Patent Application
20130133183
1. Field of the Invention
The present invention relates to a process for producing a zinc oxide varistor and, more particularly, to a process for producing a zinc oxide varistor having both a high potential gradient and a high non-linearity coefficient.
2. Description of Prior Art
Zinc oxide varistors (hereinafter referred to as ZnO varistors) due to having excellent surge-absorbing ability and superior non-ohmic characteristics are known as ideal overvoltage protectors, which are used as transient voltage suppressors in an electric power system or a circuit system to prevent transient surges and thereby protect system components.
However, as most countries in the world have planned to let one's own national power system toward extra high voltage (abbreviated as EHV) transmission system planning, new generation of ZnO varistor required for having both high potential gradient and high energy-absorbing abilities is absolutely imperative and becomes an important development trend.
To enhance the potential gradient and the energy withstand capability (or also called energy absorption capability) of ZnO varistors, known technical knowledge has suggested ZnO varistor is designed to reduce the ZnO grain size, lower the porosity, increase the number of grain boundaries and enhance the grain boundary barrier. Thus, the number of potential barriers per unit thickness of ZnO varistor becomes inversely proportional to the ZnO grain size so that the ZnO grain size and the number of grain boundaries to encapsulate the ZnO grains become important factors in determining the potential gradient of ZnO varistors.
From the known classical theories, a ZnO varistor has a breakdown voltage of approximately 3V per a single grain boundary among the ZnO grains thereof. The ZnO varistor has non-ohmic properties is resulted from the Double Schottky Barrier happened within every two ZnO grains. To have the Double Schottky Barrier enhanced more higher is to have ZnO varistors provided with more excellent properties in both non-linearity coefficient (α) and the breakdown voltage.
ZnO varistors if formulated with traditional formulas and prepared by conventional techniques have potential gradients of from about 180 to about 200 V/mm only, with energy withstand capabilities ranging from about 100 to about 140 J/cm3. Therefore, the conventional ZnO varistors are not suited for use in EHV transmission systems.
For improvement of ZnO varistors having high potential gradients, currently applicable methods generally resort to the following two approaches:
1. Rare-earth oxides are added as a source of doping ions for ZnO grains, resulted in that the produced ZnO varistors have potential gradients up to 400 V/mm.
2. Improved manufacturing methods for preparing zinc oxide ceramic powder more available use in producing ZnO varistors are made, or new techniques (e.g., high-energy ball milling and nano pulverization) are introduced, resulted in that the produced ZnO varistors have potential gradients of about 2,000 V/mm.
Nevertheless, the aforesaid approaches to increasing the potential gradient of ZnO varistors have a common drawback, i.e., once the potential gradient of the ZnO varistors is increased, the non-linearity coefficient (α) of the varistors is inevitably lowered down. This negative phenomenon leads to the ZnO varistors unfavorable in voltage-limiting effect and still unavailable use in EHV transmission systems.
In view of the above, the primary object of the present invention is to provide a process for producing a zinc oxide varistor having both a high potential gradient and a high non-linearity coefficient, which process basically includes steps of:
The process for producing a ZnO varistor of the present invention is different from the conventional ones mainly in that the doped ZnO grains sufficiently semiconductorized and the high-impedance sintering components (e.g. sintered powder or glass powder) are prepared by two separate procedures respectively. By doing so, not only the produced ZnO varistors have the following unexpected advantages, but also the produced ZnO varistors have both an ultrahigh potential gradient as well as an ultrahigh non-linearity coefficient to overcome the unfavorable limitations of ZnO varistors mentioned above if produced by conventional methods for making a ZnO varistor:
1. to have the Double Schottky Barrier enhanced more higher once happened among ZnO grains;
2. to have the number of grain boundaries deposited per unit thickness of ZnO varistor increased more greater among the ZnO grains; and
3. to have ZnO varistor increased more excellent in material composition uniformity and structural uniformity.
The present invention will be best understood by referring to the following detailed description in conjunction with the accompanying drawings, in which:
The present invention discloses a process for producing a zinc oxide varistor. The invented process of the present invention is suitable for producing a zinc oxide varistor having an ultrahigh potential gradient as well as an ultrahigh non-linearity coefficient. Preferably, the invented process is suited for use in producing a zinc oxide varistor having a potential gradient ranging from 1,200 to 9,000 V/mm, a non-linearity coefficient (α) ranging from 21.5 to 55 and a leak current (IL) ranging from 1 to 21 μA. More preferably, the invented process is suited for use in producing a zinc oxide varistor whose potential gradient exceeds 2,000 V/mm.
The process disclosed herein for producing a zinc oxide varistor includes the following steps:
a) individually advanced preparation of ZnO grains doped with non-equivalent ions required to preset a zinc oxide varistor if produced having a desired potential gradient ranged from 1200 to 9000 V/mm;
b) individually advanced preparation of sintered powders (or called glass powders) required to preset a zinc oxide varistor if produced having a desired potential gradient ranged from 1200 to 9000 V/mm;
c) preparing ground ceramic powders for making the ZnO varistors by calcining a slurry mixture of mixing the doped ZnO grains of step a) in a specific ratio with the glass powders of step b) and grounding the calcined ceramic powers into desired fineness; and
d) performing a sintering process to the ground ceramic powders of step c) to produce ZnO varistors having an ultrahigh potential gradient ranging from 1200 to 9000 V/mm and an ultrahigh non-linearity coefficient (α) ranging from 21.5 to 55.
In step a) of the disclosed process of the present invention, non-equivalent ions are doped into ZnO grains by substituting Zn2+ ions or occupying interstitial sites. This serves to suppress the growth of ZnO grains during a subsequent sintering process, and to allow the ZnO grains to be sufficiently semiconductorized.
According to the principle of crystallography, the non-equivalent ions to be doped with the ZnO grains may be ions of at least one element selected from the group consisting of lithium (Li), copper (Cu), aluminum (Al), cerium (Ce), cobalt (Co), chromium (Cr), indium (In), gallium (Ga), molybdenum (Mo), manganese (Mn), niobium (Nb), lanthanum (La), yttrium (Y), praseodymium (Pr), antimony (Sb), nickel (Ni), titanium (Ti), vanadium (V), tungsten (W), zirconium (Zr), iron (Fe), boron (B), silicon (Si) and tin (Sn). The amount of the non-equivalent ions doped with ZnO grains may vary according to practical needs and is less than 20 mol % of the zinc oxide.
Either of the following two methods can be used to prepare ZnO grains doped with non-equivalent ions:
Soluble salts containing the ions to be doped are selected according to the specified properties of the ZnO varistor, and an aqueous solution of a specific concentration is prepared from the salts. The solution is added with ZnO powder, stirred, oven-dried, and calcined at 950-1,550° C. The calcined material thus obtained is broken up and ground to a desired fineness for later use.
ZnO grains doped with the desired ions are prepared by a physical or chemical nanotechnology-based method for preparing a fine powder, depending on the specified properties of the ZnO varistor. Suitable physical methods include, for example, vapor deposition, the laser method, and the microwave method. Suitable chemical methods include precipitation, the microemulsion method, hydrothermal treatment, phase transfer, the sol-gel method, and so on.
Chemical precipitation can be carried out in the following manner. A solution containing zinc ions and a solution containing the doping ions are mixed and stirred to produce an evenly mixed solution containing both zinc ions and the doping ions. Under a stirring condition, a precipitation agent is added into the mixed solution by forward or backward addition. Once the pH value is controlled at the appropriate level, the co-precipitate is taken out, washed for several times, oven-dried, and calcined at a proper temperature. Thus, zinc oxide crystal grains containing the doping ions are obtained.
The precipitation agent can be selected from oxalic acid, urea, ammonium carbonate, ammonium bicarbonate, ammonia water, ethanolamine, and other alkaline solutions. The calcination temperature depends on the decomposition temperature of the co-precipitate.
If the sol-gel method is used, zinc ions are evenly dispersed in a sol of an inorganic salt or a metal alkoxide containing the desired doping ions. After hydrolysis and a condensation and polymerization reaction, the sol becomes a gel. The gel is cured and subjected to a heat treatment to produce zinc oxide crystal grains doped with non-equivalent ions.
ZnO grains obtained by the above two nanotechnology-based preparation techniques have a small particle size and feature a highly uniform distribution of the doping ions. Moreover, with a relatively low heat-treatment temperate ranging from 350° C. to 1,000° C., the two preparation techniques are suitable for mass production.
In the process of the present invention, steps a) and b) are two independent and different procedures. Step b) is used to prepare sintered powders (also known to be sintered as grain boundary component) whose composition may vary according to the specified properties of the ZnO varistor.
The sintered powders required for having property of high impedance can be prepared by the following two methods:
According to the specified performance of the ZnO varistor, an oxide or oxides, a hydroxide or hydroxides, a carbonate or carbonates, a nitrate or nitrates, or an oxalate or oxalates of at least one element selected from the group consisting of the following is used as the starting material: bismuth (Bi), antimony (Sb), manganese (Mn), cobalt (Co), chromium (Cr), nickel (Ni), titanium (Ti), silicon (Si), barium (Ba), boron (B), selenium (Se), lanthanum (La), praseodymium (Pr), yttrium (Y), indium (In), aluminum (Al) and tin (Sn). Once sufficiently mixed, the starting material becomes the base of a sintered material of the desired composition. The base is sintered and ground to the desired fineness to produce a high-impedance sintered powder. Alternatively, the sufficiently mixed starting material is melted at high temperature, water-quenched, oven-dried, and then ground into a sintered powder.
For instance, the starting material of the aforesaid sintered material is a mixture of at least two oxides selected from the group consisting of bismuth trioxide (Bi2O3), boron trioxide (B2O3), antimony trioxide (Sb2O3), cobalt trioxide (Co2O3), manganese dioxide (MnO2), chromium trioxide (Cr2O3), vanadium trioxide (V2O3), zinc oxide (ZnO), nickel oxide (NiO), silicon dioxide (SiO2), and a rare-earth oxide. The purpose of adding extra zinc oxide (ZnO) into the sintered powder is to enhance sintering effect between grain boundaries.
Nanoparticles having the specified components are prepared by a physical or chemical nanotechnology-based method according to the specified properties of the zinc oxide varistor. Preferably, chemical precipitation, the microemulsion method, or the sol-gel method is used in the present invention to prepare high-impedance nanoparticles. By using a suitable physical or chemical nanotechnology-based method, a sintered powder featuring a uniform distribution of its components and a small particle size can be obtained.
In step c) of the process of the present invention disclosed herein is performed as follows. The high-impedance sintered powder prepared in step b) is added with water to produce a slurry treatment. Then, under a stirring condition, the ZnO grains doped with non-equivalent ions as prepared in step a) are added to the slurry in a specific ratio. The resultant mixture is sufficiently stirred, oven-dried, calcined, and ground to produce a ceramic powder for making the zinc oxide varistor.
The ratio by weight of the doped ZnO grains of step a) to the sintered powders of step b) ranges from 100:2 to 100:50, preferably from 100:10 to 100:30.
In step d) of the disclosed method, the zinc oxide varistor is made by a conventional method which includes: having ground ceramic powders of step c) mixed with appropriate binder to form an organic slurry; forming a layer of green film made from the organic slurry by doctor blade technique; printing two or more layers of interlaced inner electrodes; calcining green film chips having the inner electrodes; and then plating the two exposed ends of the inner electrodes of each chip with external electrodes. Thus, a disc-shaped or multilayer zinc oxide varistor is obtained.
The disclosed process for producing a ZnO varistor has the following advantageous effects:
1. The height of the Schottky barrier among ZnO grains is increased
As step a) of the disclosed process is an independent procedure, the process of doping ZnO grains with non-equivalent ions is no longer subject to limitations imposed by the selected high-impedance grain boundary component. In addition, the advantages listed below increase the height of the Schottky barrier among ZnO grains, such that the resultant ZnO varistor has an ultrahigh potential gradient and an ultrahigh non-linearity coefficient.
1) The range of eligible doping ions is broadened:
2) The doping amount of the non-equivalent ions is increased:
According to the process of the present invention, the composition of grain boundary component can be adjusted to suppress the growth of ZnO grains, or an ultrafine grinding technique can be used to reduce the particle size of ZnO grains, or nanoscale ZnO grains can be used. All of the above contributes to increase the number of ZnO grains and the number of grain boundaries deposited per unit thickness of ZnO varistor, so that the resultant ZnO varistor produced is then provided with an ultrahigh potential gradient and a superior non-ohmic property.
3. The grain boundary component deposited among ZnO grains to encapsulate the ZnO grains is enhanced to increase uniformity and structural strength more and more excellent and stronger.
Step b) of the disclosed process is an independent procedure whereby the grain boundary component is made into nanoparticles each having substantially the same composition. More importantly, by grinding and calcining the grain boundary component (which includes Bi2O3) or by synthesizing the grain boundary component (which includes Bi2O3 and other selected ingredients) using a suitable nanotechnology-based method, the composition of each nanoparticle is rendered similar and contains Bi2O3. During the sintering process, the almost identical structure of the grain boundary component helps bring down the solubility of zinc oxide in fused masses of Bi2O3, lower the growth of ZnO grains, and prevent the particle size of the ZnO grains from increasing. Therefore, as the number of ZnO grains and the number of grain boundaries deposited per unit thickness of ZnO varistor are increased, the resultant ZnO varistor has a potential gradient ranging from 1,200 to 9,000 V/mm, preferably from 2,000 to 9,000 V/mm, a non-linearity coefficient (α) ranging from 21.5 to 55 and a leak current (IL) ranging from 1 to 21 μA.
A sintered powder coded G1-10 is prepared by chemical precipitation and has the compositions based on 1 mol % of ZnO as provided below.
Doped ZnO* grains are prepared by soaking zinc oxide in a solution containing the doping ions based on 1 mol % of ZnO as provided below.
After the doped ZnO* grains are evenly mixed with the sintered powder G1-10, the mixture is pressed at a pressure of 1000 kg/cm2 to form discs each having a diameter of 8.4 mm. The discs are sintered at 920° C. for eight hours. Then, the sintering of surface silver electrodes is completed at 800° C. to form disc-shaped zinc oxide varistors. As the foregoing ion doping process uses three different sets of calcination conditions separately, i.e., calcining at 950° C. for two hours, 1250° C. for two hours, and 1550° C. for two hours respectively, three types of zinc oxide varistors are produced, whose performances are listed in Table 1. All zinc oxide varistors produced have potential gradients higher than 1,200 V/mm, a non-linearity coefficient (α) ranging from 45.6 to 53.2 and a leak current (IL) ranging from 1.2 to 5.3 μA.
A sintered powder coded G1-00 is prepared by chemical precipitation and has the compositions by weight as provided below.
The doped ZnO* grains listed in Table 2 are prepared by chemical co-precipitation and each ZnO grain doped with 1 mol % indium (In) ions. Each sample of doped ZnO* grains listed in Table 2 is evenly mixed with the sintered powder G1-00, and the ratio by weight of the former to the latter is 100:10 or 100:15 or 100:30 respectively.
Next, the mixture is pressed at a pressure of 1000 kg/cm2 to form discs, which are subsequently sintered at 1065° C. for two hours. Once the coating of silver electrodes is completed at 800° C., disc-shaped zinc oxide varistors are obtained. The test results of the performances of the different types of zinc oxide varistors are shown in Table 2.
From Table 2, when the doped ZnO* grains are doped with the same kinds of doping ions, the potential gradient (or called breakdown voltage (BDV)) of the resultant ZnO varistors varies with the ratio of the doped ZnO* grains to the sintered powder. Therefore, by controlling the kinds of the doping ions doped with ZnO grains or by adjusting the ratio of the doped ZnO* grains to the sintered powder, a produced ZnO varistor having a potential gradient higher than 1,700 V/mm, even higher than 2,000 V/mm, is achievable.
The sintered powder G1-10 prepared in Embodiment 1 is used, and doped ZnO* grains are prepared by soaking zinc oxide in a solution containing the doping ions. The ion doping process is conducted at a calcination temperature of 950° C. for two hours, and the kinds and ratios of the doping ions based on 1 mol % of ZnO are listed in Table 3.
As in embodiment 1, disc-shaped zinc oxide varistors are made, and the test results of their performances are listed in Table 4.
From Table 4, the zinc oxide varistors of samples 4 through 7 all have potential gradients higher than 1,200 V/mm, non-linearity coefficients α ranging from 27.41 to 52.9 and leak currents IL ranging from 1.6 to 16.5 μA.
In particular, the zinc oxide varistor of sample 7 has a potential gradient as high as 6,023 V/mm.
The sintered powder G1-10 prepared in Embodiment 1 is used, and doped ZnO* grains are prepared by the sol-gel method. The ion doping process is carried out at a calcination temperature of 350° C. for three hours. The kinds and ratios of the doping ions are the same as those of samples 6 and 7 in embodiment 3; hence, the corresponding samples in this embodiment are identified as samples 8 and 9 respectively, with
Disc-shaped zinc oxide varistors are made in the same way as in embodiment 1, and their performances are listed in Table 5.
It should be pointed out that breakdown voltage (BDV) if higher than 6,500 V/mm is beyond the measuring range of the testing instrument. Therefore, I-V curves are plotted, and the values of V1 (I1=0.1 mA) and V2 (I2=1.0 mA) are substituted into the following equation (I) to calculate the non-linearity coefficients α.
α=1/log(V2/V1). (I)
The leak currents IL are obtained by taking the current at 80% of breakdown voltage (BDV), as is typically the case.
The I-V curves of the disc-shaped zinc oxide varistors of samples 8 and 9 are shown in
According to the I-V curves, the potential gradients of the zinc oxide varistors of both samples 8 and 9 exceed 6,800 V/mm. In particular, the zinc oxide varistor of sample 9 has a potential gradient higher than 9,000 V/mm, a non-linearity coefficient α as high as 21.50, and a leak currents IL lower than 16 μA.
The doped ZnO* grain in embodiment 1 which is doped at the calcination temperature of 1,250° C. is evenly mixed with the sintered powder G1-10 in embodiment 1. The mixture is passed through a planetary grinding machine to produce three types of ceramic powder samples whose average particle sizes are 2.1 μm, 1.1 μm, and 0.56 μm respectively. Disc-shaped zinc oxide varistors are made as in embodiment 1, and their performances are listed in Table 6.
As shown in Table 6, when the zinc oxide ceramic powder has a particle size equal to or less than 1.1 μm, the resultant zinc oxide varistor has a potential gradient higher than 1,200 V/mm. Hence, this embodiment demonstrates that the potential gradient of a zinc oxide varistor can be increased by increasing the fineness of the zinc oxide ceramic powder of which the varistor is made.
The zinc oxide ceramic powder of sample 5 in embodiment 3 is used to make 2220-type and 1210-type multilayer varistors by a conventional method for making the same, in which the sintering process is performed at 900° C. for eight hours. The electric properties of the resultant varistors are listed in Table 7.
As shown in Table 7, both the 2220ML100 and 1210ML100 multilayer varistors have potential gradients higher than 2,000 V/mm and non-linearity coefficients (a) higher than 35.
The zinc oxide ceramic powder of sample 6 in embodiment 3 is used to make 2220-type and 1210-type multilayer varistors by a conventional method for making the same, in which the sintering process is performed at 900° C. for eight hours. The electric properties of the resultant varistors are listed in Table 8.
As shown in Table 8, the 2220ML390 and 1210ML390 multilayer varistors have potential gradients of about 4,000 V/mm and non-linearity coefficients (a) exceeding 44.
Embodiments 6 and 7 demonstrate that the process of the present invention is also suited for making a multilayer varistor having both a high potential gradient and non-linear properties.
In a way similar to embodiment 1, the sintered powder G1-10 is used with either undoped ZnO grains or doped ZnO* grains to produce disc-shaped zinc oxide varistors. The performances of the resultant varistors are listed in Table 9.
Based on the sectional SEM photographs, the average particle size of undoped ZnO grains in the undoped disc sample is measured and calculated as 5.2 μm, and the average particle size of the doped ZnO* grains in the doped disc sample is 2.2 μm, the former particle size being 2.4 times the latter.
Since the two samples are sintered under the same conditions, the zinc oxide particle size of the undoped sample is 2.4 times that of the doped sample. This indicates that the doped zinc oxide can effectively suppress the growth of zinc oxide grains during the sintering process.
In addition, according to the equations for calculating the potential gradient was proportioned to the number of zinc oxide grains in per unit thickness, the potential gradient of the doped zinc oxide disc should have been 777.6 V/mm (i.e., 324 V/mm times 2.4 equals 777.6 V/mm), and yet the actual test result is 1,370 V/mm. The increase of 592.4 V/mm (i.e., 1370 V/mm minus 777.6 V/mm equals 592.4 V/mm) can be attributed to the doping of ions, which increases the height of the Schottky barrier at the zinc oxide grain boundary. By the same token, the doped zinc oxide varistor has the higher non-linearity coefficient.
Disc-shaped zinc oxide varistors are made of the sintered powder G1-10 in embodiment 1 and the doped ZnO* of each of samples 6 and 7 in embodiment 3. The leak currents of the resultant zinc oxide varistors used at different temperatures respectively are listed in Table 10.
Embodiment 9 demonstrate that the process of the present invention is also suited for making a zinc oxide varistor applicable to operation where the operating temperature is ranging from 25° C. to 200° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 100143801 | Nov 2011 | TW | national |
