CN113603476B - Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic - Google Patents
Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic Download PDFInfo
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Abstract
The invention provides a preparation method and an electrochemical test of multi-point electrode zinc oxide voltage-sensitive ceramic. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under a plurality of voltage-sensitive voltages at the same time, so that effective protection on a plurality of circuits is achieved at the same time; the multi-point electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.
Description
Technical Field
The invention relates to the technical field of zinc oxide pressure-sensitive ceramics, in particular to a preparation method and an electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramics.
Background
Zinc oxide voltage sensitive ceramics are widely used in electronic and electrical systems for detecting and limiting transient voltage surges due to their excellent current-voltage characteristics and greater energy absorption capability. The nonlinear characteristics of the zinc oxide voltage sensitive ceramics are attributed to the double schottky barriers present in the zinc oxide grain boundary layer. High non-linearity factors, i.e. faster time response and more efficient protection means, are considered to be the most important indicators. In addition, parameters such as voltage-dependent voltage, leakage current and residual voltage ratio of the zinc oxide voltage-sensitive ceramic also have great influence on practical application of the zinc oxide voltage-sensitive ceramic. In different circuit applications, the voltage-sensitive ceramic with proper voltage-sensitive voltage is needed, and even in the same circuit system, the voltage-sensitive ceramic with two or more voltage ranges is needed, so that the effective protection of the circuit is realized. The voltage-sensitive ceramic prepared by the traditional surface electrode process has specific voltage-sensitive voltage, and can not realize the protection of one voltage-sensitive ceramic on a plurality of elements with different voltage requirements.
Disclosure of Invention
The invention provides a preparation method and an electrochemical test of a multi-point electrode zinc oxide voltage-sensitive ceramic, aiming at the problem that the voltage-sensitive ceramic prepared by the traditional surface electrode process in the prior art has specific voltage-sensitive voltage and can not realize the protection of one voltage-sensitive ceramic on elements with different voltage requirements.
The invention is realized by the following technical scheme:
a preparation method of multi-point electrode zinc oxide pressure-sensitive ceramic comprises the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming and removing glue: dry-pressing the powder into a round green body under the action of hydraulic pressure by using a hydraulic press and a grinding tool, and putting the round green body into a box-type furnace for removing glue to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multi-point electrode: and a plurality of point electrodes are respectively arranged on the upper polar plate and the lower polar plate of the zinc oxide pressure-sensitive ceramic, and the point electrodes of the upper polar plate and the lower polar plate are respectively connected.
Preferably, the weighed ingredients, ultrapure water and zirconium balls required by the zinc oxide pressure sensitive ceramic are subjected to ball milling in a planetary ball mill according to the proportion of 1.
Furthermore, the ball milling time is 3-5 hours, and the rotation period is 30-60min.
Preferably, the mixed slurry after ball milling is placed in an electrothermal blowing drying oven, and the temperature is kept for more than 5 hours at 100 ℃ for drying operation.
Preferably, the dried powder is granulated by a screen, wherein the screen mesh range is as follows: 40 to 120 meshes.
Preferably, the distance between one point electrode in the lower polar plate of the zinc oxide voltage-sensitive ceramic and a plurality of point electrodes in the upper polar plate respectively represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
The multipoint electrode zinc oxide pressure-sensitive ceramic is prepared by the preparation method of the multipoint electrode zinc oxide pressure-sensitive ceramic.
An electrochemical test, comprising the following steps:
and (3) respectively assembling one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic with a plurality of point electrodes in the upper polar plate by adopting a digital source meter electrode, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a preparation method of a multi-point electrode zinc oxide voltage-sensitive ceramic, the multi-point electrode zinc oxide voltage-sensitive ceramic is obtained by the method, the designed multi-point electrode zinc oxide voltage-sensitive ceramic can realize the voltage-sensitive ceramic with a certain range of voltage-sensitive voltage by connecting different point electrodes on the surfaces of an upper polar plate and a lower polar plate of the ceramic, and the application range is wide. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under multiple voltage-sensitive voltages at the same time, so that effective protection on multiple circuits is realized at the same time; the multi-point electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.
Drawings
FIG. 1 is a schematic diagram of a multi-point electrode of a zinc oxide pressure sensitive ceramic of the present invention;
FIG. 2 is a schematic diagram of the upper plate point electrode and wiring of the multi-point electrode zinc oxide voltage-sensitive ceramic of the present invention;
FIG. 3 is a schematic diagram of the lower plate point electrode and wiring of the multi-point electrode zinc oxide voltage-sensitive ceramic of the present invention;
FIG. 4 is an SEM image of the multi-point electrode zinc oxide pressure sensitive ceramic of the invention;
FIG. 5 is a schematic view showing the inter-electrode distance of the multi-point electrode zinc oxide pressure sensitive ceramic of the present invention;
FIG. 6 is a schematic diagram of the lower plate point electrode and wiring of the 2-point electrode zinc oxide voltage-sensitive ceramic in example 1 of the present invention;
FIG. 7 is a schematic diagram of the upper plate point electrode and wiring of the 2-point electrode zinc oxide voltage-sensitive ceramic in example 1 of the present invention;
FIG. 8 is a view showing different point electrode sets U-I in example 1 of the present invention;
FIG. 9 is a schematic view of the lower plate point electrode and wiring of the 3-point electrode zinc oxide voltage-sensitive ceramic in example 2 of the present invention;
FIG. 10 is a schematic diagram of the upper plate point electrode and wiring of the 3-point electrode zinc oxide voltage-sensitive ceramic in example 2 of the present invention;
FIG. 11 is a view of different electrode groups U-I according to embodiment 2 of the present invention;
FIG. 12 is a schematic view of the bottom plate point electrode and the wiring of the 5-point electrode zinc oxide pressure sensitive ceramic in example 3 of the present invention;
FIG. 13 is a schematic diagram of the upper plate point electrode and wiring of the 5-point electrode zinc oxide pressure sensitive ceramic in example 3 of the present invention;
FIG. 14 is a diagram of different electrode groups U-I according to embodiment 3 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the invention adopts the traditional solid heat sintering method to prepare the zinc oxide pressure-sensitive ceramic, and the preparation process and the test flow mainly comprise the steps of material preparation → ball milling → drying → grinding → granulation → dry press molding → degumming → sintering → multipoint electrode silver → electrical performance test. The sample preparation and electrode design steps are described as necessary:
the invention provides a preparation method of a multi-point electrode zinc oxide voltage-sensitive ceramic, the multi-point electrode zinc oxide voltage-sensitive ceramic is obtained by the preparation method, and the voltage-sensitive ceramic with voltage-sensitive voltage in a certain range can be realized according to different point electrodes connected on the surface of the ceramic, so that the application range is wide.
Specifically, the preparation method comprises the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming, and removing glue: dry-pressing the powder into a round green body under the action of hydraulic pressure by using a hydraulic press and a grinding tool, and putting the round green body into a box-type furnace for removing glue to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multi-point electrode: arranging a plurality of point electrodes and a plurality of point electrodes of a lower polar plate on an upper polar plate of the zinc oxide pressure-sensitive ceramic, respectively connecting the plurality of point electrodes of the upper polar plate and the plurality of point electrodes of the lower polar plate, coating silver paste into silver point electrodes with proper sizes by using a silver coating grinding tool with a certain diameter to be used as welding points, and then welding a lead with each welding point by using an electric iron to ensure good and safe contact, as shown in fig. 1, 2 and 3.
Specifically, the weighed ingredients, ultrapure water and zirconium balls required by the zinc oxide pressure-sensitive ceramic are subjected to ball milling in a planetary ball mill according to the proportion of 1
Specifically, the mixed slurry after ball milling is placed in an electrothermal blowing drying oven, and the temperature is kept for more than 5 hours at 100 ℃ for drying operation.
Specifically, the dried powder is granulated through a screen, wherein the screen mesh range is as follows: 40 to 120 meshes.
Specifically, the distance between one point electrode in the lower polar plate of the zinc oxide voltage-sensitive ceramic and a plurality of point electrodes in the upper polar plate represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
Referring to fig. 2 and 3, the multi-point electrode zinc oxide pressure sensitive ceramic of the present invention is obtained by the above-mentioned preparation method of the multi-point electrode zinc oxide pressure sensitive ceramic.
The invention provides an electrochemical test, which specifically comprises the following steps:
and (3) adopting a digital source meter electrode to respectively assemble one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic with a plurality of point electrodes in the upper polar plate, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
Referring to fig. 4, a SEM image of a general zinc oxide varistor ceramic with excellent nonlinearity and relatively uniform grain distribution shows that the varistor field strength of the zinc oxide varistor ceramic is mainly affected by grain boundary resistance, double schottky barrier height and grain size, so that a varistor ceramic with uniform microstructure, excellent nonlinearity and stability can be considered to have a small change in varistor field strength along each direction, and is denoted as E 0 Therefore, the following are:
wherein d is min A distance between the upper and lower electrodes and the two point electrodes, U 0 A voltage-dependent voltage for two point electrodes facing up and down, E 0 The pressure-sensitive field strength.
Referring to fig. 5, the upper and lower plates of the multi-point electrode zinc oxide pressure-sensitive ceramic also have different point electrodes, and the direction of the pressure-sensitive field intensity, i.e. the connection direction of the upper and lower point electrodes, changes accordingly. Because the microstructure of the selected sample is uniform, the nonlinearity of the zinc oxide pressure-sensitive ceramic has certain stability. Thus, the same zinc oxide voltage-sensitive ceramic can have a certain voltage-sensitive voltage U x (E 0 d min ≤U x ≤E 0 d max ) Has high response characteristic, and has good economic benefit and application prospect.
Example 1
Preparation of a sample:
preparing materials: weighing the zinc oxide pressure sensitive ceramic making batch using an electronic balance to a total of 15g, including 95.4 mol% molZnO, 1.8mol% Bi 2 O 3 、1mol％MnO 2 、1mol％TiO 2 And 0.8mol% Sb 2 O 3 。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electric heating air blast drying box, and preserving the heat for more than 5 hours at the temperature of 100 ℃ to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, then putting the powder into a planetary ball mill to be ball-milled for 30min, then putting the mixed slurry into an electric heating blast drying box, preserving the temperature for more than 5h at 100 ℃, and then sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming, and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool under a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by virtue of appearance and uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out within 100 ℃ of the sintering temperature.
Multi-point electrode design: fig. 7 shows the point electrodes and the wiring of the upper electrode plate, and 2 point electrodes, namely the point electrode 1 and the point electrode 2, are distributed in total. The distance between the point electrode 1 and the point electrode 2 is 2mm, and according to the geometrical relationship, the connecting line distances of the electrodes 0-1 and 0-2 are respectively 1.240mm and 2.353mm, as shown in table 1. Fig. 6 shows the lower plate point electrode and the wiring, and 1 point electrode, namely point electrode 0, is distributed in total. The position of the dot electrode 0 on the lower plate is the same as the position of the dot electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
Test and test results
The electrodes of the KEITHLEY2410 type digital source meter are respectively a 0-1 point electrode assembly and a 0-2 point electrode assembly. The results of the voltage-current data of the test samples at room temperature are shown in table 1, and the voltage-current (U-I) characteristic curve is shown in fig. 8.
Table 1 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage 1mA And actual value of U' 1mA And a non-linear coefficient. In which the non-linear coefficient
(wherein U is 1mA And U 0.1mA The voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
TABLE 1 distance d between upper and lower electrodes and theoretical value U of voltage-sensitive voltage 1mA And actual value of U' 1mA And nonlinear coefficient
As shown in FIG. 8, the voltage-sensitive voltage of the ZnO varistor increases with the distance between the electrode connecting lines of the upper and lower plate points, and the 3-group-connected ZnO varistor exhibits good nonlinearity, as can be seen from Table 1, within the allowable error range, the test and theoretical analysis are consistent, i.e., the same ZnO varistor can have a certain voltage-sensitive voltage U x ＝E 0 d x (E 0 d min ≤U x ≤E 0 d max ) Wherein d is x The distance between the point electrodes of the upper and lower polar plates is the connecting line distance.
Example 2
Preparation of a sample:
preparing materials: weighing the ingredients for making the zinc oxide pressure sensitive ceramic using an electronic balance a total of 15g, including 95.4% molZnO, 1.8mol Bi 2 O 3 、1mol％MnO 2 、1mol％SiO 2 And 0.8mol% Sb 2 O 3 。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electrothermal blowing drying box, and keeping the temperature at 100 ℃ for more than 5 hours to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, putting the powder into a planet ball mill to be ball-milled for 30min, putting the mixed slurry into an electrothermal blowing drying box, keeping the temperature at 100 ℃ for more than 5h, and sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool under a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by virtue of appearance and uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out within 100 ℃ of the sintering temperature.
Multi-point electrode design: fig. 10 shows the upper plate point electrode and the wiring, and 3 point electrodes, namely, the point electrode 1, the point electrode 2 and the point electrode 3 are distributed in total. The distances between the point electrode 1 and the point electrodes 2 and 3 were 1.22mm and 1.85mm, respectively, and according to the geometrical relationship, the connection distances of the electrodes 0-1, 0-2 and 0-3 were 1.24mm, 1.74mm and 2.23mm, respectively, as shown in table 2. Fig. 9 shows the lower plate point electrode and the wiring, and 1 point electrode, namely point electrode 0, is distributed. The position of the dot electrode 0 on the lower plate is the same as the position of the dot electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
The electrodes of the KEITHLEY2410 type digital source meter are respectively connected with 0-1 point electrodes, 0-2 point electrodes and 0-3 point electrodes. The results of the voltage-current data of the test samples at room temperature are shown in Table 2, and the voltage-current (U-I) characteristic curves are shown in FIG. 11.
Table 2 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage 1mA And actual value of U' 1mA And a non-linear coefficient. Wherein the non-linear coefficient
(wherein U is 1mA And U 0.1mA The voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
Table 2 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage 1mA And actual value of U' 1mA And nonlinear coefficient
As shown in FIG. 10, the voltage-sensitive voltage of the ZnO varistor ceramic increases with the increase of the distance between the electrode connecting lines of the upper and lower plate points, and the 3-group-connected ZnO varistor ceramic shows better nonlinearity, as shown in Table 2, within the allowable error range, the test is consistent with the theoretical analysis, that is, the same ZnO varistor ceramic can have a certain voltage-sensitive voltage U x ＝E 0 d x (E 0 d min ≤U x ≤E 0 d max ) Wherein d is x The distance between the point electrodes of the upper and lower polar plates is the connecting line distance.
Example 3
Preparation of a sample:
preparing materials: weighing the zinc oxide pressure sensitive ceramic making batch using an electronic balance to a total of 15g, including 95.4 mol% molZnO, 1.8mol% Bi 2 O 3 、1mol％MnO 2 、1mol％SiO 2 And 0.8mol% Sb 2 O 3 。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electric heating air blast drying box, and preserving the heat for more than 5 hours at the temperature of 100 ℃ to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, then putting the powder into a planetary ball mill to be ball-milled for 30min, then putting the mixed slurry into an electric heating blast drying box, preserving the temperature for more than 5h at 100 ℃, and then sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool under a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by the appearance and the uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out at the temperature of not lower than the sintering temperature and within 100 ℃.
Multi-point electrode design: fig. 13 shows the point electrodes and the wiring of the upper plate, and 5 point electrodes, namely, the point electrode 1, the point electrode 2, the point electrode 3, the point electrode 4 and the point electrode 5 are distributed in total. The distances from the point electrode 1 to the point electrodes 2, 3, 4 and 5 were 1.4mm, 2.8mm, 4.2mm and 5.6mm, respectively, and according to the geometrical relationship, it was found that the connection distances of the electrodes 0-1, 0-2, 0-3, 0-4 and 0-5 were 1.24mm, 1.87mm, 3.06mm, 4.38 and 5.74mm, respectively, as shown in table 3. Fig. 12 shows the lower plate point electrode and the wiring, and 1 point electrode, namely, the point electrode 0, is distributed in total. The position of the point electrode 0 on the lower plate is the same as that of the point electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
Test and test results
The electrodes of the KEITHLEY2410 type digital source meter are respectively a 0-1 point electrode assembly, a 0-2 point electrode assembly, a 0-3 point electrode assembly, a 0-4 point electrode assembly and a 0-5 point electrode assembly. The results of the voltage-current data of the test samples at room temperature are shown in Table 3, and the voltage-current (U-I) characteristic curves are shown in FIG. 14.
Table 3 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage 1mA And actual value of U' 1mA And a non-linear coefficient. In which the non-linear coefficient
(wherein U is 1mA And I 0.1mA The voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
TABLE 3 distance d between upper and lower electrodes and theoretical value U of voltage-sensitive voltage 1mA And actual value U' 1mA And the nonlinear coefficient is as shown in fig. 14, the voltage-sensitive voltage of the zinc oxide voltage-sensitive ceramic increases with the distance between the upper and lower plate point electrode connecting lines, and the 5-group method zinc oxide voltage-sensitive ceramic shows better nonlinearity, as can be obtained from table 3, within the error allowable range, the experiment is more consistent with the theoretical analysis, that is, the same zinc oxide voltage-sensitive ceramic can have a certain voltage-sensitive voltage U x ＝E 0 d x (E 0 d min ≤U x ≤E 0 d max ) In which d is x The distance between the point electrodes of the upper and lower polar plates is shown.
In summary, the invention provides a preparation method of a multi-point electrode zinc oxide voltage-sensitive ceramic, the multi-point electrode zinc oxide voltage-sensitive ceramic is obtained by the method, the designed multi-point electrode zinc oxide voltage-sensitive ceramic can realize voltage-sensitive ceramic with a certain range of voltage-sensitive voltage by connecting different point electrodes on the surfaces of a ceramic upper polar plate and a ceramic lower polar plate, and the application range is wide. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under a plurality of voltage-sensitive voltages at the same time, so that effective protection on a plurality of circuits is achieved at the same time; the multipoint electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.
Meanwhile, the same zinc oxide voltage-sensitive ceramic obtained by electrochemical test of the multi-point electrode zinc oxide voltage-sensitive ceramic has a certain voltage-sensitive voltage U x (E 0 d min ≤U x ≤E 0 d max ) The method has high response characteristic and has good economic benefit and application prospect.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic is characterized by comprising the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming, and removing glue: using a hydraulic press and a grinding tool to dry-press the powder under the action of hydraulic pressure to obtain a round green body, and putting the round green body into a box-type furnace for rubber removal to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multi-point electrode: respectively arranging a plurality of point electrodes on an upper polar plate and a lower polar plate of the zinc oxide voltage-sensitive ceramic, and respectively connecting the plurality of point electrodes of the upper polar plate and the lower polar plate;
the distance between one point electrode in the lower polar plate of the zinc oxide voltage-sensitive ceramic and a plurality of point electrodes in the upper polar plate respectively represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
2. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic according to claim 1, wherein the weighed ingredients of the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls are subjected to ball milling in a planetary ball mill according to the ratio of 1.
3. The preparation method of the multipoint electrode zinc oxide pressure sensitive ceramic according to claim 2, wherein the ball milling time is 3-5 hours, and the rotation period is 30-60min.
4. The preparation method of the multipoint electrode zinc oxide pressure sensitive ceramic according to claim 1, wherein the ball-milled mixed slurry is placed in an electrothermal blowing drying oven and is subjected to heat preservation for more than 5 hours at 100 ℃ for drying operation.
5. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic according to claim 1, wherein the dried powder is granulated by a screen mesh, wherein the screen mesh range is as follows: 40 to 120 meshes.
6. A multi-point electrode zinc oxide pressure-sensitive ceramic obtained by the preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic of any one of claims 1 to 5.
7. An electrochemical test method is characterized by comprising the following steps:
and (3) respectively assembling one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic of claim 6 with a plurality of point electrodes in the upper polar plate by using a digital source meter electrode, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
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| CN102142308A (en) * | 2011-01-12 | 2011-08-03 | 深圳顺络电子股份有限公司 | Laminated voltage-sensitive resistor array |
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