight: 59.6% of Mn 3 O 4 25.1% of Co 3 O 4 11.5% of Ni 2 O 3 2.3% of ZnO,1.5% of La 2 O 3 。
The preparation method comprises the following steps:
(1) Weighing Mn according to the formula ratio 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing the materials, putting the weighed mixed powder and water into a ball milling tank according to the weight ratio of 1.5, and performing ball milling for 24 hours at the speed of 30 revolutions per minute;
(2) After the ball mill is cooled, transferring the slurry after ball milling to a tray and placing the tray in a drying oven at 250 ℃ for drying;
(3) Placing the crushed dried material into a muffle furnace for presintering, placing the crushed dried material into the muffle furnace for presintering, and designing an optimal presintering temperature range for improving the consistency of the high-resistance porcelain powder presynthesizing process, increasing the activity of finished powder and improving the distribution of particle size: 900 plus or minus 10 ℃;
(4) The secondary batching changes the ball-milling technology into rolling ball-milling earlier and then sanding, through the process of grinding in grades, improves the powder homogeneity, and the specific surface area standard range of final definite material: 10 +/-2 m 2 /g；
Preparing a chip NTC thermistor: mixing the high-reliability chip NTC thermistor material with a casting agent carrier to prepare slurry, and then obtaining the chip NTC thermistor by the technologies of a casting process, an isostatic pressing process, a high-precision cutting process, a sintering process and the like. The effect of the sintering time on the NTC thermal sensitive ceramic microstructure was investigated as shown in fig. 2. As can be seen from the figure, the porcelain body which is insulated for 5h at 1190 ℃ still has more air holes, while the porcelain body which is insulated for 10h at 1190 ℃ has no air holes basically, and the consistency is better.
And (3) testing the performance of the chip NTC thermistor: the resistance value is 10.0K omega, the B value is 3500, the performance requirement of 0805-10K omega products is met, the resistance value is tested in a constant-temperature oil tank at 25 ℃, the hit rate of 10 +/-5 percent is improved from 70 percent to 90 percent, the aging is carried out for 1000 hours at 150 ℃, and the resistance change rate is less than 1 percent. Aging for 1000h
Comparative example 1
The comparison example provides an NTC heat-sensitive material, which comprises the following components in percentage by mass: mnO 2 45.4％、Co 3 O 4 36.2％、Ni 2 O 3 18.4％、
The NTC thermal sensitive material of the comparative example is used for preparing the chip type NTC thermistor, and the method steps and the process parameters are the same as those of the examples 1 to 5. The obtained chip NTC thermistor was tested for relevant performance and the results are shown in table 1.
Table 1 results of performance test of chip NTC thermistors of examples 1 to 5 and comparative example 1
As can be seen from Table 1, the chip NTC thermistor products obtained in the comparative example 1 are poor in consistency, the hit rate is only 70%, the aging performance at 150 ℃ is poor, and the change rate is large, while the chip NTC thermistors obtained in the examples 1-5 are good in resistance consistency, the hit rate is uniform and reaches 90%, and the samples of the comparative example are superior to those of the chip NTC thermistor products in the poor aging performance at 150 ℃.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A high-reliability chip NTC thermistor material is characterized in that Mn is used 3 O 4 、Co 3 O 4 、Ni 2 O 3 As main formula material, znO and La are used 2 O 3 As a doping material; the material is prepared by ball milling, drying, presintering and ball milling and sanding the main formula material and the doping material; comprises the following components in percentage by weight: 40 to 60% of Mn 3 O 4 20 to 40 percent of Co 3 O 4 5 to 15% of Ni 2 O 3 2 to 8 percent of ZnO,0.5 to 1.5 percent of La 2 O 3 。
2. The high-reliability chip NTC thermistor material of claim 1, comprising the following components in percentage by weight: 45 to 55 percent of Mn 3 O 4 25 to 35 percent of Co 3 O 4 10 to 15% of Ni 2 O 3 2 to 8 percent of ZnO and 0.5 to 1.5 percent of La 2 O 3 。
3. A method for preparing a high-reliability chip NTC thermistor material according to claim 1 or 2, comprising the steps of:
(1) Weighing Mn according to the formula 3 O 4 、Co 3 O 4 、Ni 2 O 3 、ZnO、La 2 O 3 Mixing, adding water into the mixed powder, and performing ball milling;
(2) Drying the ball-milled slurry, crushing the dried slurry and then pre-burning;
(3) Ball-milling the presintered powder and then sanding to obtain the powder with the specific surface area of 10 +/-2 m 2 The ceramic powder is high-reliability chip NTC thermistor material.
4. The method for preparing a highly reliable chip NTC thermistor material according to claim 3, wherein in step (1), the mass ratio of the mixed powder to the added water is 1.5 to 1.8; the ball milling speed is 30-50 rpm/min, and the ball milling time is 20-30 h.
5. The method for preparing a high-reliability chip NTC thermistor material of claim 3, wherein in the step (2), the baking temperature is 250 ± 10 ℃, the pre-firing temperature is 900 ± 50 ℃, and the pre-firing time is 2 hours.
6. The method for preparing a high-reliability chip NTC thermistor material of claim 3, wherein in the step (3), the ball milling rotation speed is 30 r/min, and the ball milling time is 4 hours; the sanding speed is 1200 r/min, and the sanding time is 8 hours.
7. Use of the high-reliability chip NTC thermistor material of any of claims 1 to 3 in an electronic component.
8. The use of the high-reliability chip NTC thermistor material in electronic components of claim 7, wherein the high-reliability chip NTC thermistor material is mixed with a solvent to prepare a slurry, and the slurry is cast, isostatic pressed, cut and sintered to obtain the high-reliability chip NTC thermistor.
9. The use of the high-reliability chip NTC thermistor material of claim 7 in electronic components, characterized in that the sintering temperature is 1200 ± 50 ℃ and the temperature is kept for 8-10 h.
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