Moisture sensitive element

BACKGROUND OF THE INVENTION
The present invention relates to a moisture sensitive element of the type which detects variations in humidity with electric resistance.
Moisture sensitive elements which detect variations in humidity by sensing variations of electric signals are used as moisture sensors in automatic humidity control apparatus such as room air conditioners.
One known type of moisture sensor is described, for example, in Japanese Pat. Publications No. 31836/79 and No. 49705/80. It is comprised of an insulative substrate on which a pair of electrodes are disposed, and moisture located between the electrodes will be detected
This sensor, however, cannot detect delicate variations of humidity in the surrounding atmosphere.
Another type of prior art moisture sensor comprises a porous metal oxide ceramic plate and a pair of electrodes formed on the same surface or on opposite surface of the ceramic plate. This type of the sensor relies on the excellent hygroscopicity generally exhibited by the metal oxide ceramic. The metal oxide ceramic exhibits significant variation in electric resistance in response to the variation of humidity in the surrounding atmosphere. It is supposed that the variation in electric resistance of the metal oxide ceramic is caused by the movement of protons in the H.sub.2 O molecule adsorbed on the surface and on the wall of porosity of the metal oxide ceramic.
However, the humidity-resistance characteristics of this moisture sensor change as time passes because of the adsorption of contaminants such as oil mist, powdered dust, miscellaneous gases and so on onto and into the ceramic as well as the chemisorption occurring between the metal oxide ceramic and part of H.sub.2 O molecule adsorbed thereon. In the worst case the moisture sensor would not even exhibit humidity-resistance characteristics.
To eliminate the above-mentioned defect, a method which heats the ceramic at a high temperature so as to desorb the oil mist, powdered dust, miscellaneous gases and H.sub.2 O molecule from the ceramics was employed.
In this method, however, the effect of heating is not enough when the temperature of heat is less than 400.degree. C. Therefore, a great deal of electric power is required to effectively heat the moisture sensor and it is not efficient to apply this method to general electronic control circuits. Further, the material disposed around or on which the moisture sensor is mounted must be comprised of an incombustible material. Still further, the moisture sensitive element has to be heated every 30-60 minutes so as to desorb the contaminants. Further, since the moisture sensor cannot be operated during the heating and cooling process, it cannot monitor the humidity continuously if heating is used to remove contaminants.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide a moisture sensitive element in which the humidity-resistance characteristics do not significantly change as time passes.
In accordance with the preferred embodiment of this invention, the moisture sensitive element includes an improved moisture sensing element which exhibits significantly better and more consistent response in electric resistance variations in response to variations in relative humidity. A predetermined amount of phosphorus or sulfur is incorporated into the porous metal oxide ceramic and adhered thereto and is thus supported by the ceramic material. The phosphorus or sulfur can be applied either in a pure form or an oxide form. Further, the moisture sensitive element made according to this composition exhibits stable characteristics even over a relatively long lapse of time.

BRIEF DESCRIPTION OF THE DRAWINGS
This invention can be more fully understood from the following detailed description when taken in connection with reference to the accompanying drawing, in which:
FIG. 1A shows a plan view of a preferred embodiment of the invention;
FIG. 1B shows a section of the device taken along the line 1B--1B of FIG. 1A looking in the direction of the arrows;
FIG. 2 illustrates a graph showing relationship between the humidity and electric resistance of the moisture sensitive element according to the present invention which the phosphorus is supported by a ZnO ceramics body, and a prior art moisture sensitive element, respectively, in which a and b are the initial values, and a' and b' are the values of 500 hours after;
FIG. 3 illustrates a graph showing relationship between the humidity and electric resistance of the moisture sensitive element according to the present invention which the phosphorus is supported by an Fe.sub.2 O.sub.3 layer, and a prior art moisture sensitive element, respectively, in which a and b are the initial values, and a' and b' are the values of 500 hours after;
FIGS. 4 to 8, 9 to 12, and 13 to 16 illustrate graphs showing the relationship between the humidity and electric resistance of moisture sensitive elements produced according to the present invention which the phosphorus is supported by a ceramic body having ZnO, SnO.sub.2 and Cr.sub.2 O.sub.3 as a principal component, and prior art moisture sensitive elements, respectively, in which a and b are the initial values, and a' and b' are the values of 1000 hours after.

DESCRIPTION OF THE PREFERRED EXEMPLARY EMBODIMENTS
This invention is based on the discovery that the humidity-resistance characteristics of the moisture sensitive element comprised of the porous metal oxide ceramic on which at least either phosphorus (hereinafter P) or sulfur (hereinafter S) is supported, at least in a pure form or in an oxide form does not significantly change even after a long period of time in comparison with its initial characteristics.
It is not fully understood why the moisture sensitive element of the present invention shows such an excellent retention of its characteristics but it is assumed that the surface of the metal oxide ceramic is reformed to a stable property with respect to moisture.
In the moisture sensitive element of the present invention, the amount of P or S supported in pure form i.e., elemental phosphorus or sulfur, is present in the range of about 0.1 to about 2.0 percent by weight. However, the phosphorus or sulfur may also be in the form of an oxide. Further, both phosphorus and sulphur can be combined and incorporated into or supported on the ceramic substrate and in this instance, as well, the amount of the combination of phosphorus and sulphur can also range from about 0.1 to about 2.0 weight percent. However, when the amount of P or S supported is less than about 0.1 weight percent, the humidity-resistance characteristics are not improved because the amount of adsorption of P or S on the surface of the ceramic is not sufficient. Likewise, when the amount of P or S supported is in excess of about 2.0 weight percent, the electric resistance of the moisture sensitive element elevates too high for the measurement of the resistance.
In the moisture sensitive element of the invention, any porous metal oxide ceramic having the humidity-resistance characteristics may be employed. For example, ZnO, Fe.sub.2 O.sub.3, SnO.sub.2, MgO, Cr.sub.2 O.sub.3, BaO, TiO.sub.2, Fe.sub.3 O.sub.4, MgO.Cr.sub.2 O.sub.3, BaO.TiO.sub.2 or MnO.Fe.sub.2 O.sub.3, or another compounded oxide which other oxide is added to the above mentioned oxide is usually used.
The following compounded oxides containing ZnO as the main element exhibit excellent humidity-resistance characteristics when at least either P or S is supported by them. The compounded oxide comprises about 70 to about 99 mole percent of ZnO and about 1 to about 30 mole percent of at least one material selected from the group consisting of MgO, CaO, CoO and MnO, about 40 to about 99 mole percent of ZnO and about 1 to about 60 mole percent of at least one material selected from the group consisting of TiO.sub.2, SnO.sub.2, ZrO.sub.2 and SiO.sub.2, about 60 to about 90 mole percent of ZnO and about 10 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3, about 60 to about 99 mole percent of ZnO and about 1 to about 40 mole percent of at least either Cr.sub.2 O.sub.3 or Fe.sub.2 O.sub.3, or about 85 to about 95 mole percent of ZnO and about 5 to about 15 mole percent of V.sub.2 O.sub.5.
The following compounded oxides containing SnO.sub.2 as the main element also exhibit excellent humidity-resistance characteristics when at least either P or S is supported by them. The compounded oxide is comprised of about 50 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 50 mole percent of at least one material selected from the group consisting of MgO, CaO, CoO, MnO, SrO, NiO and CuO, about 60 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3, about 60 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 40 mole percent of at least one material selected from the group consisting of Al.sub.2 O.sub.3, Ga.sub.2 O.sub.3 and In.sub.2 O.sub.3, or about 75 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 25 mole percent of at least one material selected from the group consisting of V.sub.2 O.sub.5, Nb.sub.2 O.sub.5 and Ta.sub.2 O.sub.5.
Further, the following compounded oxides containing Cr.sub.2 O.sub.3 as the main element also exhibit excellent humidity-resistance characteristics when either P or S is supported by them. The compounded oxide is comprised of about 30 to about 80 mole percent of Cr.sub.2 O.sub.3 and about 20 to about 70 mole percent of at least one material selected from the group consisting of MgO, NiO, CoO and MnO, about 40 to about 80 mole percent of Cr.sub.2 O.sub.3 and about 20 to about 60 mole percent of at least one material selected from the group consisting of TiO.sub.2, SnO.sub.2, ZrO.sub.2 and SiO.sub.2, about 60 to about 90 mole percent of Cr.sub.2 O.sub.3 and about 10 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3, about 70 to about 90 mole percent of Cr.sub.2 O.sub.3 and about 10 to about 30 mole percent of at least one material selected from the group consisting of V.sub.2 O.sub.5, Nb.sub.2 O.sub.5 and Ta.sub.2 O.sub.5.
When the content of each element in these compounded oxides is out of the above-mentioned range, the electric resistance of the ceramics elevates so high (about over 5000 K.OMEGA.) that the variation of electric resistance of the ceramic reduced as compared with the variation of humidity. As a result, the moisture sensitive element cannot be put to practical use. Further, the compounded oxides within the above composition ranges have excellent sintering properties and mechanical strength.
The moisture sensitive element of this invention may be prepared in the following manner. Raw material oxides accurately weighed out in prescribed amount are mixed together with, for example, ethyl alcohol or ethylene glycol in a ball mill and then dried. The mixed oxides are calcined at 700 degrees to 1000 degrees C. as occasion demands and pulverized into powder. The powder thus obtained is mixed with a binder such as polyvinyl alcohol (PVA) and liquid paraffin, and the mixture is shaped under a pressure of about 500 to 2000 kg/cm.sup.2, into, for example, a plate having a width of 10 mm, a length of 20 mm and a thickness of 1 mm. The plate is sintered at about 1000 degrees to 1300 degrees C. generally in air. During sintering, it is kept at a maximum temperature for 0.5 to 2 hours.
In this invention, the ceramic has to have a porous structure and preferably the integral distribution of the porosity of over 10 Angstroms in size is 0.1 to 0.002 cc/g to the weight (g) of the ceramic. Since the porous structure may be obtained under the condition which, for example, the grain size of raw material oxide is 0.1 to 2.0 .mu.m, the shaping pressure is 500 to 2000 kg/cm.sup.2, the sintering temperature, 1000 to 1300 degrees C. and the sintering time is 0.5 to 2 hours.
A pair of electrodes are formed on the same surface or each opposite surface of the ceramic prepared as above by painting a conductive paste such as a gold paste, a platinum paste, a ruthenium oxide paste or a carbon paste on the ceramic and then burning it together. Finally, the pure form and/or oxide form of at least either P or S is supported by the ceramics. Either P or S may be supported by the ceramic in the following manner. A solution containing either P or S is impregnated into the ceramics and then decomposed by heat. Either the pure form or the oxide of either P or S in the solution is retained on the surface of the ceramic or on the walls of pores of the ceramic by the thermal decomposition in the heat treatment. The solution comprises, for example, organic phosphorous acid solution such as triethyl phosphate, trimethyl phosphate, tributyl phosphate, tri-p-cresyl phosphate and tri-o-cresyle phosphate, inorganic phosphorous acid solution such as phosphoric acid, phosphorous acid and pyrophosphoric acid, or organic sulfur solution such as ethyl sulfide, vinyl sulfide, phenyl sulfide, benzyl sulfide, methyl sulfide, triethylphosphine sulfide and diethyl sulfide. These solutions may be mixed or used singly.
It is preferable that the impregnation of the solution is carried out under a reduced pressure or a vacuum to uniformly impregnate the solution into even the center of the ceramic.
The ceramic thus obtained is thereafter heated. The temperature must be about the temperature of thermal decomposition of the solution. However, the upper limit of the temperature is 700 degrees C., preferably 550 degrees C. When the temperature is over 700 degrees C. the effect of supporting is not enough because P or S supported by the ceramic is vaporized or coagulated. Conversely, when the temperature is too low, the effect of supporting is not also enough because P or S cannot adhere to the ceramic.
The moisture sensitive element of the present invention also may be produced by supporting P or S by a metal oxide layer formed on a substrate such as an alumina or magnesia by the thick film method, for example, sputtering vacuum evaporation.
The moisture sensitive element of the present invention constructed as above has excellent humidity-resistance characteristics. Namely, the change of the humidity resistance characteristics with passage of time is very small so that continuous and reliable monitoring of humidity is possible.
This invention will be more clearly understood with reference to the following exemplary Examples.
EXAMPLE 1
Powder of ZnO with the particle size of 0.1 to 2.0 .mu.m was dried at 150 degrees C. for two hours and then mixed with 5 percent polyvinyl alcohol of 8 weight percent for about 20 minutes by mixer. The mixture thus obtained was placed in a cylinder and a pressure of 1000 kg/cm.sup.2 at about 25 degrees C. was applied to make a ceramic disc.
The ceramic disc was heated in an electric furnace at 1100 degrees C. for an hour and then ground by silicon abrasives of #3000. Thus, a ceramic disc having a diameter of 10 mm and a thickness of 1.0 mm was obtained as shown in FIG. 1A at 20. This ceramic disc 20 had 0.050 cc/g of the integral distribution of pores of over 37 Angstroms in size. A gold paste was spread on both surfaces of disc 20 and then gold mesh type electrodes 22 and 22' having the diameter of 8.0 mm were formed by baking at 750 degrees C.
The ceramic disc was steeped in triethyl phosphate including P of 18 weight percent at 10.sup.-3 Torr for 2 hours and was dried at 100 degrees C. for an hour. The ceramic disc thus obtained was heated in an electric furnace at 550 degrees C. for half an hour. The moisture sensitive element prepared as above was found in the chemical analysis that P supported by the ceramic was 0.8 weight percent to the weight of the ceramic.
Copper lead lines 24 and 26 were connected to the gold electrodes 22 and 22', respectively and an impedance measuring circuit was connected to the copper lines. The relationship between relative humidity (percent) and electric resistance (K.OMEGA.), which are initial humidity-resistance characteristics, were then measured under a constant temperature and humidity. The result is shown in FIG. 2 and Example 1 of Table 1. The humidity-resistance characteristics were measured again after 500 hours and the result is also shown in FIG. 2 and Example 1 of Table 1. In FIG. 2 curve "a" presents the initial characteristics while curve "a'" presents the characteristics after 500 hours of use.
Table 1 shows the initial electric resistance values R.sub.1 and R.sub.2 under the relative humidity of 30 percent and 90 percent, respectively, the electric resistance values R.sub.1 ', and R.sub.2 ' of 500 hours after under the relative humidity of 30 percent and 90 percent, respectively, and the change rate (R.sub.1 '-R.sub.1)/R.sub.1 .times.100 and (R.sub.2 '-R.sub.2)/R.sub.2 .times.100.
As a comparison, the humidity-resistance characteristics of a prior art element formed of ZnO ceramic by which P was not supported are also shown in FIG. 2 and control 1 of Table 1. In FIG. 2a curve "b" presents the initial characteristics and a curve "b'" presents the characteristics of 500 hours after.
As is apparent from the above results, the humidity-resistance characteristics of the prior art element exhibit a great change with passage of time. However, that of the moisture sensitive element of the present invention does not significantly change with passage of time. Therefore, the moisture sensitive element of the present invention has a great reliability when used in continuous monitoring applications.
EXAMPLE 2
A ZnO ceramic disc was made in the same manner as in Example 1. S was supported by the ZnO ceramic disc in the same manner as Example 1 except for use of 35 weight percent ethyl sulfide as an impregnation solution. The moisture sensitive element thus obtained had 0.9 weight percent of S.
In the same manner as Example 1, the humidity-resistance characteristics of the disc initially and after 500 hours were measured. The result was shown in Example 2 of Table 1.
EXAMPLES 3 TO 16
A plurality of moisture sensitive elements, on which either P or S was supported by ceramic discs made of metal oxide shown in EXAMPLES 3 to 16 of Table 1, were manufactured, and several kinds of moisture sensitive elements (controls 2 to 8) on which neither P nor S was supported by the ceramic disc were manufactured. The characteristics of the example elements and control elements were measured and are as shown in Table 1.
As shown in Table 1 and FIG. 2, according to the present invention the rate of moisture sensitive variation is very small so that the continuous and reliable monitoring of humidity is possible.
EXAMPLES 17 TO 23
A plurality of moisture sensitive elements, on which both P and S were supported by the ceramic discs made of the metal oxide shown in EXAMPLES 17 to 23 of Table 2, were made again in the same manner as in Example 1 except that the impregnation solution was changed to a mixture of triethyl phosphate containing P of 18 weight percent and ethyl sulfide containing S of 35 weight percent (mixed rate: 1:1).
The amount of P and S supported by the metal oxide ceramic were equal to each other.
The characteristics of the moisture sensitive elements were measured, and are shown in Table 2.
As Table 2 shows, the rate of electric resistance variation is very small.
EXAMPLE 24
A sintered alumina having a length of 20 mm, a width of 10 mm and a thickness of 0.5 mm was prepared. A pair of interdigital metal electrodes were formed on the sintered alumina. On the thick film type moisture sensitive element thus prepared, P was supported, and the characteristics were measured. The results are set forth in Example 24 of FIG. 3 and Table 3. As a comparison, the characteristics of an element on which P is not supported were measured, and are also shown in control 9 of FIG. 3 and Table 3. As FIG. 3 and Table 3 shows, the rate of moisture sensitive variation of the element of the invention is small.
EXAMPLES 25 TO 132
The moisture sensitive elements, which satisfy the specification as shown in Examples 25 to 132 and controls 10 to 67 of Table 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 and 28, were made in the same manner as in Example 1.
The humidity-resistance characteristics of these moisture sensitive elements were measured, and are shown in Tables 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27 and 29 and the characteristics of Examples 25, 34, 46, 52, 59, 63, 74, 83, 92, 100, 109, 117 and 125 and controls 10, 15, 20, 24, 29, 33, 37, 41, 45, 49, 54, 59 and 64 are shown in FIGS. 4 to 16.
From these results it is clear that moisture sensitive elements can be formed using either ZnO, SnO.sub.2 or Cr.sub.2 O.sub.3 as the base element forming the porous metal oxide ceramic on which either P or S was supported. Each form exhibited excellent humidity resistance characteristics and the rate of moisture sensitive variation was very small.
Exemplary structured formed using ZnO, SnO.sub.2 and Cr.sub.2 O.sub.3 as the base material for the porous ceramic are as follows:
(1) ZnO as the porous metal oxide ceramic with various compounded oxides as follows:
(a) about 70 to about 99 mole percent of ZnO and about 1 to about 30 mole percent of at least one material selected from the group consisting of MgO, CaO, CoO and MnO,
(b) about 40 to about 99 mole percent of ZnO and about 1 to about 60 mole percent of at least one material selected from the group consisting of TiO.sub.2, SnO.sub.2, ZrO.sub.2 and SiO.sub.2,
(c) about 60 to about 90 mole of ZnO and about 10 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3,
(d) about 60 to about 99 mole percent of ZnO and about 1 to about 40 mole percent of at least either Cr.sub.2 O.sub.3 or Fe.sub.2 O.sub.3, or
(e) about 85 to about 90 mole percent of ZnO and about 5 to about 15 mole percent of V.sub.2 O.sub.5.
(2) SnO.sub.2 as the porous metl oxide ceramic with various compounded oxides as follows:
(a) about 50 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 50 mole percent of at least one material selected from the group consisting of MgO, CaO, CoO, MnO, SrO, NiO and CuO,
(b) about 60 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3,
(c) about 60 to about 99.9 mole percent of SnO.sub.2 and about 0.1 to about 40 mole percent of at least one material selected from the group consisting of Al.sub.2 O.sub.3, Ga.sub.2 O.sub.3 and In.sub.2 O.sub.3, or
(d) about 75 to about 99.5 mole percent of SnO.sub.2 and about 0.1 to about 25 mole percent of at least one material selected from the group consisting of V.sub.2 O.sub.5, Nb.sub.2 O.sub.5 and Ta.sub.2 O.sub.5.
(3) Cr.sub.2 O.sub.3 as the porous metal oxide ceramic with various compounded oxides as follows:
(a) about 30 to about 80 mole percent of Cr.sub.2 O.sub.3 and about 20 to about 70 mole percent of at least one material selected from the group consisting of MgO, NiO, CoO and MnO,
(b) about 40 to about 80 mole percent of Cr.sub.2 O.sub.3 and about 20 to about 60 mole percent of at least one material selected from the group consisting of TiO.sub.2, SnO.sub.2, ZrO.sub.2 and SiO.sub.2,
(c) about 60 to about 90 mole percent of Cr.sub.2 O.sub.3 and about 10 to about 40 mole percent of at least either WO.sub.3 or MoO.sub.3, or
(d) about 70 to aout 90 mole percent of Cr.sub.2 O.sub.3 and about 10 to about 30 mole percent of at least one material selected from the group consisting of V.sub.2 O.sub.5, Nb.sub.2 O.sub.5 and Ta.sub.2 O.sub.5.
As described above, the moisture sensitive element according to the present invention has the excellent humidity-resistance characteristics and that the rate of moisture sensitive variation is very small.
While in many changes and modifications in the above-described embodiments can, of course, be carried out without departing from the scope of the present invention, that scope is intended to be limited only by the scope of the appended claims.
TABLE 1__________________________________________________________________________COMPOSITIONOF MOISTURE INITIAL 500 HOURS AFTER RATE OF VARIATIONSENSITIVE Supporting Amount R.sub.1 R.sub.2 R.sub.1 R.sub.2 ' (R.sub.1 ' - R.sub.1)/R.sub .1 (R.sub.2 ' - R.sub.2)/R.sub.2ELEMENT Material (wt %) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (%) (%)__________________________________________________________________________Example 1 ZnO P 0.8 3200 45 3600 48 +12.5 +6.7Example 2 ZnO S 0.9 1800 24 2068 26 +14.9 +8.3Example 3 Fe.sub.2 O.sub.3 P 0.6 2200 30 2150 29 -2.3 -3.3Example 4 SnO.sub.2 " 0.7 1250 98 1290 96 13.2 -2.0Example 5 Cr.sub.2 O.sub.3 " " 18300 290 18000 265 -1.6 -8.6Example 6 Fe.sub.3 O.sub.4 " 0.6 1150 85 1170 93 +1.7 +9.4Example 7 MgO.Cr.sub.2 O.sub.3 " 0.7 5100 270 5100 255 0 - 5.6Example 8 BaO.TiO.sub.2 " 0.8 920 38 900 40 -2.2 +5.6Example 9 MnO.Fe.sub.2 O.sub.3 " " 3550 720 3470 680 -2.3 -5.6Example 10 Fe.sub.2 O.sub.3 S 0.7 1580 44 1660 46 +5.1 +4.5Example 11 SnO.sub.2 " 0.8 875 21 900 22 12.9 14.8Example 12 Cr.sub.2 O.sub.3 " " 17700 205 17300 195 2.3 -4.9Example 13 Fe.sub.3 O.sub.4 " " 980 90 1020 91 +4.1 +1.1Example 14 MgO.Cr.sub.2 O.sub.3 " " 4000 250 5100 265 +4.1 +6Example 15 BaO.TiO.sub.2 " 0.9 640 32 610 28 -1.7 -12.5Example 16 MnO.Fe.sub.2 O.sub.3 " " 3500 640 3350 600 -4.3 -6.3Control 1 ZnO -- -- 2100 43 5200 720 +148 +1574Control 2 Fe.sub.2 O.sub.3 -- -- 1300 50 1100 280 -15.4 +460Control 3 SnO.sub.2 -- -- 980 115 760 195 -22.4 +69.6Control 4 Cr.sub.2 O.sub.3 -- -- >20000 230 >20000 1200 -- +422Control 5 Fe.sub.3 O.sub.4 -- -- 1070 65 2120 143 1981 +120Control 6 MgO.Cr.sub.2 O.sub.3 -- -- 5500 300 >20000 1000 >1264 +233Control 7 BaO.TiO.sub.2 -- -- 660 23 1210 85 +83.3 +270Control 8 MnO.Fe.sub.2 O.sub.3 -- -- 4350 1020 5600 3100 +28.7 +204__________________________________________________________________________
TABLE 2__________________________________________________________________________COMPOSITIONOF MOISTURE RATIO SUPPORTING INITIAL 500 HOURS AFTER RATE OF THE VARIATIONSENSITIVE OF AMOUNT R.sub.1 R.sub.2 R.sub.1 ' R.sub.2 ' (R.sub.1 ' - R.sub.1)/R.sub .1 (R.sub.2 ' - R.sub.2)/R.sub.2ELEMENT P & S (wt %) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (%) (%)__________________________________________________________________________Example 17 ZnO 1 0.8 2800 40 2850 43 11.8 17.5Example 18 Fe.sub.2 O.sub.3 " 0.7 2300 45 2150 41 -6.5 -8.9Example 19 SnO.sub.2 " " 1070 85 1200 78 112.1 -8.2Example 20 Cr.sub.2 O.sub.3 " " 16000 350 14300 310 -10.6 -11.4Example 21 Fe.sub.3 O.sub.4 " " 1200 80 1310 85 19.2 +6.3Example 22 MgO.Cr.sub.2 O.sub.3 " 0.8 6200 215 6450 220 +4.0 +2.3Example 23 MnO.Fe.sub.2 O.sub.3 " " 4030 920 3900 830 -3.2 -9.8__________________________________________________________________________
TABLE 3__________________________________________________________________________COMPOSITIONOF MOISTURE INITIAL 500 HOURS AFTER RATE OF THE VARIATIONSENSITIVE SUPPORTING AMOUNT R.sub.1 R.sub.2 R.sub.1 ' R.sub.2 ' (R.sub.1 ' - R.sub.1)/R.sub .1 (R.sub.2 ' - R.sub.2)/R.sub.2ELEMENTS MATERIAL (Wt %) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (k.OMEGA.) (%) (%)__________________________________________________________________________Example 24 Fe.sub.2 O.sub.3 P 0.6 2100 25 2300 27 +9.5 +8.0Control 9 Fe.sub.2 O.sub.3 -- -- 880 41 780 200 -11.4 +388__________________________________________________________________________
TABLE 4__________________________________________________________________________ SINTER- SHAPING ING SINTER- HEATING PRES- TEMPER- ING CONSIS- TEMPER-COMPOSITION SURE ATURE TIME SOLU- TENCY ATUREZnO CaO CoO MgO MnO BINDER (Kg/cm.sup.2) (.degree. C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 25 86.5 13.5 -- -- -- PVA 1,000 1100 2 Triethyl 18 550 PhosphateExample 26 " " -- -- -- " " " " Ethyl 35 " SulfideExample 27 99.4 0.6 -- -- -- " " " " Triethyl 18 550 PhosphateExample 28 93.5 6.5 -- -- -- " " " " " " "Example 29 78.8 21.2 -- -- -- " " " " " 20 "Example 30 89.0 -- -- 11.0 -- " " " " " " "Example 31 85.0 -- 9.8 5.2 -- " " " " " " "Example 32 77.6 6.9 5.1 5.5 4.9 " " " " " " "Example 33 89.0 -- -- 11.0 -- " " " " Ethyl 35 " SulfideControl 10 86.5 13.5 -- -- -- " " " " -- --Control 11 99.7 0.3 -- -- -- " " " " Triethyl 18 550 PhosphateControl 12 70.5 29.5 -- -- -- " " " " " " "Control 13 86.5 13.5 -- -- -- " " " " " " 700Control 14 89.0 -- -- 11.0 -- " " " " " " "__________________________________________________________________________
TABLE 5__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R.sub.1 ' R.sub.2 'ZnO CaO CoO MgO MnO MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.__________________________________________________________________________Example 25 8.0 20 -- -- -- P 0.9 3200 45 3700 49Example 26 " " -- -- -- S 1.0 4900 87 5100 91Example 27 99.0 1.0 -- -- -- P 0.9 4600 390 4800 420Example 28 90 10 -- -- -- " " 2700 190 2900 220Example 29 70 30 -- -- -- " " 6500 240 6800 280Example 30 80 -- -- 20 -- " " 4300 82 4500 84Example 31 " -- 10 10 -- " " 3700 67 3900 70Example 32 70 10 5 " 5 " " 7700 310 7900 330Example 33 80 -- -- 20 -- S 1.0 5200 69 5300 71Control 10 " 20 -- -- -- -- -- 1060 35 5800 230Control 11 99.5 0.5 -- -- -- P 0.9 5900 870 6100 900Control 12 60 40 -- -- -- " " 25000 3300 26000 3900Control 13 80 20 -- -- -- " " 2300 49 1900 240Control 14 " -- -- 20 -- " " 4600 95 7800 540__________________________________________________________________________
TABLE 6__________________________________________________________________________ SINTER- SHAPING ING SINTER HEATING PRES- TEMPER- ING CONSIS- TEMPER-COMPOSITION BIND- SURE ATURE TIME SOLU- TENCY ATUREZnO TiO.sub.2 SnO.sub.2 ZrO.sub.2 SiO.sub.2 ER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.__________________________________________________________________________ C.)Example 34 70.4 29.6 -- -- -- PVA 1,000 1200 2 Triethyl 18 500 PhosphateExample 35 " " -- -- -- " " " " Ethyl 35 " SulfideExample 36 99.0 1.0 -- -- -- " " " " Triethyl 18 500 PhosphateExample 37 80.3 19.7 -- -- -- " " " " " " "Example 38 60.4 39.6 -- -- -- " " " " " " "Example 39 55.7 -- 44.3 -- -- " " " " " " "Example 40 60.7 -- -- 39.3 -- " " " " " " "Example 41 76.0 -- -- -- 24.0 " " " " " " "Example 42 64.7 18.2 17.1 -- -- " " " " " " "Example 43 54.1 8.9 16.7 13.6 6.7 " " " " " " "Example 44 55.7 -- 44.3 -- -- " " " " Ethyl 35 " SulfideExample 45 64.7 18.2 17.1 -- -- " " " " " " "Control 15 70.4 29.6 -- -- -- " " " " -- -- --Control 16 99.5 0.5 -- -- -- " " " " Triethyl 18 500 PhosphateControl 17 30.4 69.6 -- -- -- " " " " " " "Control 18 70.4 29.6 -- -- -- " " " " " " 700Control 19 64.7 18.2 17.1 -- -- " " " " " " "__________________________________________________________________________
TABLE 7__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R.sub.1 ' R.sub.2 'ZnO TiO.sub.2 SnO.sub.2 ZrO.sub.2 SiO.sub.2 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 34 70 30 -- -- -- P 0.8 1900 60 1950 65Example 35 " " -- -- -- S 0.9 2200 80 2300 90Example 36 99 1 -- -- -- P 0.8 3200 210 3300 230Example 37 80 20 -- -- -- " " 2500 105 2600 110Example 38 60 40 -- -- -- " " 2100 120 2200 130Example 39 70 -- 30 -- -- " " " 80 " 90Example 40 " -- -- 30 -- " " 2400 90 2500 100Example 41 " -- -- -- 30 " " 2900 140 2900 145Example 42 " 20 10 -- -- " " 1800 45 1900 55Example 43 60 10 " 10 10 " " 2300 100 2100 110Example 44 70 -- 30 -- -- S " 2600 " 2800 "Example 45 " 20 10 -- -- " " 2100 80 2200 90Control 15 " 30 -- -- -- -- 1250 10 3400 135Control 16 99.5 0.5 -- -- -- P 0.8 4700 560 5000 570Control 17 30 70 -- -- -- " " 3700 400 3800 420Control 18 70 30 -- -- -- " " 1600 30 2900 90Control 19 " 20 10 -- -- " " 1700 50 2800 120__________________________________________________________________________
TABLE 8__________________________________________________________________________ SINTERING HEATING SHAPING TEMPERA- SINTERING CONSIS- TEMPERA-COMPOSITION PRESSURE TURE TIME TENCY TUREZnO WO.sub.3 MoO.sub.3 BINDER (Kg/cm.sup.2) (.degree.C.) (hr) SOLUTION (wt %) (.degree.C.)__________________________________________________________________________Example 46 69.3 -- 30.7 PVA 1,000 1000 1 Triethyl 18 550 PhosphateExample 47 " " " " " " Ethyl 35 " SulfideExample 48 83.6 -- 16.4 " " " " Triethyl 18 550 PhosphateExample 49 45.9 -- 55.1 " " " " " " "Example 50 58.4 41.6 -- " " " " " " "Example 51 63.4 22.6 14.0 " " " " " " "Control 20 69.3 30.7 " " " " -- -- --Control 21 91.5 -- 8.5 " " " " Triethyl 18 550 PhosphateControl 22 40.9 -- 59.1 " " " " " " "Control 23 69.3 -- 30.7 " " " " " " 700__________________________________________________________________________
TABLE 9__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R.sub.1 ' R.sub.2 'ZnO WO.sub.2 MoO.sub.3 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 46 80 -- 20 P 0.8 2700 160 2800 180Example 47 " -- " S 0.9 3000 140 3100 160Example 48 90 -- 10 P 0.8 3400 290 3600 310Example 49 60 -- 40 " " 3700 340 3900 360Example 50 80 20 -- " " 2400 210 2500 220Example 51 " 10 10 " " 2600 190 2800 210Control 20 " 20 -- -- 2200 100 6400 460Control 21 95 -- 5 P 0.8 6700 850 6800 860Control 22 55 -- 45 " " 4400 560 4600 600Control 23 80 -- 20 " " 2500 130 4200 340__________________________________________________________________________
TABLE 10__________________________________________________________________________ SINTERING HEATING SHAPING TEMPERA- SINTERING CONSIS- TEMPERA-COMPOSITION PRESSURE TURE TIME SOLU- TENCY TUREZnO Cr.sub.2 O.sub.3 Fe.sub.2 O.sub.3 BINDER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 52 82.8 17.2 -- PVA 1000 1200 2 Triethyl 18 550 PhosphateExample 53 " " -- " " " " Ethyl 35 " SulfideExample 54 98.1 1.9 -- " " " " Triethyl 18 " PhosphateExample 55 44.5 55.5 -- " " " " " 20 "Example 56 67.1 -- 22.9 " " " " " " "Example 57 67.6 15.8 16.6 " " " " " 16 "Example 58 " " " " " " " Diethyl 35 " SulfideControl 24 82.8 17.2 -- " " " " -- -- --Control 25 99.1 0.9 -- " " " " Ethyl 18 550 SulfideControl 26 39.6 60.4 -- " " " " " " "Control 27 82.8 17.2 -- - - - - - - 700Control 28 67.6 15.8 16.6 " " " " " " "__________________________________________________________________________
TABLE 11__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R'.sub.1 R'.sub.2ZnO Cr.sub.2 O.sub.3 Fe.sub.2 O.sub.3 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 52 90 10 -- P 0.8 2500 67 2600 72Example 53 90 10 -- S 0.9 2800 85 2900 100Example 54 99 1 -- P 0.8 3900 270 4300 310Example 55 60 40 -- P 0.7 3600 240 3700 270Example 56 80 -- 20 P 0.8 3200 120 3300 135Example 57 80 10 10 P 0.8 2300 45 2400 50Example 58 80 10 10 S 0.8 2500 110 2600 120Control 24 90 10 -- -- -- 1700 25 7300 185Control 25 99.5 0.5 -- S 0.8 5700 680 5900 730Control 26 55 45 -- S 0.8 4900 560 5000 580Control 27 90 10 -- S 0.7 2100 40 4200 320Control 28 80 10 10 S 0.7 1900 70 4500 390__________________________________________________________________________
TABLE 12__________________________________________________________________________ SINTERING HEATING SHAPING TEMPERA- SINTERING CON- TEMPERA-COMPOSITION PRESSURE TURE TIME SISTENCY TUREZnO V.sub.2 O.sub.3 BINDER (Kg/cm.sup.2) (.degree.C.) (hr) SOLUTION (wt %) (.degree.C.)__________________________________________________________________________Example 59 80.1 19.9 PVA 1,000 1100 0.5 Triethyl 18 550 PhosphateExample 60 80.1 19.9 " " " " Ethyl 35 SulfideExample 61 89.5 10.5 " " " " Triethyl 18 500 PhosphateExample 62 71.7 28.3 " " " " Triethyl 18 500 PhosphateControl 29 80.1 19.9 " " " " -- -- --Control 30 95.6 4.4 " " " " Triethyl 18 500 PhosphateControl 31 64.1 35.9 " " " " Triethyl 18 500 PhosphateControl 32 80.1 19.9 " " " " Triethyl 18 700 Phosphate__________________________________________________________________________
TABLE 13__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R'.sub.1 R'.sub.2ZnO V.sub.2 O.sub.5 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 59 90 10 P 0.8 3200 270 3200 280Example 60 90 10 S 0.9 3500 240 3600 240Example 61 95 5 P 0.8 5000 240 5100 250Example 62 85 15 P 0.8 4100 290 4200 310Control 29 90 10 -- -- 3000 100 6300 290Control 30 98 2 P 0.8 8000 900 8000 950Control 31 80 20 P 0.8 7500 800 7700 830Control 32 90 10 P 0.8 3000 260 4000 650__________________________________________________________________________
TABLE 14__________________________________________________________________________ Sintering Heating Shaping Temp- Sintering Con- Temp-COMPOSITION Pressure erature Time Solu- sistency eratureSnO.sub.2 MgO CaO CoO MnO SrO NiO CuO Binder (Kg/cm.sup.2) (.degree.C.) (hr) tion (wt (.degree.C.)__________________________________________________________________________Example 63 89.0 -- -- 11.0 -- -- -- -- PVA 1000 1200 2 Tri- 18 550 ethyl Phos- phateExample 64 89.0 -- -- 11.0 -- -- -- -- " " " " Ethyl 35 550 SulfideExample 65 99.95 -- -- 0.05 -- -- -- -- " " " " Tri- 18 500 ethyl Phos- phateExample 66 94.8 -- -- 5.2 -- -- -- -- " " " " Tri- " " ethyl Phos- phateExample 67 75.1 -- -- 24.9 -- -- -- -- " " " " Tri- " " ethyl Phos- phateExample 68 66.8 -- -- 33.2 -- -- -- -- " " " " Tri- " " ethyl Phos- phateExample 69 90.8 -- 3.8 -- 5.4 -- -- -- " " " " Tri- " " ethyl Phos- phateExample 70 82.8 3.2 -- -- -- 8.1 5.9 -- " " " " Tri- " " ethyl Phos- phateExample 71 83.7 -- 4.0 5.9 -- -- -- 6.4 " " " " Tri- " " ethyl Phos- phateExample 72 86.8 -- -- -- -- 7.5 -- 5.7 " " " " Ethyl 35 " SulfideExample 73 90.6 -- 3.8 -- -- -- 5.6 -- " " " " Ethyl " " SulfideControl 33 89.0 -- -- 11.0 -- -- -- -- " " " " -- --Control 34 57.3 -- -- 42.7 -- -- -- -- " " " " Tri- 18 500 ethyl Phos- phateControl 35 89.0 -- -- 11.0 -- -- -- -- " " " " Tri- " 700 ethyl Phos- phateControl 36 83.7 -- 4.0 5.9 -- -- -- 6.4 " " " " Tri- " " ethyl Phos- phate__________________________________________________________________________
TABLE 15__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R'.sub.1 R'.sub.2SnO.sub.2 MgO CaO CoO MnO SrO NiO CuO MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 63 80 -- -- 20 -- -- -- -- P 0.8 920 25 940 30Example 64 80 -- -- 20 -- -- -- -- S 0.9 1300 40 1400 50Example 65 99.9 -- -- 0.1 -- -- -- -- P 0.7 1200 35 1300 40Example 66 90 -- -- 10 -- -- -- -- " 0.8 960 30 980 40Example 67 60 -- -- 40 -- -- -- -- " " 1300 70 1400 80Example 68 50 -- -- 50 -- -- -- -- " " 2000 120 2200 140Example 69 80 -- 10 -- 10 -- -- -- " " 970 30 980 40Example 70 70 10 -- -- -- 10 10 -- " " 1100 70 1200 80Example 71 70 -- 10 10 -- -- -- 10 " " 1400 60 1500 80Example 72 80 -- -- -- -- 10 -- 10 S 0.9 1500 80 1600 90Example 73 80 -- 10 -- -- -- 10 -- " " 1600 100 1700 110Control 33 80 -- -- 20 -- -- -- -- -- 810 20 2300 62Control 34 40 -- -- 60 -- -- -- -- P 0.8 2900 340 3100 380Control 35 80 -- -- 20 -- -- -- -- " " 900 30 1500 90Control 36 70 -- 10 10 -- -- -- 10 " " 1300 50 2700 210__________________________________________________________________________
TABLE 16__________________________________________________________________________ HEATING SHAPING CONSIS- TEMPERA-COMPOSITION PRESSURE SINTERING SINTERING TENCY TURESnO.sub.2 WO.sub.3 MoO.sub.3 BINDER (Kg/cm.sup.2) (.degree.C.) (hr) SOLUTION (wt %) (.degree.C.)__________________________________________________________________________Example 74 85.4 14.6 -- PVA 1000 1200 2 Triethyl 18 550 PhosphateExample 75 85.4 14.6 -- " " " " Ethyl 35 " SulfideExample 76 99.8 0.2 -- " " " " Triethyl 18 " PhosphateExample 77 72.2 27.8 -- " " " " Triethyl " " PhosphateExample 78 60.3 39.7 -- " " " " Triethyl " " PhosphateExample 79 49.4 50.6 -- " " " " Triethyl " " PhosphateExample 80 90.4 -- 9.6 " " " " Triethyl " " PhosphateExample 81 76.3 14.6 9.1 " " " " Triethyl " " PhosphateExample 82 90.4 -- 9.6 " " " " Ethyl 35 " SulfideControl 37 85.4 14.6 -- " " " " -- -- --Control 38 39.4 60.6 -- " " " " Triethyl 18 550 PhosphateControl 39 85.4 14.6 -- " " " " Triethyl " 700 PhosphateControl 40 90.4 -- 9.6 " " " " Triethyl " " Phosphate__________________________________________________________________________
TABLE 17__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R'.sub.1 R'.sub.2SnO.sub.2 WO.sub.3 MoO.sub.3 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 74 90 10 -- P 0.7 2800 105 2900 120Example 75 90 10 -- S 0.9 2900 70 3000 80Example 76 99.9 0.1 -- P 0.7 3700 190 3900 200Example 77 80 20 -- " " 2300 70 2400 80Example 78 70 30 -- " " 2500 90 2600 100Example 79 60 40 -- " " 3000 140 3100 150Example 80 90 -- 10 " " 2200 90 2300 95Example 81 80 10 10 " " 1700 55 1800 60Example 82 90 -- 10 S " 3100 80 3200 90Control 37 90 10 -- -- -- 2100 86 3400 290Control 38 50 50 -- P -- 3400 390 3500 400Control 39 90 10 -- " -- 2400 80 3600 350Control 40 90 -- 10 " -- 2600 140 3800 560__________________________________________________________________________
TABLE 18__________________________________________________________________________ Sintering Heating Shaping Temp- Sintering Temp-Composition Pressure erature Time Consistency eratureSnO.sub.2 Al.sub.2 O.sub.2 Ga.sub.2 O.sub.3 In.sub.2 O.sub.3 Binder (Kg/cm.sup.2) (.degree.C.) (hr) Solution (wt %) (.degree.C.)__________________________________________________________________________Example 83 76.4 -- 23.6 -- PVA 1000 1200 12 Triethyl 18 500 PhosphateExample 84 76.4 -- 23.6 -- " " " " Ethyl 35 500 SulfideExample 85 99.9 -- 0.1 -- " " " " Triethyl 18 " PhosphateExample 86 79.0 -- 21.0 -- " " " " Triethyl " " PhosphateExample 87 65.3 -- 44.7 -- " " " " Triethyl " " PhosphateExample 88 54.8 -- 45.2 -- " " " " Triethyl " " PhosphateExample 89 68.5 -- -- 31.5 " 800 " " Triethyl " " PhosphateExample 90 80.7 6.8 12.5 -- " " " " Triethyl " " PhosphateExample 91 64.5 6.4 11.7 17.4 " 1000 " " Ethyl 35 " SulfideControl 41 76.4 -- 23.6 -- " " " " -- --Control 42 44.6 -- 55.4 -- " " " " Triethyl 18 500 PhosphateControl 43 76.4 -- 23.6 -- " " " " Triethyl " 700 PhosphateControl 44 68.5 -- -- 31.5 " " " " Triethyl " " Phosphate__________________________________________________________________________
TABLE 19__________________________________________________________________________ INITIAL 1,000 Hours AfterCOMPOSITION SUPPORTING AMOUNT R.sub.1 R.sub.2 R'.sub.1 R'.sub.2SnO.sub.2 Al.sub.2 O.sub.3 Ga.sub.2 O.sub.3 In.sub.2 O.sub.3 MATERIAL (wt %) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.) (K.OMEGA.)__________________________________________________________________________Example 83 80 -- 20 -- P 0.7 2200 65 2400 80Example 84 80 -- 20 -- S 1.1 2800 70 3000 80Example 85 99.9 -- 0.1 -- P 1.6 3400 95 3500 110Example 86 90 -- 10 -- " 1.2 2700 80 2900 100Example 87 70 -- 30 -- " 0.6 1300 40 1400 50Example 88 60 -- 40 -- " 0.5 980 60 990 65Example 89 80 -- -- 20 " 0.5 2900 90 3000 100Example 90 80 10 10 -- " 0.9 3200 80 3300 90Example 91 70 10 10 10 S 1.5 3400 100 3500 120Control 41 80 -- 20 -- -- -- 1700 20 6600 250Control 42 50 -- 50 -- P 0.5 300 90 310 115Control 43 80 -- 20 -- " 0.6 2100 45 1100 250Control 44 80 -- -- 20 " 0.7 2500 70 5100 310__________________________________________________________________________
TABLE 20__________________________________________________________________________ SIN- TERING HEATING SHAPING TEM- SIN- TEM- PRES- PERA- TERING CONSIS- PERA-COMPOSITION SURE TURE TIME SOLU- TENCY TURESnO.sub.2 V.sub.2 O.sub.5 Nb.sub.2 O.sub.5 Ta.sub.2 O.sub.5 BINDER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 92 88.2 11.8 -- -- PVA 1000 1200 2 Triethyl 18 550 PhosphateExample 93 " " -- -- " " " " Ethyl 35 " SulfideExample 94 99.9 0.1 -- -- " " " " Triethyl 18 550 PhosphateExample 95 76.8 23.2 -- -- " " " " Triethyl " " PhosphateExample 96 71.3 28.7 -- -- " " " " Triethyl " " PhosphateExample 97 83.6 -- 16.4 -- " " " " Triethyl " " PhosphateExample 98 75.5 -- -- 24.5 " " " " Triethyl " " PhosphateExample 99 72.9 11.0 16.1 -- " " " " Triethyl " " PhosphateControl 45 88.2 11.8 -- -- " " " " -- --Control 46 65.9 34.1 -- -- " " " " Triethyl 18 550 PhosphateControl 47 88.2 11.8 -- -- " " " " Triethyl " 700 PhosphateControl 48 83.6 -- 16.4 -- " " " " Triethyl " " Phosphate__________________________________________________________________________
TABLE 21__________________________________________________________________________ COMPOSITION SUPPORTING AMOUNT INITIAL 1,000 Hours After SnO.sub.2 V.sub.2 O.sub.5 Nb.sub.2 O.sub.5 Ta.sub.2 O.sub.5 MATERIAL (wt %) R.sub.1 (K.OMEGA.) R.sub.2 (K.OMEGA.) R'.sub.1 R'.sub.2 (K.OMEGA.)__________________________________________________________________________Example 92 90 10 -- -- P 0.6 2000 80 2200 90Example 93 90 10 -- -- S 1.0 4900 87 5100 91Example 94 99.9 0.1 -- -- P 1.2 1700 50 1800 60Example 95 80 20 -- -- P 0.5 2800 140 2900 150Example 96 75 25 -- -- P 0.4 3700 230 3900 250Example 97 90 -- 10 -- P 0.8 2400 90 2500 110Example 98 90 -- -- 10 P 1.0 2300 110 2400 120Example 99 80 10 10 -- P 0.7 3100 240 3200 260Control 45 90 10 -- -- -- -- 1600 27 2900 180Control 46 70 30 -- -- P 0.4 4400 580 4600 600Control 47 90 10 -- -- P 0.6 1800 70 3900 240Control 48 90 -- 10 -- P 0.8 2100 90 3800 230__________________________________________________________________________
TABLE 22__________________________________________________________________________ SHAPING SINTERING SIN- CON- HEATING PRES- TEMPERA- TERING SIS- TEMPERA-COMPOSITION BIND- SURE TURE TIME SOLU- TENCY TURECr.sub.2 O.sub.3 MgO NiO CoO MnO ER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 82.7 -- 17.3 -- -- PVA 1000 1300 2 Triethyl 18 550100 PhosphateExample 82.7 -- 17.3 -- -- " 1000 " " Ethyl 35 550101 SulfideExample 89.1 -- 10.9 -- -- " 2000 " " Triethyl 18 550102 PhosphateExample 67.0 -- 33.0 -- -- " 500 " " Triethyl 9 550103 PhosphateExample 46.5 -- 53.5 -- -- " 1000 " " Triethyl 18 550104 PhosphateExample 89.8 10.2 -- -- -- " 1500 " " Triethyl 18 550105 PhosphateExample 82.5 -- -- 17.5 -- " 1000 " " Triethyl 18 550106 PhosphateExample 82.9 -- 11.6 -- 5.5 " 1000 " " Triethyl 18 550107 PhosphateExample 89.8 10.2 -- -- -- " 2000 " " Diethyl 35 550108 SulfideControl 49 82.7 -- 17.3 -- -- " 1000 " " -- -- --Control 50 94.8 -- 5.2 -- -- " 2000 " " Triethyl 18 550 PhosphateControl 51 33.7 -- 66.3 -- -- " 800 " " Triethyl 18 550 PhosphateControl 52 82.6 -- 17.4 -- -- " 1000 " " Triethyl 18 700 PhosphateControl 53 82.5 -- -- 17.5 -- " 1000 " " Triethyl 18 700 Phosphate__________________________________________________________________________
TABLE 23__________________________________________________________________________ COMPOSITION SUPPORTING AMOUNT INITIAL 1,000 Hours After Cr.sub.2 O.sub.3 MgO NiO CoO MnO MATERIAL (wt %) R.sub.1 (K.OMEGA.) R.sub.2 (K.OMEGA.) R'.sub.1 R'.sub.2 (K.OMEGA.)__________________________________________________________________________Example 100 70 -- 30 -- -- P 0.8 2900 35 3100 45Example 101 70 -- 30 -- -- S 1.2 3400 60 3500 70Example 102 80 -- 20 -- -- P 0.7 4700 190 4900 200Example 103 50 -- 50 -- -- P 0.1 3200 60 3300 80Example 104 30 -- 70 -- -- P 0.6 3400 170 3600 180Example 105 70 30 -- -- -- P 2.0 3200 40 3400 50Example 106 70 -- -- 30 -- P 1.5 3400 60 3500 80Example 107 70 -- 20 -- 10 P 1.2 3200 45 3300 60Example 108 70 30 -- -- -- S 2.0 3600 90 3800 100Control 49 70 -- 30 -- -- -- -- 1900 13 3400 150Control 50 90 -- 10 -- -- P 0.3 8900 560 9200 600Control 51 20 -- 80 -- -- P 0.6 3800 420 3900 430Control 52 70 -- 30 -- -- P 1.0 2600 30 5100 150Control 53 70 -- -- 30 -- P 1.8 3100 45 3200 60__________________________________________________________________________
TABLE 24__________________________________________________________________________ SHAPING SINTERING SIN- CON- HEATING PRES- TEMPERA- TERING SIS- TEMPERA-COMPOSITION BIND- SURE TURE TIME SOLU- TENCY TURECr.sub.2 O.sub.3 TiO.sub.2 SnO.sub.2 ZrO.sub.2 SiO.sub.2 ER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 60.2 -- 39.8 -- -- PVA 1,000 1300 2 Triethyl 18 550109 PhosphateExample 60.2 -- 39.8 -- -- " " " " Ethyl 35 550110 SulfideExample 80.1 -- 19.9 -- -- " " " " Triethyl 18 550111 PhosphateExample 40.2 -- 59.8 -- -- " " " " Triethyl 18 550112 PhosphateExample 74.0 26.0 -- -- -- " " " " Triethyl 18 550113 PhosphateExample 62.5 -- 20.7 16.8 -- " " " " Triethyl 18 550114 PhosphateExample 68.4 -- 22.6 -- 9.0 " " " " Triethyl 18 550115 PhosphateExample 74.0 26.0 -- -- -- " " " " Ethyl 35 550116 SulfideControl 60.2 -- 39.8 -- -- " " " " -- -- --54Control 90.1 -- 9.9 -- -- " " " " Triethyl 18 55055 PhosphateControl 30.1 -- 69.9 -- -- " " " " Triethyl 18 55056 PhosphateControl 60.2 -- 39.8 -- -- " " " " Triethyl 18 70057 PhosphateControl 74.0 26.0 -- -- -- " " " " Triethyl 18 70058 Phosphate__________________________________________________________________________
TABLE 25__________________________________________________________________________ COMPOSITION SUPPORTING AMOUNT INITIAL 1,000 Hours After Cr.sub.2 O.sub.3 TiO.sub.2 SnO.sub.2 ZrO.sub.2 SiO.sub.2 MATERIAL (wt %) R.sub.1 (K.OMEGA.) R.sub.2 (K.OMEGA.) R'11 R'.sub.2 (K.OMEGA.)__________________________________________________________________________Example 109 60 -- 40 -- -- P 0.7 3500 120 3600 130Example 110 60 -- 40 -- -- S 0.8 3800 200 4000 210Example 111 80 -- 20 -- -- P 0.7 4400 190 4600 220Example 112 40 -- 60 -- -- P 0.7 2900 170 3100 180Example 113 60 40 -- -- -- P 0.7 4000 180 4100 200Example 114 60 -- 20 20 -- P 0.7 3200 140 3300 150Example 115 60 -- 20 -- 20 P 0.7 2900 170 3100 190Example 116 60 40 -- -- -- S 0.8 4100 160 4200 170Control 54 60 -- 40 -- -- -- -- 1700 80 6400 460Control 55 90 -- 10 -- -- P 0.7 8900 670 9200 690Control 56 30 -- 70 -- -- P 0.7 3400 360 3600 380Control 57 60 -- 40 -- -- P 0.7 2200 100 4900 620Control 58 60 40 -- -- -- P 0.7 3000 105 5300 450__________________________________________________________________________
TABLE 26__________________________________________________________________________ SHAPING SINTERING CON- HEATING COMPOSITION BIND- PRESSURE TEMPERA- SINTERING SOLU- SISTENCY TEMPERA- Cr.sub.2 O.sub.3 WO.sub.3 MoO.sub. 3 ER (Kg/cm.sup.2) TURE (.degree.C.) TIME (hr) TION (wt %) TURE__________________________________________________________________________ (.degree.C.)Example 117 72.4 27.6 -- PVA 1,000 1200 2 Triethyl 18 550 PhosphateExample 118 72.4 27.6 -- " " " " Ethyl 35 550 SulfideExample 119 85.5 14.5 -- " " " " Triethyl 18 550 PhosphateExample 120 60.5 39.5 -- " " " " Triethyl 18 550 PhosphateExample 121 49.6 50.4 -- " " " " Triethyl 20 550 PhosphateExample 122 80.9 -- 19.1 " " " " Triethyl 20 550 PhosphateExample 123 76.4 14.6 9.0 " " " " Triethyl 20 550 PhosphateExample 124 80.9 -- 19.1 " " " " Ethyl 35 550 SulfideControl 59 72.4 27.6 -- " " " " -- --Control 60 92.6 7.4 -- " " " " Triethyl 18 550 PhosphateControl 61 39.6 60.4 -- " " " " Triethyl 18 550 PhosphateControl 62 72.4 27.6 -- " " " " Triethyl 18 700 PhosphateControl 63 80.9 -- 19.1 " " " " Triethyl 18 700 Phosphate__________________________________________________________________________
TABLE 27__________________________________________________________________________ COMPOSITION SUPPORTING AMOUNT INITIAL 1,000 Hours After Cr.sub.2 O.sub.3 WO.sub.3 MoO.sub.3 MATERIAL (wt %) R.sub.1 (K.OMEGA.) R.sub.2 (K.OMEGA.) R'.sub.1 (K.OMEGA.) R'.sub.2__________________________________________________________________________ (K.OMEGA.)Example 117 80 20 -- P 0.8 1800 60 1900 75Example 118 80 20 -- S 0.9 2300 105 2400 120Example 119 90 10 -- P 0.8 2700 95 2800 100Example 120 70 30 -- P 0.7 2200 110 2300 120Example 121 60 40 -- P 0.7 3400 210 3600 220Example 122 80 -- 20 P 0.8 1900 90 2100 100Example 123 80 10 10 P 0.8 2000 70 2100 90Example 124 80 -- 20 S 0.8 2500 120 2600 130Control 59 80 20 -- -- -- 1000 23 2900 210Control 60 95 5 -- P 0.8 6700 450 6800 170Control 61 50 50 -- P 0.6 4800 480 5000 490Control 62 80 20 -- P 0.8 1700 45 3000 230Control 63 80 -- 20 P 0.8 2200 80 1700 310__________________________________________________________________________
TABLE 28__________________________________________________________________________ SHAPING SINTERING CON- HEATING PRES- TEMPERA- SINTERING SIS- TEMPERA-COMPOSITION BIND- SURE TURE TIME SOLU- TENCY TURECr.sub.2 O.sub.3 V.sub.2 O.sub.5 Nb.sub.2 O.sub.5 Ta.sub.2 O.sub.5 ER (Kg/cm.sup.2) (.degree.C.) (hr) TION (wt %) (.degree.C.)__________________________________________________________________________Example 77.0 23.0 -- -- PVA 1,000 1200 2 Triethyl 18 550125 PhosphateExample 77.0 23.0 -- -- " " " " Ethyl 35 550126 SulfideExample 88.3 11.7 -- -- " " " " Triethyl 18 500127 PhosphateExample 66.1 33.9 -- -- " " " " Triethyl 20 500128 PhosphateExample 69.6 -- 30.4 -- " " " " Triethyl 20 500129 PhosphateExample 57.9 -- -- 42.1 " " " " Triethyl 20 500130 PhosphateExample 73.1 10.9 16.0 -- " " " " Triethyl 20 500131 PhosphateExample 67.2 10.1 -- 22.7 " " " " Ethyl 18 500132 SulfideControl 77.0 23.0 -- -- " " " " -- -- --64Control 94.1 5.9 -- -- " " " " Triethyl 18 50065 PhosphateControl 55.6 44.4 -- -- " " " " Triethyl 18 50066 PhosphateControl 77.0 23.0 -- -- " " " " Triethyl 18 70067 Phosphate__________________________________________________________________________
TABLE 29__________________________________________________________________________ COMPOSITION SUPPORTING AMOUNT INITIAL 1,000 Hours After Cr.sub.2 O.sub.3 V.sub.2 O.sub.5 Nb.sub.2 O.sub.5 Ta.sub.2 O.sub.5 MATERIAL (wt %) R.sub.1 (K.OMEGA.) R.sub.2 (K.OMEGA.) R'.sub.1 R'.sub.2 (K.OMEGA.)__________________________________________________________________________Example 125 80 20 -- -- P 0.8 3200 100 3300 110Example 126 80 20 -- -- S 0.8 3400 95 3500 110Example 127 90 10 -- -- P 0.7 4900 130 5000 150Example 128 70 30 -- -- P 0.7 2900 140 3000 150Example 129 80 -- 20 -- P 0.7 3100 130 3200 140Example 130 80 -- -- 20 P 0.7 2700 120 2800 130Example 131 80 10 10 -- P 0.7 3100 130 320 140Example 132 80 10 -- 10 S 0.7 3300 170 3400 180Control 64 80 20 -- -- -- -- 2100 71 8200 210Control 65 95 5 -- -- P 0.7 9300 940 9500 960Control 66 60 40 -- -- P 0.7 3900 410 4000 440Control 67 80 20 -- -- P 0.7 2900 80 5700 370__________________________________________________________________________

Number	Date	Country
55-108242	Aug 1980	JPX
55-111608	Aug 1980	JPX
55-111613	Aug 1980	JPX
55-111615	Aug 1980	JPX
55-111619	Aug 1980	JPX

Number	Date	Country
54-31836	Oct 1979	JPX
55-49705	Dec 1980	JPX

Moisture sensitive element

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