Electrical resistors, electrical resistor paste and method for making the same

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a fixed chip resistor or a thick-film type electrical resistor provided in circuit boards and the like and, more particularly, to an electrical resistor capable of being obtained by sintering in a non-oxidizing atmosphere. The present invention also relates to a method for making such resistors.
2. Statement of the Prior Art
Electrical circuits of electronic equipment are generally constructed by mounting various electrical elements such as resistors, capacitors, diodes and transistors to circuit boards. With miniaturization of electronic equipment, however, much use has been made of circuit boards capable of increasing the density of such mounted electrical elements.
The resistors mounted to such circuit board include a thick-film resistor formed by printing and firing a paste of a resistor material directly onto a circuit, a fixed chip resistor made by forming such a thick-film resistor across a pair of electrode terminals of a rectangular ceramic chip, and the like.
Hitherto, such a thick-film resistor has generally been formed on a circuit board in the following manner. A paste of a conductor material such as Ag or Ag-Pd is applied and fired on the surface of an alumina substrate obtained by sintering at, e.g., about 1500.degree. C. Afterwards, a paste containing, e.g., RuO.sub.2 as the main material of the resistor is applied on that surface by means of screen printing, etc., followed by firing at 750.degree. to 850.degree. C. and, if required, adjustment of a resistance value by means of laser trimming, etc.
However, recent heavy demands for reductions in the weight, thickness, size and cost of electronic equipment, etc. have led to intensive studies for reducing in the size and cost of circuit boards.
Referring to concrete measures to meet the former size reduction, multilayered circuit boards deserve the first mention, and formed resistors the second mention. Known examples of multilayered circuit boards include a multilayered circuitry board obtained by laminating ceramic green sheets, each having a paste of a conductor material such as Ag or Ag-Pd printed thereon, and simultaneously sintering them at 800.degree. to 1100.degree. C. in the air, while known examples of the formed resistor include a multilayered with a formed resistor, obtained by printing a paste of a RuO.sub.2 base resistor material on a ceramic green sheet having said paste of a conductive material printed thereon, laminating such sheets, and then simultaneously sintering them.
Referring to concrete measures to achieve the latter cost reduction, multilayered circuitry boards have been put to practical use, and are obtained by using conductive materials based on inexpensive base metals such as Ni or Cu in place of those based on noble metals such as Ag or Ag-Pd, and sintering them simultaneously with green ceramic at 800.degree. to 1100.degree. C. in a neutral or reducing atmosphere to avoid any increase in resistance due to their oxidation, such as a nitrogen gas or a hydrogen-containing nitrogen gas. As disclosed in Japanese Patent Laid-Open (Kokai) Publication No. 56-153702 in particular, there are also known thick-film resistors, etc. which are obtained by applying a resistor material comprising MoSi.sub.2 -TaSi.sub.2 and glass on an alumina substrate including a copper (Cu) conductor, followed by a heat treatment.
Where it is intended to simultaneously reduce the size and cost of circuit boards, the RuO.sub.2 base resistor material undergoes a reducing reaction, when it is sintered simultaneously with green ceramic in a nitrogen gas or hydrogen-containing nitrogen atmosphere, and it does not provide any resistor.
Simultaneous sintering of the resistor material comprising MoSi.sub.2 -TaSi.sub.2 and glass and the green ceramic sheet in a non-oxidizing atmosphere also offers the problems that the substrate may warp due to a difference in the dislocation shrinkage curve, or may tend to swell easily due to the gas generated by the decomposing reaction of MoSi.sub.2 -TaSi.sub.2. To solve such problems, it is known by way of example to use a resistor material comprising MoSi.sub.2 -salts of metal fluorides (e.g., calcium fluoride) and glass, as disclosed in Japanese Patent Laid-Open (Kokai) Publication No. 60-198703. In this example, such warping or swelling of the substrate as mentioned above is not found.
However, when allowed to stand alone in a relative humidity of 95% for 1000 hours, the thick-film resistor obtained by applying such a resistor material comprising MoSi.sub.2 -metal fluorides and glass on a green ceramic sheet and simultaneously sintering them shows a 5 to 10% increase in the resistance value and, hence, cannot perform its own resistor function.
Further, the conventional electrical resistors as mentioned above have posed some problem, when used as the resistor element for a circuit needing precise work, since it is impossible to decrease the temperature dependence coefficient of their resistance value to 1000 ppm/.degree.C. or lower.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide an electrical resistor which can be used as a fixed chip resistor or for general circuit boards, and can also be laminated with a conductive material of a base metal and formed in a multilayered substrate.
A second object of the present invention is to provide an electrical resistor, the resistance value of which is stabilized.
A third object of the present invention is to provide an electrical resistor, in which the temperature coefficient of resistance value can be decreased.
A fourth object of the present invention is to provide an electrical resistor having excellent properties, which can be obtained even by sintering a resistor material in a reducing atmosphere.
A fifth object of the present invention is to provide an electrical resistor which can meet the reductions in both the size and cost of circuit substrates.
A sixth object of the present invention is to provide a method for making said electrical resistors, which can realize the performance thereof and further improve the properties thereof.
According to the present invention, the aforesaid objects are achieved by the provision of an electrical resistor obtained using at least one molybdate selected from the group consisting of (A) to (G) with or without a fluoride of an alkaline earth metal, and an electrical resistor paste obtained using the aforesaid components with or without a carbonate of an alkaline earth metal:
(A) Molybdates of alkaline earth metals,
(B) Molybdate of zinc,
(C) Molybdates of elements Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and complex molybdates of two or more of said elements,
(D) Molybdate of aluminium
(E) Molybdates of elements zirconium and hafnium, and complex molybdates thereof, and
(G) Molybdates of manganese.
According to the present invention, there is also provided a method for making electrical resistors which have their properties improved by using a heat-treated resistor material, and an electrical resistor of the particulate structure obtained by the growth of acicular particles from bulk particles so as to improve its properties.

BRIEF DESCRIPTION OF THE DRAWINGS
The aforesaid and other objects and features of the present invention will become apparent from the following detailed description with reference to the accompanying drawings, which are given for the purpose of illustration alone, and in which:
FIG. 1 is a schematical view showing the structure of the electrical resistor according to the present invention;
FIG. 2 is a view of one embodiment of the production of the electrical resistor according to the present invention, in which a resistive film and a conductive are applied on a substrate, and are being formed into a multilayered structure, prior to sintering;
FIG. 3 is a sectional view of that sintered body taken on line III--III;
FIG. 4 is a sectional view of a sintered body of a multilayered structure obtained using a conventional resistor material;
FIG. 5 is a view further illustrating that sintered body which is evolving gas;
FIG. 6 is an X-ray diffraction pattern, where the corresponding molybdate is detected from the electrical resistor of Sample No. 1 according to the example of the present invention;
FIG. 7 is a TEM 900,000 times enlargement photograph showing the structure of the electrical resistor, and
FIG. 8 is a TEM 900,000 times enlargement photograph showing the structure of the electrical resistor obtained by using the resistor material without the fluoride and the carbonate in the resistor material in FIG. 7.

DETAILED DESCRIPTION OF THE INVENTION
As illustrated as an example in FIG. 1, the electrical resistor according to the present invention is of the structure wherein spherical particles b and acicular particles c are dispersed throughout glass a. In this example, the acicular particles are deposited to the spherical particles, or are allowed to be present in the vicinity thereof. A current may pass through such a structure formed by contacting particles or particles in the vicinity thereof. For instance, such a structure may be formed by the sintering treatment of bulk particles of a resistor material, thereby growing the products formed on the surfaces thereof in the acicular form.
As such a resistor body material, at least one molybdate group selected from the group consisting of (A) to (G) may be used. For example, mentioned are the following molybdates are representative of the invention.
(A) Molybdates of Alkaline Earth Metals
Preferable molybdates to this end are expressed in terms of the following general formulae:
MeMoO.sub.4, Me.sub.3 MoO.sub.6, Me.sub.2 MoO.sub.5, Me.sub.2 Mo.sub.7, MeMo.sub.4 O.sub.r3, MeMo.sub.7 O.sub.24, MeMo.sub.3 O.sub.10, Me.sub.2 MoO.sub.5, Me.sub.2 Mo.sub.3 O.sub.11 and the like,
wherein Me is the alkaline earth metal. For example, the following groups may be mentioned: e.g., MgMoO.sub.4, CaMoO.sub.4, SrMoO.sub.4, BaMoO.sub.4, BaMo.sub.2 O.sub.7, BaMo.sub.4 O.sub.13, BaMo.sub.7 O.sub.24, BaMo.sub.3 O.sub.10, Ca.sub.3 MoO.sub.8, Sr.sub.3 MoO.sub.6, Ba.sub.3 MoO.sub.6, Ba.sub.2 MoO.sub.5, Mg.sub.2 Mo.sub.3 O.sub.11 and the like.
The following complex molybdates are also exemplified.
(Mg.sub.x Ca.sub.y)MoO.sub.4, provided that x+y=1,
(Ca.sub.x Sr.sub.y)MoO.sub.4, provided that x+y=1,
(Mg.sub.x Ba.sub.y)MoO.sub.4, provided that x+y=1,
(Mg.sub.x Ca.sub.y Ba.sub.z)MoO.sub.4, provided that x+y+z=1,
(Ca.sub.x Sr.sub.y Ba.sub.z)MoO.sub.4, provided that x+y+z=1,
(Mg.sub.x Ca.sub.y Sr.sub.z Ba.sub.w)MoO.sub.4, provided that x+y+z+w=1
(Ca.sub.x Sr.sub.y)MoO.sub.6, provided that x+y=1,
(Sr.sub.x Ba.sub.y)MoO.sub.6, provided that x+y=1.
(B) Molybdates of Zinc
For instance, ZnMoO.sub.4, ZnMo.sub.2 O.sub.7, Zn.sub.3 Mo.sub.2 O.sub.9 are mentioned.
(C) Molybdates of Elements Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and Complex Molybdates of Two or More of Said Elements
Examples of such molybdates are tabulated in the following table.
__________________________________________________________________________Molybdates of Various Elements and Complex Molybdates thereof__________________________________________________________________________Y.sub.6 MoO.sub.12 Y.sub.2 Mo.sub.3 O.sub.12 Y.sub.2 MoO.sub.5 Y.sub.4 MoO.sub.9La.sub.6 MoO.sub.12 La.sub.2 Mo.sub.3 O.sub.12 La.sub.2 MoO.sub.6 La.sub.2 Mo.sub.2 O.sub.9 La.sub.3 Mo.sub.2 O.sub.10 La.sub.2 Mo.sub.4 O.sub.15 La.sub.4 MoO.sub.9 La.sub.3 Mo.sub.2 O.sub.9 La.sub.4 MoO.sub.8Ce.sub.6 MoO.sub.12 CeMo.sub.2 O.sub.8 Ce.sub.2 Mo.sub.3 O.sub.13Pr.sub.6 MoO.sub.12 Pr.sub.2 Mo.sub.3 O.sub.12 Pr.sub.2 MoO.sub.6Nd.sub.6 MoO.sub.12 Nd.sub.2 Mo.sub.3 O.sub.12 Nd.sub.2 MoO.sub.6 Nd.sub.5 Mo.sub.3 O.sub.16Sm.sub.6 MoO.sub.12 Sm.sub.2 Mo.sub.3 O.sub.12 Sm.sub.2 MoO.sub.6 Sm.sub.2 Mo.sub.2 O.sub.7 Sm.sub.2 Mo.sub.2 O.sub.9 Sm.sub.18 Mo.sub.4 O.sub.39Eu.sub.6 MoO.sub.12 Eu.sub.2 Mo.sub.3 O.sub.12 Eu.sub.2 MoO.sub.6 EuMoO.sub.4 Eu.sub.2 Mo.sub.2 O.sub.7Gd.sub.6 MoO.sub.12 Gd.sub.2 Mo.sub.3 O.sub. 12 Gd.sub.2 MoO.sub.6 Gd.sub.2 Mo.sub.6 O.sub.21 Gd.sub.2 Mo.sub.4 O.sub.15Tb.sub.6 MoO.sub.12 Tb.sub.2 Mo.sub.3 O.sub.12 Tb.sub.2 MoO.sub.6 Tb.sub.2 Mo.sub.2 O.sub.9Dy.sub.6 MoO.sub.12 Dy.sub.2 MoO.sub.6Ho.sub.6 MoO.sub.12 Ho.sub.2 Mo.sub.3 O.sub.12 Ho.sub.2 MoO.sub.6 Ho.sub.10 Mo.sub.2 O.sub.21Er.sub.6 MoO.sub.12 Er.sub.2 MoO.sub.6Tm.sub.6 MoO.sub.12 Tm.sub.2 MoO.sub.6Yb.sub.6 MoO.sub.12 Yb.sub.2 Mo.sub.4 O.sub.15Lu.sub.6 MoO.sub.12 Lu.sub.2 Mo.sub.3 O.sub.12 Lu.sub.2 Mo.sub.2 O.sub.9__________________________________________________________________________
The following complex molybdates of two or more elements are also mentioned.
(Y.sub.x Ce.sub.y)MoO.sub.12, provided that x+y=6,
(Pr.sub.x Ey.sub.y)MoO.sub.12, provided that x+y=6,
(Gd.sub.x Dy.sub.y)MoO.sub.12, provided that x+y=6,
(Ho.sub.x Tm.sub.y Yb.sub.z)MoO.sub.12, provided that x+y+z=6.
(D) Molybdates of Aluminium
For instance, Al.sub.2 Mo.sub.3 O.sub.12 is mentioned.
(E) Molybdates of Elements Zirconium and Hafnium, and Molybdates of Said Elements
For instance, ZrMo.sub.2 O.sub.3, HfMo.sub.2 O.sub.8 and (Zr.sub.x Hf.sub.y)Mo.sub.2 O.sub.3, provided that x+y=1, are mentioned.
(F) Molybdates of Elements Niobium and Tantalum
For instance, Nb.sub.2 Mo.sub.3 O.sub.14, Ta.sub.2 Mo.sub.3 O.sub.14 and (Nb.sub.x Ta.sub.y)Mo.sub.3 O.sub.14, provided that x+y=1, are mentioned.
(G) Molybdates of Manganese
For instance, MnMoO.sub.4 is mentioned.
For use, at least one molybdate is selected from at least one molybdate group selected from the groups (A) to (G). When plural molybdates are selected from said at least one molybdate group, however, the single molybdates and/or complex molybdates of elements may be used.
The molybdates belonging to the aforesaid respective groups can be synthesized by the heat treatment of the oxides of the respective elements and molybdenum oxide (MoO.sub.3), but may be synthesized by the heat treatment of their precursors. For instance, the molybdates of alkaline earth metals may also be synthesized by mixing substances which provide the precursors of the respective oxides of alkaline earth metals with molybdenum oxide (MoO.sub.3) or its precursor in the predetermined molar ratio and heat-treating the resulting mixture. As an example, calcium carbonate (CaCO.sub.3) or calcium hydroxide [Ca(OH).sub.2 ] which is, for instance, the precursor of CaO is mixed with molybdenum oxide (MoO.sub.3) or its precursor, for instance, molybdic acid (H.sub.2 MoO.sub.4) in the predetermined molar ratio, and the mixture is heat-treated. The heat-treatment conditions in this case are 600.degree. to 1000.degree. C. and 1 to 3 hours.
In the present invention, glass is preferably used. As such glass, use may be made of glass generally known in the art. Although the present invention is not limited to glass having a specific composition, it is to be noted that oxides such as Pb.sub.3 O.sub.4, Bi.sub.2 O.sub.3, SnO.sub.2 and CdO may be reduced to metals which are likely to change the resistance value of resistors, when resistor materials containing them are sintered in a non-oxidizing atmosphere. Accordingly, where such a phenomenon is unpreferred, it is preferred that the glass used should not contain such oxides.
Preferable as the glass components are SiO.sub.2, B.sub.2 O.sub.3, ZnO, CaO, SrO, ZrO.sub.2 and the like. It is preferred that the compositional ratio of such oxides are:
SiO.sub.2 : 12 to 33% by weight
B.sub.2 O.sub.3 : 20 to 35% by weight
ZnO or SrO: 13 to 33% by weight
CaO: 10 to 25% by weight
ZrO.sub.2 : 15 to 45% by weight.
To make glass from the compositions of such oxides, the respective oxides are weighed and mixed together in the aforesaid compositional ratio. The mixture is charged in a crucible, in which it is molten at a temperature of 1200.degree. to 1500.degree. C. Thereafter, the melt is poured in, e.g., water for rapid cooling, and the thus obtained coarse glass powders are pulverized to the desired particle size (of, e.g., 10 .mu.m or less) by a pulverizer such as a ball mill or vibration mill to obtain glass powders.
The precursors of the respective oxides may wholly or partly be used and molten into glass. For instance, CaO (calcium oxide) and B.sub.2 O.sub.3 (boron oxide) are obtained by the heat treatment of CaCO.sub.3 (calcium carbonate) and boric acid (H.sub.3 BO.sub.3), respectively. Hence, CaCO.sub.3 and H.sub.2 BO.sub.3 may be used in place of the whole or a part of CaO and B.sub.2 O.sub.3. The same also holds for other componential oxides.
The fluorides of alkaline earth metals used in the present invention are expressed in terms of the general formula:
Me'F.sub.2
wherein Me' is the metal. As Me', use is made of alkaline earth metals, i.e., Mg, Ca, Sr and Ba. The respective salts of these metals may preferably be used alone or in admixture. In the present invention, however, the fluorides of other metals may also be used in addition to those of alkaline earth metals.
The molybdates of the elements belonging to said element groups and the glass powders obtained in the aforesaid manner are mixed together with or without the fluorides of alkaline earth metals, etc., and the mixtures may be used directly as resistor materials. In view of the resistance temperature properties of resistors, however, it is preferred to heat-treat and pulverize such mixtures and sinter the thus pulverized bodies as the resistor materials. The temperature for this heat treatment is preferably 800.degree. to 1200.degree. C. At a temperature departing from such a temperature range, the resistance value of the resulting resistors are apt to be influenced by delicate variations in the compositional ratio, which are caused by the operational conditions for the respective steps of processing the resistor materials into the electrical resistors. As a consequence, it is difficult to stably obtain the desired resistance value.
The heat treatment is desirously effected in a non-oxidizing atmosphere. To this end, use is preferably made of nitrogen gas or other inert gas, which may or may not contain hydrogen gas.
To prepare a fixed chip resistor or a resistor for thick-film resistors from the thus obtained resistor material powders, the powders are applied on, e.g., a ceramic green sheet, and the resulting product is sintered. In this case, for instance, the aforesaid molybdate forming the resistor body is preferably used in the form of bulk particles such as spherical, oval or polygonal particles. This is because it is preferable to allow the original matrixes of the acicular particles to remain in the process of the growth of the acicular particles during sintering. In order to form such a resistor body material into bulk particles, a binder such as glass may also be used.
For the purpose of applying such a resistor material comprising a molybdate and e.g., glass, a vehicle is mixed with the powders of such a resistor material so as to enable, e.g., screen printing. Prepared in this case, however, is a coating liquid to which a carbonate of an alkaline earth metal is added.
Such a carbonate may be expressed in terms of the general formula:
Me"CO.sub.3
wherein Me" is preferably but not exclusively the alkaline earth metal such as Mg, Ca, Sr and Ba. However, carbonates of other metals may be used.
Although varying dependent upon the type and combination of the molybdates of the elements selected from the groups (A) to (G) as already referred to, the compositional ratio of the respective components of the resistor materials should preferably be within the following range, when one or plural molybdates are selected from the same group.
__________________________________________________________________________Preferred Composition in weight %Group A B C D E F G__________________________________________________________________________Molybdate 40-95 65-95 60-95 45-95 50-95 55-95 65-95Glass Powders 4-59 4-34 4-39 4-54 4-49 4-44 4-34Fluoride of Alkaline 0.5-25 0.5-20 0.5-10 0.5-20 0.5-15 0.5-15 0.5-15Earth MetalCarbonate of Alkaline 0.5-50 0.5-30 0.5-25 0.5-25 0.5-45 0.5-40 0.5-25Earth Metal__________________________________________________________________________
Otherwise, when at least one molybdate is selected from at least one molybdate group of the groups (A) to (G) as already referred to, preferred compositions are composed of 34.8 to 95.0% by weight of the molybdate, 2.1 to 49.5% by weight of glass powders, 0.3 to 29.9% by weight of the fluoride of an alkaline earth metal and 0.3 to 33.3% by weight of the carbonate of an alkaline earth metal.
It is noted that when the carbonate of an alkaline earth metal is not used, it is preferable to apply the following compositional ratio.
__________________________________________________________________________Preferred Composition in weight %Group A B C D E F G__________________________________________________________________________Molybdate 30-95 60-95 55-95 40-95 40-95 50-95 55-95Glass Powders 4.5-69.5 4.5-39.5 4.5-44.5 4.5-59 4.5-54.5 4.5-49.5 4.5-44.5Fluoride of Alkaline 0.5-40 0.5-20 0.3-30 0.5-30 0.5-20 0.5-25 0.3-30Earth Metal__________________________________________________________________________
Otherwise, it is to be understood, however, that when at least one molybdate is selected from each of at least two groups of the aforesaid groups (A) to (G), preferred compositions are composed of 35.0 to 95.6% by weight of the molybdate, 2.8 to 49.9% by weight of the glass powders and 0.5 to 30.0% by weight of the fluoride of an alkaline earth metal.
An amount of the molybdate short excessively of the lower limit of the defined range and an amount of glass exceeding excessively the upper limit of the defined range are unpreferred, since the resistance value of the electrical resistor completed by sintering may become too high. On the contrary, when the amount of the said molybdate is too large and the amount of glass is too small, the binder ability of materials at the time of sintering may drop to such a degree that it is impossible to stably retain the sintered body on a circuit substrate. It is to be noted, however, that when the resistor is for instance laminated on and embedded in a circuit substrate, the molybdate and the fluoride of an alkaline earth metal may be used in an amount of not only higher than their upper limits but also 100%.
An amount of the fluoride of an alkaline earth metal either exceeding excessively the upper limit or short excessively of the lower limit may also be unpreferred, since the temperature dependence coefficient of the finished electrical resistor exceeds .+-.500 ppm/.degree.C. (the absolute value of .+-.500 is larger than 500), when the carbonate of an alkaline earth metal is present, the value may be made not to exceed .+-.300 ppm/.degree.C.
It is further noted that when it is not intended to use both the carbonate and fluoride of an alkaline earth metal, it is preferable to apply the following compositional ratio.
__________________________________________________________________________Preferred Composition in weight %Group A B C D E F G__________________________________________________________________________Molybdate 30-96 55-95 50-96 35-96 40-96 45-96 50-96Glass Powders 4-70 4-45 4-50 4-65 4-60 4-55 4-50__________________________________________________________________________
Otherwise, it is to be understood, however, that when at least one molybdate is selected from each of at least two groups of the aforesaid groups (A) to (G), preferred compositions are composed of 50-96% by weight of the molybdate and 4 to 50% by weight of the glass powders.
It is to be noted, however, that the fluorides of an alkaline earth metal and the carbonate of an alkaline earth metal may be used in an amount of departing from the defined range, if improvements in the temperature dependence coefficient of resistance is achieved.
Preferably, the aforesaid vehicle should be burned off anywhere prior to sintering. Preferable to this end are organic vehicles, i.e., in which resins are dissolved or dispersed in organic solvents, if required, with the addition of various additives such as plasticizers and dispersants. Examples of the organic solvents include butyl carbitol acetate, butyl carbitol and turpentine oil, whilst examples of the resins include cellulose derivatives such as ethyl cellulose and nitrocellulose and other resins.
Although the proportion of the organic vehicles with the resistor material powders varies depending upon, e.g., the organic solvents and resins used, the ratio of the organic solvents to the resins to be applied should suitably be in a range of 20 to 50% by weight of the former with respect to 80 to 50% by weight of the latter. These components are pasted with the resistor material by three-roll milling.
The thus obtained resistor material paste is applied on a substrate, and is further subjected to the treatments to be described later to make a resistor. The substrate may be prepared not only by sintering a ceramic green sheet along with a conductive material and a resistor material, but also by previously sintering a ceramic green sheet and applying thereon a resistor material and a conductor material, followed by sintering. Such procedures may also be applied to the formation of laminates.
As the aforesaid ceramic green sheet, use may be made of that obtained by slip-casting a slurry, etc., said slurry being prepared by mixing the organic vehicle with an oxide mixture of ceramic constituents comprising, for instance, 35 to 45% by weight of aluminium oxide (Al.sub.2 O.sub.3), 25 to 35% by weight of silicon oxide (SiO.sub.2), 10 to 15% by weight of boron oxide (B.sub.2 O.sub.3), 7 to 13% by weight of calcium oxide (CaO) and 7 to 10% by weight of magnesium oxide (MgO). In this case, when the molybdate of the aforesaid groups is not used with glass, an increased amount of a glassy component may be contained in the aforesaid ceramic green sheet so as to achieve an effect similar to that achieved by the use of glass. The aforesaid organic vehicles may be comprised of acrylic resins such as acryl ester, resins such as polyvinyl butyral, plasticizers such as glycerin and diethyl phthalate, dispersants such as carbonates, and solvents such as organic solvents.
It is preferred that the aforesaid resistive material paste is applied on the ceramic green sheet by means of, e.g., screen printing and, after drying, is heat-treated at 400.degree. to 500.degree. C. to decompose and burn the resinous component.
In this case, a paste of a conductive material of a base metal such as Ni or Cu or a noble metal such as Ag or Ag-Pd is also simultaneously applied on the ceramic green sheet in the same manner.
The paste compositions of the conductive material of a base metal such as Ni or Cu or a noble metal such as Ag or Ag-Pd are exemplified by those obtained by adding 2 to 15% by weight of glass frits to 98 to 85% by weight of the powders of the respective metals.
The resistor material and/or the conductive material are/is incorporated into the ceramic green sheet in this manner. In the case of a fixed chip resistor, by this sintering it is possible to form the conductive material and/or the thick-film resistor material simultaneously into/on the substrates. On the other hand, in the case of the laminate, another similar ceramic green sheet is further put thereon, and after repeating this process, the multilayered board is sintered.
When the conductor material of a base metal such as Ni or Cu is used as the conductor material in this case, sintering should preferably be carried out in a nonoxidizing atmosphere so as to prevent any increase in the resistance value due to its oxidation. The sintering temperature is exemplified by, e.g., 800.degree. to 1100.degree. C., and the sintering time is exemplified by, e.g., 0.5 to 2 hours. A nitrogen gas or other inert gases which may or may not contain a hydrogen gas may be used as the nonoxidizing atmosphere. When the conductor material of a noble metal such as Ag or Ag-Pd is used, on the other hand, sintering may be carried out in an oxidizing atmosphere of air, for instance.
The circuitry substrate having the conductor and/or resistor incorporated thereinto is completed in the manner as mentioned above. According to the present invention, however, any cracking, distortion, swelling, etc., which may be caused by sintering, are not found in the sintered substrate and the resistor, to say nothing of in the sintered substrate and the conductor, and the resistor shows a resistance value change within only .+-.0.1% with respect to changes in a relative humidity of 10 to 90% at 25.degree. C. Further, even after the resistor has been allowed to stand for at least 1000 hours in a high-temperature and-humidity atmosphere, the change in its resistance value is limited to within .+-.2%, and the temperature-dependent coefficient of its resistance value in the case of using the fluorides can be reduced not to exceed .+-.500 ppm/.degree.C., while that in the case of using the fluorides and carbonates not to exceed .+-.300 ppm/.degree.C. Such effects appear to be due to the fact that the resistor is well matched with the conductor and the sintered substrate and on the basis of the unique humidity resistance of the resistor comprising the sintered body comprised of the molybdate of the aforesaid groups and glass; however, details thereon are not yet clarified. By X-ray diffraction analysis, the resistor has been found to contain the molybdate. Also, the presence of the bulk and acicular particles has been observed under a transmission type electron microscope (TEM).
In the present invention, the molybdates selected as mentioned above may be used; however, the whole or a part of the precursors of such molybdates may be used in place thereof by a heat treatment. In either case, it is preferable that they are mixed with glass and heat-treated, and the resulting product is pulverized into a resistor material. Alternatively, the molybdates and/or their precursors may be mixed with the aforesaid vehicles, etc. without any heat treatment to prepare a paste, which is applied on, e.g., a ceramic green sheet, heat-treated for the removal of the organics, and is thereafter sintered directly into a resistor.
Referring to the glass used, it is to be understood that the mixed material of the oxides forming it may result in a sinterable state with the molybdate selected. The whole or a part of such oxides is put to a pasty state together with the molybdate selected and/or its precursor. The paste is then applied on the substrate, and the aforesaid glassy components are formed into glass in the process of either one of the steps of burning off the organics and the later sintering step. The glass is sintered with the molybdate selected and/or its precursor to thereby prepare a resistor. For instance, since CaO (calcium oxide) and B.sub.2 O.sub.3 (boron oxide) that are the components of glass materials may be obtained from CaCO.sub.3 (calcium carbonate) and H.sub.3 BO.sub.3 (boric acid) by heating, HCO.sub.3 and H.sub.3 BO.sub.3 may be used in place of the whole or a part of CaO and B.sub.2 O.sub.3, respectively. By the resistor material referred to in the present disclosure is meant a material which may be comprised of the molybdate selected, the glass and the fluoride of an alkaline earth metal as a result of the treating processes involved.
EXAMPLES
The present invention will now be explained with reference to the following non-restrictive examples.
EXAMPLE 1
The respective components were weighed and mixed together according in the compositional ratio calculated as oxides and specified in Table 1.
TABLE 1______________________________________Compositional Ratio in % by WeightSiO.sub.2 B.sub.2 O.sub.3 ZnO CaO SrO ZrO.sub.2______________________________________Glass A 20.0 29.0 13.0 10.0 11.0 17.0Glass B 18.0 28.5 20.2 10.5 -- 23.0______________________________________
The respective mixtures of Glass A and Glass B were separately molten in alumina crucibles at 1400.degree. C., and the obtained melts were poured in water for rapid cooling. The thus cooled products were taken out of the water, and were milled together with ethanol, and were pulverized by alumina balls into glass powders having a particle size of 10 .mu.m or lower.
The respective molybdates belonging to the aforesaid groups (A) to (G) were synthesized from molybdenum oxide and the oxides of the respective elements. However, the molybdate of an alkaline earth metal was prepared by mixing molybdenum oxide with the carbonate of an alkaline earth metal in a molar ratio of 1:1 and heat-treating the mixture at 700.degree. C. for 1 hour.
The powders obtained from each of Glass A and Glass B, the aforesaid molybdates and the fluorides of alkaline earth metals were weighed and mixed together in the proportions specified in the respective columns of Tables 2-9.
TABLE 2__________________________________________________________________________(Ex. 1)(Group A)Composition Glass Glass Fluorides CarbonatesMolybdates A B (wt. %) (wt. %)Nos. (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ MgMoO.sub.4 1 25 58.4 -- 8.3 8.3 2 41.7 41.7 -- 8.3 8.3 3 62.5 20.9 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 41.7 -- 41.7 8.3 8.3 6 62.5 -- 20.9 8.3 8.3 7 40 -- 59 0.5 0.5 8 40 -- 5 5 50 9 60 -- 5 30 5 10 60 -- 20 10 10 11 80 -- 10 5 5 12 80 -- 7 3 10 13 95 -- 4 0.5 0.5 14 40 -- 59 0.5 0.5 15 40 -- 5 5 50 16 60 -- 5 30 5 17 60 -- 20 10 10 18 80 -- 10 5 5 19 80 -- 7 3 10 20 95 -- 4 0.5 0.5 21 60 -- 20 10 10 22 80 -- 7 3 10 23 60 -- 20 10 10 24 80 -- 7 3 10 25 60 -- 20 10 10 26 80 -- 7 3 10 27 60 -- 10 20 10 28 80 -- 10 5 5 29 60 -- 10 20 10 30 80 -- 10 5 5 31 60 -- 10 20 10 32 80 -- 10 5 5 33 40 -- 5 2 2 1 25 25 34 60 -- 20 5 5 3 3 4 Mg.sub.2 Mo.sub.3 O.sub.11 35 25 -- 58.4 8.3 8.3 36 41.7 -- 41.7 8.3 8.3 37 62.5 -- 20.9 8.3 8.3 38 80 -- 3.4 8.3 8.3 39 41.7 41.7 -- 8.3 8.3 40 62.5 20.9 -- 8.3 8.3 41 40 -- 59 0.5 0.5 42 30 -- 5 5 50 43 60 -- 5 30 5 44 60 -- 20 10 10 45 80 -- 10 5 5 46 80 -- 7 3 10 47 95 -- 4 0.5 0.5 48 60 20 10 10 49 80 7 3 10 50 60 20 10 10 51 80 -- 7 3 10 52 60 20 10 10 53 80 7 3 10 54 60 -- 10 20 10 55 80 -- 10 5 5 56 60 -- 10 20 10 57 80 -- 10 5 5 58 60 -- 10 20 10 59 80 -- 10 5 5 60 40 -- 5 2 1 2 25 25 61 60 -- 20 5 5 3 3 4 MgMoO.sub.4 Mg.sub.2 Mo.sub.3 O.sub.11 62 40 40 3.4 8.3 8.3 63 30 30 -- 20 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 CaMoO.sub.4 64 25 58.4 -- 8.3 8.3 65 41.7 41.7 -- 8.3 8.3 66 62.5 20.9 -- 8.3 8.3 67 80 3.4 -- 8.3 8.3 68 41.7 -- 41.7 8.3 8.3 69 62.5 -- 20.9 8.3 8.3 70 40 59 0.5 0.5 71 40 5 5 50 72 60 -- 5 30 5 73 60 -- 20 10 10 74 80 -- 10 5 5 75 80 -- 7 3 10 76 95 -- 4 0.5 0.5 77 40 59 0.5 0.5 78 40 5 5 50 79 60 -- 5 30 5 80 60 -- 20 10 10 81 80 -- 10 5 5 82 80 -- 7 3 10 83 95 -- 4 0.5 0.5 84 60 -- 20 10 10 85 80 -- 7 3 10 86 60 -- 20 10 10 87 80 -- 7 3 10 88 60 -- 20 10 10 89 80 -- 7 3 10 90 60 -- 10 20 10 91 80 -- 10 5 5 92 60 -- 10 20 10 93 80 -- 10 5 5 94 60 -- 10 20 10 95 80 -- 10 5 5 96 40 -- 5 2 1 2 25 25 97 60 -- 20 5 5 3 3 4 Ca.sub.3 MoO.sub.6 98 25 -- 58.4 8.3 8.3 99 41.7 -- 41.7 8.3 8.3100 62.5 -- 20.9 8.3 8.3101 80 -- 3.4 8.3 8.3102 41.7 41.7 -- 8.3 8.3103 62.5 20.9 -- 8.3 8.3104 40 -- 59 0.5 0.5105 30 -- 5 5 50106 60 -- 5 30 5107 60 -- 20 10 10108 80 -- 10 5 5109 80 -- 7 3 10110 95 4 0.5 0.5111 60 20 10 10112 80 7 -- 3 10113 60 20 -- 10 10114 80 -- 7 3 10115 60 20 10 10116 80 7 3 10117 60 -- 10 20 10118 80 -- 10 5 5119 60 -- 10 20 10120 80 -- 10 5 5121 60 -- 10 20 10122 80 -- 10 5 5123 40 -- 5 2 2 1 25 25124 60 -- 20 5 5 3 3 4 CaMoO.sub.4 Ca.sub.3 MoO.sub.6125 40 40 3.4 -- 8.3 8.3126 30 30 -- 20 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 SrMoO.sub.4127 25 58.4 -- 8.3 8.3128 41.7 41.7 -- 8.3 8.3129 62.5 20.9 -- 8.3 8.3130 80 3.4 -- 8.3 8.3131 41.7 -- 41.7 8.3 8.3132 62.5 -- 20.9 8.3 8.3133 40 59 0.5 0.5134 40 5 5 50135 60 -- 5 30 5136 60 -- 20 10 10137 80 -- 10 5 5138 80 -- 7 3 10139 95 -- 4 0.5 0.5140 40 59 0.5 0.5141 40 5 5 50142 60 -- 5 30 5143 60 -- 20 10 10144 80 -- 10 5 5145 80 -- 7 3 10146 95 -- 4 0.5 0.5147 60 -- 20 10 10148 80 -- 7 3 10149 60 -- 20 10 10150 80 -- 7 3 10151 60 -- 20 10 10152 80 -- 7 3 10153 60 -- 10 20 10154 80 -- 10 5 5155 60 -- 10 20 10156 80 -- 10 5 5157 60 -- 10 20 10158 80 -- 10 5 5159 40 -- 5 2 2 1 25 25160 60 -- 20 5 5 3 3 4 Sr.sub.3 MoO.sub.6161 25 -- 58.4 8.3 8.3162 41.7 -- 41.7 8.3 8.3163 62.5 -- 20.9 8.3 8.3164 80 -- 3.4 8.3 8.3165 41.7 41.7 -- 8.3 8.3166 62.5 20.9 8.3 8.3167 40 -- 59 0.5 0.5168 40 -- 5 5 50169 60 -- 5 30 5170 60 -- 20 10 10171 80 -- 10 5 5172 80 -- 7 3 10173 95 4 0.5 0.5174 60 20 10 10175 80 7 3 10176 60 20 10 10177 80 -- 7 3 10178 60 20 10 10179 80 7 3 10180 60 -- 10 20 10181 80 -- 10 5 5182 60 -- 10 20 10183 80 -- 10 5 5184 60 -- 10 20 10185 80 -- 10 5 5186 40 -- 5 2 1 2 25 25187 60 -- 20 5 5 3 3 4 SrMoO.sub.4 Sr.sub.3 MoO.sub.6188 40 40 3.4 8.3 8.3189 30 30 -- 20 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 BaMoO.sub.4190 25 58.4 -- 8.3 8.3191 41.7 41.7 -- 8.3 8.3192 62.5 20.9 -- 8.3 8.3193 80 3.4 -- 8.3 8.3194 41.7 -- 41.7 8.3 8.3195 62.5 -- 20.9 8.3 8.3196 40 -- 59 0.5 0.5197 40 -- 5 5 50198 60 -- 5 30 5199 60 -- 20 10 10200 80 -- 7 3 10201 95 -- 4 0.5 0.5202 60 -- 20 10 10203 60 -- 20 10 10204 60 -- 20 10 10205 80 -- 7 3 10206 80 -- 10 3 10207 80 -- 7 3 10208 40 -- 5 5 0.5209 40 -- 5 5 10210 40 -- 5 2.5 2.5 10 Ba.sub.2 MoO.sub.5211 25 -- 58.4 8.3 8.3212 41.7 -- 41.7 8.3 8.3213 62.5 -- 20.9 8.3 8.3214 80 -- 3.4 8.3 8.3215 40 -- 59 0.5 0.5216 40 -- 5 5 50217 60 -- 20 10 10218 60 -- 5 30 5219 80 -- 7 3 10220 95 -- 4 0.5 0.5221 60 -- 20 10 3 3 4222 60 -- 20 10 10223 60 -- 20 10 10224 80 -- 7 3 10225 80 -- 7 3 10226 80 -- 7 3 10227 60 -- 5 20 10 5228 60 -- 5 20 10 2.5 2.5229 60 -- 5 10 10 10 3 2 Ba.sub.3 MoO.sub.6230 41.7 41.7 8.3 8.3231 62.5 20.9 8.3 8.3232 41.7 -- 41.7 8.3 8.3233 62.5 -- 20.9 8.3 8.3234 40 -- 59 0.5 0.5235 40 -- 5 5 50236 60 -- 20 10 10237 60 -- 5 30 5238 80 -- 7 3 10239 95 -- 4 0.5 0.5240 60 -- 20 10 10241 60 -- 20 10 10242 60 -- 20 10 10243 80 -- 7 3 10244 80 -- 7 3 10245 80 7 3 10 BaMoO.sub.4 Ba.sub.3 MoO.sub.6246 40 40 7 1.5 1.5 5 5 BaMoO.sub. 4 Ba.sub.2 MoO.sub.5 Ba.sub.3 MoO.sub.6247 30 20 20 7 1 0.5 0.5 1 3 3 2 2248 20.8 20.8 20.8 8.4 8.4249 (Mg.sub.0.3 Ca.sub.0.7)MoO.sub.4 41.7 41.7 -- 8.3 8.3250 (Mg.sub.0.7 Ca.sub.0.3)MoO.sub.4 41.7 41.7 -- 8.3 8.3251 (Ca.sub.0.3 Sr.sub.0.7)MoO.sub.4 41.7 41.7 -- 8.3 8.3252 (Ca.sub.0.7 Sr.sub.0.3)MoO.sub.4 41.7 41.7 -- 8.3 8.3253 (Mg.sub.0.3 Ba.sub.0.7)MoO.sub.4 41.7 41.7 -- 8.3 8.3254 (Mg.sub.0.7 Ba.sub.0.3)MoO.sub.4 41.7 41.7 -- 8.3 8.3255 (Mg.sub.0.2 Ca.sub.0.2 Ba.sub.0.6)MoO.sub.4 41.7 41.7 -- 8.3 8.3256 (Mg.sub.0.3 Ca.sub.0.4 Ba.sub.0.3)MoO.sub.4 41.7 41.7 -- 8.3 8.3257 (Ca.sub.0.2 Sr.sub.0.6 Ba.sub.0.2)MoO.sub.4 41.7 41.7 -- 8.3 8.3258 (Ca.sub.0.4 Sr.sub.0.3 Ba.sub.0.3)MoO.sub.4 41.7 41.7 -- 8.3 8.3259 (Mg.sub.0.2 Ca.sub.0.2 Sr.sub.0.2 Ba.sub.0.4)MoO.sub. 41.7 41.7 -- 8.3 8.3260 (Mg.sub.0.2 Ca.sub.0.3 Sr.sub.0.3 Ba.sub.0.2)MoO.sub. 41.7 41.7 -- 8.3 8.3261 (Ca.sub.2.0 Sr.sub.1.0)MoO.sub.6 41.7 41.7 -- 8.3 8.3262 (Ca.sub.1.0 Sr.sub.2.0)MoO.sub.6 41.7 41.7 -- 8.3 8.3263 (Sr.sub.2.0 Ba.sub.1.0)MoO.sub. 6 41.7 41.7 -- 8.3 8.3264 (Sr.sub.1.0 Ba.sub.2.0)MoO.sub.6 41.7 41.7 -- 8.3 8.3265 MgMoO.sub.4 29.2 -- 20.8 8.3 8.3 Ca.sub.3 MoO.sub.6 33.4266 CaMoO.sub.4 29.2 -- 20.8 8.3 8.3 Sr.sub.3 MoO.sub.6 33.4267 SrMoO.sub.4 29.2 -- 20.8 8.3 8.3 Ba.sub.2 MoO.sub.5 33.4268 BaMoO.sub.4 29.2 -- 20.8 8.3 8.3 Mg.sub.2 Mo.sub.3 O.sub.11 33.4269 MgMoO.sub.4 20.8 -- 20.8 8.3 8.3 Sr.sub.3 MoO.sub.6 20.8 Ba.sub.3 MoO.sub.6 20.8270 Mg.sub.2 Mo.sub.3 O.sub.11 12.5 -- 20.8 8.3 8.3 CaMoO.sub.4 16.7 SrMoO.sub.4 16.7 BaMoO.sub.4 16.7271 MgMoO.sub.4 30 -- 20 10 10 Ca.sub.3 MoO.sub.6 30272 CaMoO.sub.4 30 -- 20 10 10 Sr.sub.3 MoO.sub.6 30273 SrMoO.sub.4 30 -- 20 10 10 Ba.sub.2 MoO.sub.5 30274 BaMoO.sub.4 30 -- 20 10 10 Mg.sub.2 Mo.sub.3 O.sub.11 30275 MgMoO.sub.4 20 -- 20 10 10 Sr.sub.3 MoO.sub.6 20 Ba.sub.3 MoO.sub.6 20276 Mg.sub.2 Mo.sub.3 O.sub.11 15 -- 20 10 10 CaMoO.sub.4 15 SrMoO.sub.4 15 BaMoO.sub.4 15__________________________________________________________________________
TABLE 3__________________________________________________________________________(Ex. 1 - Group B) Glass Glass Fluorides CarbonateMolybdate A B (wt. %) (wt. %)NOs (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ ZnMoO.sub.4 1 45.9 37.5 -- 8.3 8.3 2 54.2 29.2 -- 8.3 8.3 3 66.7 16.7 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 54.2 -- 29.2 8.3 8.3 6 66.7 -- 16.7 8.3 8.3 7 65 -- 34 0.5 0.5 8 65 -- 4 1 30 9 75 -- 4 20 110 75 -- 10 3 1211 85 -- 5 5 512 95 -- 4 0.5 0.513 65 -- 4 1 3014 75 -- 10 3 1215 65 -- 4 1 3016 75 -- 10 3 1217 65 -- 4 1 3018 75 -- 10 3 1219 75 -- 4 20 120 85 -- 5 5 521 75 -- 4 20 122 85 -- 5 5 523 75 -- 4 20 124 85 -- 5 5 525 75 -- 10 3 6 626 75 -- 10 1.5 1.5 6 627 75 -- 10 1 1 1 4 4 4 ZnMo.sub.2 O.sub.728 45.9 37.5 -- 8.3 8.329 54.2 29.2 -- 8.3 8.330 66.7 16.7 -- 8.3 8.331 80 3.4 -- 8.3 8.332 54.2 -- 29.2 8.3 8.333 66.7 -- 16.7 8.3 8.334 65 -- 34 0.5 0.535 65 -- 4 1 3036 75 -- 4 20 137 75 -- 10 3 1238 85 -- 5 5 539 95 -- 4 0.5 0.540 65 -- 4 1 3041 75 -- 10 3 1242 65 -- 4 1 3043 75 -- 10 3 1244 65 -- 4 1 3045 75 -- 10 3 1246 75 -- 4 20 147 85 -- 5 5 548 75 -- 4 20 149 85 -- 5 5 550 75 -- 4 20 151 85 -- 5 5 552 65 -- 4 1 15 1553 65 -- 4 0.5 0.5 20 1054 65 -- 4 0.5 0.5 15 15 Zn.sub.3 Mo.sub.2 O.sub.955 54.2 29.2 -- 8.3 8.356 66.7 16.7 -- 8.3 8.357 54.2 -- 29.2 8.3 8.358 66.7 -- 16.7 8.3 8.359 65 -- 34 0.5 0.560 65 -- 4 1 3061 75 -- 4 20 162 75 -- 10 3 1263 85 -- 5 5 564 95 -- 4 0.5 0.565 65 -- 4 1 3066 75 -- 10 3 1267 65 -- 4 1 3068 75 -- 10 3 1269 65 -- 4 1 3070 75 -- 10 3 1271 75 -- 4 20 172 85 -- 5 5 573 75 -- 4 20 174 85 -- 5 5 575 75 -- 4 20 176 85 -- 5 5 577 85 -- 5 5 2.5 2.578 85 -- 5 2.5 2.5 2.5 2.579 85 -- 5 2.5 2.5 1 3 180 ZnMoO.sub.4 35 -- 10 3 12 ZnMo.sub.2 O.sub.7 4081 ZnMoO.sub.4 25 16.7 -- 8.3 8.3 ZnMo.sub.2 O.sub.7 25 Zn.sub.3 Mo.sub.2 O.sub.9 16.782 ZnMoO.sub.4 20 -- 10 1.5 1.5 6 6 ZnMo.sub.2 O.sub.7 25 Zn.sub.3 Mo.sub.2 O.sub.9 3083 ZnMoO.sub.4 20 -- 10 1 1 0.5 0.5 3 3 3 3 ZnMo.sub.2 O.sub.7 25 Zn.sub.3 Mo.sub.2 O.sub.9 30__________________________________________________________________________
TABLE 4__________________________________________________________________________(Ex. 1 - Group C)Composition Molybdate Fluorides Carbonate Al.sub.2 Mo.sub.3 O.sub.12 Glass A Glass B (wt. %) ( %)NOs (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ 1 41.7 41.7 -- 8.3 8.3 2 54.2 29.2 -- 8.3 8.3 3 66.7 16.7 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 41.7 -- 41.7 8.3 8.3 6 54.2 -- 29.3 8.3 8.3 7 66.7 -- 16.7 8.3 8.3 8 80 -- 3.4 8.3 8.3 9 66.8 8.3 8.3 8.3 8.310 60 -- 39 0.5 0.511 60 -- 5 10 2512 75 -- 10 5 1013 85 -- 7 3 514 95 -- 4 0.5 0.515 60 -- 39 0.5 0.516 60 -- 5 10 2517 75 -- 10 5 1018 85 -- 7 3 519 95 -- 4 0.5 0.520 75 -- 10 5 1021 85 -- 7 3 522 75 -- 10 5 1023 85 -- 7 3 524 75 -- 10 5 1025 85 -- 7 3 526 75 -- 10 5 1027 85 -- 7 3 528 75 -- 10 5 1029 85 -- 7 3 530 75 -- 10 5 1031 85 -- 7 3 532 75 -- 10 5 5 533 75 -- 10 2.5 2.5 5 534 75 -- 10 2 2 1 3 4 335 85 -- 7 1 1 1 2 2 1__________________________________________________________________________
TABLE 5__________________________________________________________________________(Ex. 1 - Group D)Composition Fluorides CarbonatesMolybdate Glass A Glass B (wt. %) (wt. %)NOs (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ ZrMo.sub.2 O.sub.8 1 29.2 54.2 -- 8.3 8.3 2 45.9 37.5 -- 8.3 8.3 3 62.5 20.9 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 45.9 -- 37.5 8.3 8.3 6 62.5 -- 20.9 8.3 8.3 7 45 -- 54 0.5 0.5 8 45 -- 4 1 50 9 60 -- 20 5 1510 60 -- 10 20 1011 80 -- 10 5 512 80 -- 7 10 313 95 -- 4 0.5 0.514 45 -- 54 0.5 0.515 45 -- 4 1 5016 60 -- 20 5 1517 60 -- 10 20 1018 80 -- 10 5 519 80 -- 7 10 320 95 -- 4 0.5 0.521 60 -- 20 5 1522 80 -- 10 5 523 60 -- 20 5 1524 80 -- 10 5 525 60 -- 20 5 1526 80 -- 10 5 527 60 -- 10 20 1028 80 -- 7 10 329 60 -- 10 20 1030 80 -- 7 10 331 60 -- 10 20 1032 80 -- 7 10 333 45 -- 4 1 30 2034 45 -- 4 0.5 0.5 20 20 10 HfMo.sub.2 O.sub.835 29.2 -- 54.2 8.3 8.336 45.9 -- 37.5 8.3 8.337 62.5 -- 20.9 8.3 8.338 80 -- 3.4 8.3 8.339 45.9 37.5 -- 8.3 8.340 62.5 20.9 -- 8.3 8.341 45 -- 54 0.5 0.542 45 -- 4 1 5043 60 -- 20 5 1544 60 -- 10 20 1045 80 -- 10 5 546 80 -- 7 10 347 95 -- 4 0.5 0.548 60 -- 20 5 1549 80 -- 10 5 550 60 -- 20 5 1551 80 -- 10 5 552 60 -- 20 5 1553 80 -- 10 5 554 60 -- 10 20 1055 80 -- 7 10 356 60 -- 10 20 1057 80 -- 7 10 358 60 -- 10 20 1059 80 -- 7 10 360 45 -- 4 1 30 2061 45 -- 4 0.5 0.5 20 10 2062 (Zr.sub.0.5 Mo.sub.0.5)Mo.sub.2 O.sub.8 -- 10 1 2 1 1 1 1 1 2 8063 ZrMo.sub.2 O.sub.8 40 -- 10 5 5 HfMo.sub.2 O.sub.8 4064 ZrMo.sub.2 O.sub.8 40 -- 10 1 2 1 1 1 1 1 2 HfMo.sub.2 O.sub.8 40__________________________________________________________________________
TABLE 6__________________________________________________________________________(Ex. 1 - Group E)Composition Fluorides CarbonateMolybdates Glass A Glass B (wt. %) ( %)NOs (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ Y.sub.6 MoO.sub.12 1 33.4 50 -- 8.3 8.3 2 45.9 37.5 -- 8.3 8.3 3 62.5 20.9 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 45.9 -- 37.5 8.3 8.3 6 62.5 -- 20.9 8.3 8.3 7 50 -- 49 0.5 0.5 8 50 -- 20 10 20 9 50 -- 4 1 4510 65 -- 10 15 1011 65 -- 20 10 512 80 -- 10 5 513 80 -- 5 7.5 7.514 95 -- 4 0.5 0.515 50 -- 49 0.5 0.516 50 -- 20 10 2017 50 -- 4 1 4518 65 -- 10 15 1019 65 -- 20 10 520 80 -- 10 5 521 80 -- 5 7.5 7.522 95 -- 4 0.5 0.523 50 -- 20 10 2024 80 -- 10 5 525 50 -- 20 10 2026 80 -- 10 5 1027 50 -- 20 10 2028 80 -- 10 5 529 65 -- 20 10 530 80 -- 10 5 531 65 -- 20 10 532 80 -- 10 5 533 65 -- 20 10 534 80 -- 10 5 535 50 -- 20 10 10 1036 50 -- 20 5 5 10 1037 50 -- 20 3 4 3 5 5 1038 50 -- 20 3 3 2 2 5 5 5 5 La.sub.6 MoO.sub.1239 33.4 -- 50 8.3 8.340 45.9 -- 37.5 8.3 8.341 62.5 -- 20.9 8.3 8.342 80 -- 3.4 8.3 8.343 45.9 37.5 -- 8.3 8.344 62.5 20.9 -- 8.3 8.345 50 -- 49 0.5 0.546 50 -- 20 10 2047 50 -- 4 1 4548 65 -- 10 15 1049 65 -- 20 10 550 80 -- 10 5 551 80 -- 5 7.5 7.552 95 -- 4 0.5 0.553 80 -- 5 7.5 7.554 50 -- 20 5 5 2055 50 -- 20 5 5 2056 50 -- 20 4 3 3 20 Ce.sub.6 MoO.sub.1257 45.9 37.5 -- 8.3 8.358 62.5 -- 20.9 8.3 8.359 80 -- 5 7.5 7.5 Pr.sub.6 MoO.sub.1260 45.9 37.5 -- 8.3 8.361 62.5 -- 20.9 8.3 8.362 80 -- 5 7.5 7.5 Nd.sub.6 MoO.sub.1263 45.9 37.5 -- 8.3 8.364 62.5 -- 20.9 8.3 8.365 80 -- 5 7.5 7.5 Sm.sub.6 MoO.sub.1266 45.9 37.5 -- 8.3 8.367 62.5 -- 20.9 8.3 8.368 80 -- 5 7.5 7.5 Eu.sub.6 MoO.sub.1269 45.9 37.5 -- 8.3 8.370 62.5 -- 20.9 8.3 8.371 80 -- 5 7.5 7.5 Gd.sub.6 MoO.sub.1272 45.9 37.5 -- 8.3 8.373 62.5 -- 20.9 8.3 8.374 80 -- 5 7.5 7.5 Tb.sub.6 MoO.sub.1275 45.9 37.5 -- 8.3 8.376 62.5 -- 20.9 8.3 8.377 80 -- 5 7.5 7.5 Dy.sub.6 MoO.sub.1278 45.9 37.5 -- 8.3 8.379 62.5 -- 20.9 8.3 8.380 80 -- 5 7.5 7.5 Ho.sub.6 MoO.sub.1281 45.9 37.5 -- 8.3 8.382 62.5 -- 20.9 8.3 8.383 80 -- 5 7.5 7.5 Er.sub.6 MoO.sub.1284 45.9 37.5 -- 8.3 8.385 62.5 -- 20.9 8.3 8.386 80 -- 5 7.5 7.5 Tm.sub.6 MoO.sub.1287 45.9 37.5 -- 8.3 8.388 62.5 -- 20.9 8.3 8.389 80 -- 5 7.5 7.5 Yb.sub.6 MoO.sub.1290 45.9 37.5 -- 8.3 8.391 62.5 -- 20.9 8.3 8.392 80 -- 5 7.5 7.5 Lu.sub.6 MoO.sub.1293 45.9 37.5 -- 8.3 8.394 62.5 -- 20.9 8.3 8.395 80 -- 5 7.5 7.596 (Y.sub.3.0 Ce.sub.3.0)MoO.sub.12 65 -- 20 10 597 (Pr.sub.3.0 Eu.sub.3.0)MoO.sub.12 65 -- 20 10 598 (Gd.sub.3.0 Dy.sub.3.0)MoO.sub.12 65 -- 20 10 599 (La.sub.2.0 Nd.sub.2.0 Tb.sub.2.0)MoO.sub.12 -- 20 10 5 65100 (Ho.sub.2.0 Tm.sub.2.0 Yb.sub.2.0)MoO.sub.12 -- 20 10 5 65101 Y.sub.6 MoO.sub.12 40 -- 5 7.5 7.5 La.sub.6 MoO.sub.12 40102 Nd.sub.6 MoO.sub.12 40 -- 5 7.5 7.5 Sm.sub.6 MoO.sub.12 40103 Gd.sub.6 MoO.sub.12 40 -- 5 7.5 7.5 Dy.sub.6 MoO.sub.12 40104 Ho.sub.6 MoO.sub.12 20 -- 5 7.5 7.5 Er.sub.6 MoO.sub.12 30 Tm.sub.6 MoO.sub.12 30105 Yb.sub.6 MoO.sub.12 20 -- 5 7.5 7.5 Lu.sub.6 MoO.sub.12 30 Eu.sub.6 MoO.sub.12 30__________________________________________________________________________
TABLE 7__________________________________________________________________________(Ex. 1 - Group F)CompositionMolybdates Fluorides CarbonatesNb.sub.2 Mo.sub.3 O.sub.14 Glass A Glass B (wt. %) (wt. %)NOs (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________ Nb.sub.2 Mo.sub.3 O.sub.14 1 37.5 45.9 -- 8.3 8.3 2 54.2 29.2 -- 8.3 8.3 3 66.7 16.7 -- 8.3 8.3 4 80 3.4 -- 8.3 8.3 5 54.2 -- 29.2 8.3 8.3 6 66.7 -- 16.7 8.3 8.3 7 55 -- 44 0.5 0.5 8 55 -- 4 1 40 9 70 -- 10 15 510 70 -- 10 5 1511 80 -- 7 3 1012 95 -- 4 0.5 0.513 70 -- 10 15 514 80 -- 7 3 1015 70 -- 10 15 516 80 -- 7 3 1017 70 -- 10 15 518 80 -- 7 3 1019 55 -- 4 1 4020 70 -- 10 5 1521 55 -- 4 1 4022 70 -- 10 5 1523 55 -- 4 1 4024 70 -- 10 5 1525 70 -- 10 5 10 526 70 -- 10 2.5 2.5 5 5 5 Ta.sub.2 Mo.sub.3 O.sub.1427 37.5 -- 45.9 8.3 8.328 54.2 -- 29.2 8.3 8.329 66.7 -- 16.7 8.3 8.330 80 -- 3.4 8.3 8.331 54.2 29.2 -- 8.3 8.332 66.7 16.7 -- 8.3 8.333 55 -- 44 0.5 0.534 55 -- 4 1 4035 70 -- 10 15 536 70 -- 10 5 1537 80 -- 7 3 1038 95 -- 4 0.5 0.539 70 -- 10 15 540 80 -- 7 3 1041 70 -- 10 15 542 80 -- 7 3 1043 70 -- 10 15 544 80 -- 7 3 1045 55 -- 4 1 4046 70 -- 10 5 1547 55 -- 4 1 4048 70 -- 10 5 1549 55 -- 4 1 4050 70 -- 10 5 1551 70 -- 10 2.5 2.5 10 552 70 -- 10 2 2 1 5 5 553 (Nb.sub.1.0 Ta.sub.1.0)Mo.sub.3 O.sub.14 7 1 1 0.5 0.5 3 3 2 2 8054 Nb.sub.2 Mo.sub.3 O.sub.14 40 -- 7 1 1 0.5 0.5 3 3 2 2 Ta.sub.2 Mo.sub.3 O.sub.14 40__________________________________________________________________________
TABLE 8__________________________________________________________________________(Ex. 1-Group G)CompositionMolybdate Glass Glass Fluorides CarbonatesMnMoO.sub.4 A B (wt. %) (wt. %)Nos (wt. %) (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________1 41.7 41.7 -- 8.3 8.32 54.2 29.2 -- 8.3 8.33 66.7 16.7 -- 8.3 8.34 80 3.4 -- 8.3 8.35 41.7 -- 41.7 8.3 8.36 54.2 -- 29.2 8.3 8.37 66.7 -- 16.7 8.3 8.38 80 -- 3.4 8.3 8.39 66.8 8.3 8.3 8.3 8.310 65 -- 34 0.5 0.511 65 -- 5 5 2512 75 -- 10 5 1013 75 -- 5 15 514 85 -- 7 3 515 95 -- 4 0.5 0.516 65 -- 34 0.5 0.517 65 -- 5 5 2518 75 -- 10 5 1019 75 -- 5 15 520 85 -- 7 3 521 95 -- 4 0.5 0.522 75 -- 10 5 1023 85 -- 7 3 524 75 -- 10 5 1025 85 -- 7 3 526 75 -- 10 5 1027 85 -- 7 3 528 75 -- 5 15 529 85 -- 7 3 530 75 -- 5 15 531 85 -- 7 3 532 75 -- 5 15 533 85 -- 7 3 534 65 -- 5 5 15 1035 65 -- 5 2.5 2.5 15 1036 65 -- 7 1 1 1 10 5 10__________________________________________________________________________
TABLE 9__________________________________________________________________________(Ex. 1-plural Groups) Glass Fluo- Car-Nos A B C D E F G A B rides bonates__________________________________________________________________________ 1 MgMoO.sub.4 ZnMoO.sub.4 MgF.sub.2 MgCo.sub.3 24.7 24.8 49.5 0.5 0.5 2 CaMoO.sub.4 Y.sub.6 MoO.sub.12 MgF.sub.2 MgCo.sub.3 25.0 25.0 33.3 8.3 8.3 3 SrMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 MgF.sub.2 MgCo.sub.3 25.0 25.0 21.4 14.3 14.3 4 BaMoO.sub.4 ZrMo.sub.2 O.sub.8 MgF.sub.2 MgCo.sub.3 25.0 25.0 12.5 18.7 18.8 5 Mg.sub.2 Mo.sub.3 O.sub.11 Nb.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 MgCo.sub.3 24.2 24.2 5.4 23.1 23.1 6 Ca.sub.3 MoO.sub.6 MnMoO.sub.4 CaF.sub.2 MgCo.sub.3 47.5 47.5 4.0 0.5 0.5 7 ZnMo.sub.2 O.sub.7 La.sub.2 Mo.sub.2 O.sub.9 CaF.sub.2 CaCo.sub.3 22.6 22.6 45.3 9.0 0.5 8 Zn.sub.3 Mo.sub.2 O.sub.9 Al.sub.2 Mo.sub.3 O.sub.12 CaF.sub.2 CaCo.sub.3 23.1 23.1 30.8 15.4 7.6 9 ZnMoO.sub.4 HfMo.sub.2 O.sub.8 CaF.sub.2 CaCo.sub.3 23.3 23.3 20.0 20.0 13.410 ZnMo.sub.2 O.sub.7 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 CaCo.sub.3 23.1 23.1 11.6 24.9 17.311 Zn.sub.3 Mo.sub.2 O.sub.9 MnMoO.sub.4 SrF.sub.2 CaCo.sub.3 32.0 32.0 7.1 0.4 28.512 CeMo.sub.2 O.sub.8 Al.sub.2 Mo.sub.3 O.sub.12 SrF.sub.2 CaCo.sub.3 30.0 30.0 2.5 6.3 31.213 Pr.sub.2 MoO.sub.6 ZrMo.sub.2 O.sub.8 SrF.sub.2 SrCo.sub.3 20.7 20.7 41.5 16.6 0.514 Nd.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 SrCo.sub.3 21.4 21.4 28.6 21.4 7.215 Sm.sub.6 MoO.sub.12 MnMoO.sub.4 SrF.sub.2 SrCo.sub.3 21.5 21.5 18.4 26.4 12.316 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 BaF.sub.2 SrCo.sub.3 30.7 30.7 15.3 0.4 22.917 Al.sub. 2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 SrCo.sub.3 30.0 30.0 6.7 6.7 26.618 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 BaF.sub.2 SrCo.sub.3 28.2 28.2 2.4 11.8 29.419 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 BaCo.sub.3 19.2 19.2 38.3 22.9 0.420 HfMo.sub.2 O.sub.8 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 19.6 19.6 26.1 28.1 6.621 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 BaCo.sub.3 29.0 29.0 24.9 0.4 16.722 Sr.sub.3 MoO.sub.6 ZnMoO.sub.4 Eu.sub.2 Mo.sub.2 O.sub.7 MgF.sub.2 BaCo.sub.3 28.6 14.3 14.3 14.3 7.1 21.423 BaMo.sub.2 O.sub.7 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 MgF.sub.2 BaCo.sub.3 18.8 18.8 18.8 6.1 12.5 25.024 Ba.sub.3 MoO.sub.6 Zn.sub.3 Mo.sub.2 O.sub.9 ZrMo.sub.2 O.sub.8 MgF.sub.2 BaCo.sub.3 22.2 22.2 8.9 2.2 16.7 27.825 MgMoO.sub.4 ZnMoO.sub.4 Nb.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 MgCo.sub.3 13.9 7.0 13.9 34.8 30.0 0.426 CaNoO.sub.4 ZnMo.sub.2 O.sub.7 MnMoO.sub.4 CaF.sub.2 MgCo.sub.3 18.1 18.1 18.1 36.2 0.5 9.027 SrMoO.sub.4 Gd.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 CaF.sub.2 MgCo.sub.3 7.7 23.1 23.1 23.1 7.7 15.328 BaMo.sub.4 O.sub.13 Tb.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 CaF.sub.2 MgCo.sub.3 13.3 26.7 13.3 13.3 13.4 20.029 Mg.sub.2 Mo.sub.3 O.sub.11 Dy.sub.2 MoO.sub.6 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 MgCo.sub.3 23.5 23.5 5.9 5.9 17.6 23.630 Ca.sub.3 MoO.sub.6 Ho.sub.6 MoO.sub.12 MnMoO.sub.4 CaF.sub.2 MgCo.sub.3 8.3 20.7 20.7 2.1 22.3 25.931 Sr.sub.3 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 SrF.sub.2 CaCo.sub.3 9.9 29.7 9.9 49.5 0.5 0.532 BaMo.sub.7 O.sub.24 Al.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 CaCo.sub.3 8.3 25.0 16.7 33.3 8.3 8.433 MgMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 SrF.sub.2 CaCo.sub.3 14.3 14.3 21.4 21.4 14.3 14.334 CaMoO.sub.4 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 CaCo.sub.3 25.0 12.5 12.5 12.5 18.7 18.835 SrMoO.sub.4 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 CaCo.sub.3 16.4 16.4 16.4 5.5 23.5 21.836 BaMoO.sub.4 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 CaCo.sub.3 26.6 10.6 20.6 2.7 0.3 33.237 Zn.sub.3 Mo.sub.2 O.sub.9 Er.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 BaF.sub.2 SrCo.sub.3 18.1 18.1 9.0 45.3 9.0 0.538 ZnMoO.sub.4 Tm.sub.6 MoO.sub.12 HfMo.sub.2 O.sub.8 BaF.sub.2 SrCo.sub.3 7.7 23.1 15.4 30.8 15.3 7.739 ZnMo.sub.2 O.sub.7 Yb.sub.2 Mo.sub.4 O.sub.15 Ta.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 SrCo.sub.3 6.7 13.3 26.7 20.0 20.0 13.340 Zn.sub.3 Mo.sub.2 O.sub.9 Lu.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 BaF.sub.2 SrCo.sub.3 12.3 12.3 11.6 11.6 24.9 17.341 ZnMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 MgF.sub.2 SrCo.sub.3 28.5 28.5 7.1 7.1 0.4 28.442 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 SrCo.sub.3 25.0 18.8 16.2 2.5 6.3 31.243 Zn.sub.3 Mo.sub.2 O.sub.9 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 MgF.sub.2 BaCo.sub.3 16.6 16.6 8.2 41.5 16.6 0.544 ZnMoO.sub.4 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 BaCo.sub.3 14.3 14.3 14.3 28.6 21.4 7.145 ZnMo.sub.2 O.sub.7 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 MgF.sub.2 BaCo.sub.3 18.4 18.4 6.1 18.4 26.4 12.346 Zn.sub.3 Mo.sub.2 O.sub.9 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 BaCo.sub.3 23.0 23.0 15.3 15.3 0.4 23.047 Y.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 CaF.sub.2 BaCo.sub.3 6.7 26.7 26.7 6.7 6.7 26.548 La.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 BaCo.sub.3 29.4 9.4 17.6 2.4 11.8 29.449 Ce.sub.2 Mo.sub.3 O.sub.13 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 CaF.sub.2 MgCo.sub.3 23.0 7.7 7.7 38.3 23.0 0.350 Pr.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 MgCo.sub.3 19.6 13.1 6.5 22.1 28.1 6.651 Nd.sub.2 MoO.sub.4 HfMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 MgCo.sub.3 24.9 24.9 8.3 24.9 0.4 16.652 Sm.sub.6 MoO.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 MgCo.sub.3 21.4 28.6 7.1 14.3 7.1 21.553 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 MgCo.sub.3 18.7 18.7 18.7 6.3 12.6 25.054 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 MgCo.sub.3 16.7 16.7 20.0 2.2 16.7 27.755 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 CaCo.sub.3 7.0 13.9 13.9 34.8 30.0 0.456 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 CaCo.sub.3 9.0 18.1 27.1 36.2 0.5 9.157 Mg.sub.2 Mo.sub.3 O.sub.11 ZnMoO.sub.4 EuMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 BaF.sub.2 CaCo.sub.3 7.7 15.4 15.4 15.4 23.1 7.7 15.358 Ca.sub.3 MoO.sub.6 ZnMo.sub.2 O.sub.7 Gd.sub.2 Mo.sub.6 O.sub.21 HfMo.sub.2 O.sub.8 BaF.sub.2 CaCo.sub.3 13.3 13.3 13.3 13.3 13.3 13.4 20.159 Sr.sub.3 MoO.sub.6 Zn.sub.3 Mo.sub.2 O.sub.9 Tb.sub.6 MoO.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 CaCo.sub.3 8.8 8.8 17.6 17.6 5.9 17.6 23.760 Ba.sub.2 MoO.sub.5 ZnMoO.sub.4 Dy.sub.6 MoO.sub.12 MnMoO.sub.4 BaF.sub.2 CaCo.sub.3 15.5 15.5 15.5 3.1 2.1 22.3 26.061 MgMoO.sub.4 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 MgF.sub.2 SrCo.sub.3 10 10 10 20 49.5 0.5 0.562 CaMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.9 Al.sub.2 Mo.sub. 3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 SrCo.sub.3 12.5 12.5 12.5 12.5 33.3 8.3 8.463 SrMoO.sub.4 ZnMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 MgF.sub.2 SrCo.sub.3 14.3 14.3 10.7 10.7 21.4 14.3 14.364 BaMoO.sub.4 ZnMo.sub.2 O.sub.7 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 SrCo.sub.3 9.4 15.6 15.6 9.4 12.5 18.8 18.765 Mg.sub.2 Mo.sub.3 O.sub.11 Zn.sub.3 Mo.sub.2 O.sub.9 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 MgF.sub.2 SrCo.sub.3 10.9 10.9 13.7 13.7 5.5 23.5 21.866 Ca.sub.3 MoO.sub.6 ZnMoO.sub.4 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 15.9 15.9 15.9 15.9 2.4 0.3 33.367 Sr.sub.3 MoO.sub.6 Ho.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 CaF.sub.2 BaCo.sub.3 9.0 13.6 13.6 9.0 45.2 9.0 0.568 BaMo.sub.3 O.sub.10 Er.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 BaCo.sub.3 7.7 15.4 7.7 15.4 30.8 15.4 7.669 MgMoO.sub.4 Tm.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 CaF.sub.2 BaCo.sub.3 13.3 10.0 10.0 13.3 20.0 20.0 13.470 CaMoO.sub.4 Yb.sub.6 MoO.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 BaCo.sub.3 17.3 5.8 17.3 5.8 11.6 24.9 17.371 SrMoO.sub.4 Lu.sub.6 MoO.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 BaCo.sub.3 17.8 14.2 17.8 14.2 7.1 0.4 28.572 BaMoO.sub.4 Yb.sub.6 MoO.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 BaCo.sub.3 18.7 18.7 18.7 3.8 2.5 6.3 31.373 Mg.sub.2 Mo.sub.3 O.sub.11 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 MgCo.sub.3 12.4 12.4 8.3 8.3 41.5 16.7 0.474 Ca.sub.3 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 MgCo.sub.3 7.1 14.3 14.3 7.1 28.6 21.4 7.275 Sr.sub.3 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 MgCo.sub.3 12.3 12.3 9.2 9.2 18.4 26.4 12.276 BaMo.sub.2 O.sub.7 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 MgCo.sub.3 15.3 15.3 15.3 15.3 15.3 0.4 23.177 ZnMo.sub.2 O.sub.7 La.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 BaF.sub.2 MgCo.sub.3 13.3 6.7 20.0 20.0 6.7 6.7 26.678 Zn.sub.3 Mo.sub.2 O.sub.9 Pr.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 MgCo.sub.3 8.8 14.7 20.6 12.4 2.4 11.7 29.479 ZnMoO.sub.4 Nd.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 BaF.sub.2 CaCo.sub.3 7.7 7.7 7.7 15.3 38.3 22.9 0.480 ZnMo.sub.2 O.sub.7 Sm.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 CaCo.sub.3 9.8 9.8 9.8 9.8 26.1 28.1 6.681 Zn.sub.3 Mo.sub.2 O.sub.9 Eu.sub.2 MoO.sub.6 HfMo.sub.2 O.sub.8 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 12.4 16.6 12.4 16.6 24.9 0.4 16.182 ZnMoO.sub.4 Gd.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 14.3 14.3 14.3 14.3 14.3 7.1 21.483 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 CaCo.sub.3 15.6 15.6 12.5 12.5 6.3 12.5 25.084 Zn.sub.3 Mo.sub.2 O.sub.9 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 13.3 13.3 13.3 13.3 2.2 16.7 27.985 ZnMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 SrCo.sub.3 7.0 7.0 7.0 13.9 34.8 30.0 0.386 ZnMo.sub.2 O.sub.7 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 13.6 13.6 13.6 13.6 36.2 0.4 9.087 Tb.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub. 8 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 SrCo.sub.3 11.5 15.4 11.5 15.4 23.1 7.7 15.488 Dy.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 13.3 13.3 13.3 13.3 13.3 13.4 20.189 Ho.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 11.8 11.8 11.8 17.6 5.9 17.6 23.590 Er.sub.6 MoO.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 12.4 12.4 12.4 12.4 2.0 22.4 26.091 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 BaCo.sub.3 9.9 19.8 9.9 9.9 49.5 0.5 0.592 MgMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.4 Tm.sub. 6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 SrF.sub.2 BaCo.sub.3 8.3 16.7 8.3 8.3 8.3 33.4 8.3 8.493 CaMoO.sub.4 ZnMoO.sub.4 Yb.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 BaCo.sub.3 7.1 14.3 14.3 7.1 7.1 21.5 14.3 14.394 SrMoO.sub.4 ZnMo.sub.2 O.sub.7 Lu.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 MnMoO.sub.4 SrF.sub.2 BaCo.sub.3 12.5 12.5 12.5 6.3 6.3 12.5 18.7 18.795 BaMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.9 Y.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 BaCo.sub.3 10.9 5.5 10.9 10.9 10.9 5.5 23.5 21.996 Mg.sub.2 Mo.sub.3 O.sub.11 ZnMoO.sub.4 La.sub.2 MoO.sub.6 HfMo.sub.2 O.sub.8 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 13.3 10.6 13.3 13.3 13.3 2.6 0.3 33.397 Ca.sub.3 MoO.sub.6 ZnMo.sub.2 O.sub.7 Pr.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 MgCo.sub.3 9.0 9.0 9.0 9.0 9.0 45.3 9.2 0.598 Sr.sub.3 MoO.sub.6 Zn.sub.3 Mo.sub.2 O.sub.9 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 BaF.sub.2 MgCo.sub.3 7.7 7.7 15.4 7.7 7.7 30.8 15.4 7.699 Ba.sub.3 MoO.sub.4 ZnMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 BaF.sub.2 MgCo.sub.3 6.7 13.3 13.3 6.7 6.7 20.0 20.0 13.3100 MgMoO.sub.4 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 MgCo.sub.3 5.8 11.6 11.6 11.6 5.8 11.6 24.8 17.2101 CaMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.9 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 MgCo.sub.3 14.2 14.2 14.2 14.2 7.1 7.1 0.4 28.6102 SrMoO.sub.4 Ce.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MgF.sub.2 MgCo.sub.3 12.5 12.5 12.5 12.5 10.0 2.5 6.2 31.3103 BaMoO.sub.4 Pr.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 8.3 8.3 8.3 8.3 8.3 41.5 16.6 0.4104 Mg.sub.2 Mo.sub.3 O.sub.11 Nd.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 7.1 7.1 7.1 7.1 14.3 28.6 21.5 7.7105 Ca.sub.3 MoO.sub.6 Sm.sub.2 Mo.sub.2 O.sub.7 HfMo.sub.2 O.sub. 8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 MgF.sub.2 CaCo.sub.3 6.1 6.1 6.1 12.3 12.3 18.4 26.4 12.3106 Sr.sub.3 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 CaCo.sub.3 7.7 15.3 15.3 15.3 7.7 15.3 0.4 23.0107 ZnMoO.sub.4 Eu.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 CaF.sub.2 CaCo.sub.3 6.7 13.3 13.3 13.3 13.3 6.7 6.7 26.7108 ZnMo.sub.2 O.sub.7 Gd.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 MnMoO.sub.4 CaF.sub.2 CaCo.sub.3 9.4 11.8 11.8 11.8 11.8 2.3 11.7 29.4109 Zn.sub.3 Mo.sub.2 O.sub.9 Tb.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 7.7 7.7 7.7 7.7 7.7 30.3 22.9 0.3110 ZnMoO.sub.4 Dy.sub.6 MoO.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 CaF.sub.2 SrCo.sub.3 6.5 13.1 6.5 6.5 6.5 26.2 28.1 6.6111 ZnMo.sub.2 O.sub.7 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 SrCo.sub.3 16.6 16.6 8.3 8.3 8.3 24.9 0.4 16.6112 Ho.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 SrCo.sub.3 14.3 14.3 14.3 7.1 7.1 14.3 7.1 21.5113 MgMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.9 Er.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 SrF.sub.2 SrCo.sub.3 6.3 12.5 12.5 12.5 6.3 6.3 6.3 12.4 24.9114 CaMoO.sub.4 ZnMoO.sub.4 Tm.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 MnMoO.sub.4 SrF.sub.2 SrCo.sub.3 5.6 11.1 11.1 20 8.9 9.6 2.2 16.7 27.7115 SrMoO.sub.4 ZnMo.sub.2 O.sub.7 Yb.sub.6 MoO.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 SrF.sub.2 BaCo.sub.3 3.5 3.5 7.0 7.0 7.0 7.0 34.8 29.9 0.3116 BaMoO.sub.4 Zn.sub.3 Mo.sub.2 O.sub.9 Lu.sub.6 MoO.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 9.0 9.0 9.0 9.0 9.0 9.0 36.3 0.5 9.2117 Mg.sub.2 Mo.sub.3 O.sub.11 ZnMoO.sub.4 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 15.4 7.7 7.7 7.7 7.7 7.7 23.1 7.7 15.3118 Ca.sub.3 MoO.sub.6 Y.sub.2 Mo.sub.3 O.sub.12 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 13.3 13.3 6.7 6.7 6.7 6.7 13.3 13.3 20.0119 ZnMo.sub.2 O.sub.7 La.sub.2 MoO.sub.6 Al.sub.2 Mo.sub.3 O.sub.12 HfMo.sub.2 O.sub.8 Ta.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 11.8 11.8 11.8 5.9 5.9 5.9 5.8 17.6 23.5120 Sr.sub.3 MoO.sub.6 Zn.sub.3 Mo.sub.2 O.sub.9 CeMo.sub.2 O.sub.8 Al.sub.2 Mo.sub.3 O.sub.12 ZrMo.sub.2 O.sub.8 Nb.sub.2 Mo.sub.3 O.sub.14 MnMoO.sub.4 BaF.sub.2 BaCo.sub.3 5.2 5.2 5.2 9.2 10.3 10.3 8.3 2.1 22.3 25.9__________________________________________________________________________
It is understood that Tables 2 to 8 correspond to the groups (A) to (G), and Table 9 indicates the proportions of the components selected from two or more groups.
The respective samples of the aforesaid components were heat-treated at 1000.degree. C. for 1 hour in a gaseous atmosphere consisting of 98.5% by volume of nitrogen (N.sub.2) and 1.5% by volume of hydrogen (H.sub.2), and were thereafter pulverized together with ethanol in a pot mill and dried to obtain the heat-treated resistor material powders having a particle size of 10 .mu.m and composed of the glass, the molybdates of the corresponding elements and the fluorides of alkaline earth metals.
The respective samples were then mixed with the carbonates of alkaline earth metals in the proportions specified in the tables. After mixing, 25 parts by weight of the organic vehicle (90 parts by weight of butyl carbitol plus 10 parts by weight of ethyl cellulose) were added to and mixed with 100 parts by weight of the resulting powdery mixtures in a ball mill to obtain the respective resistor material pastes.
On the other hand, 8 parts by weight of polyvinyl buryral, 8 parts by weight of diethyl phthalate, 0.5 parts by weight of oleic acid, 10 parts by weight of acetone, 20 parts by weight of isopropyl alcohol and 20 parts by weight of methyl ethyl ketone were added to and mixed with 100 parts by weight of ceramic material powders consisting of 40.0% by weight of Al.sub.2 O.sub.3, 35.0% by weight of SiO.sub.2, 13.0% by weight of B.sub.2 O.sub.3, 7.0% by weight of CaO and 5.0% by weight of MgO by means of a ball mill to prepare a slurry, which was defoamed. Thereafter, the slurry was formed by the doctor blade process into a long ceramic green sheet of 200 .mu.m in thickness. Cut out of this ceramic green sheet were a green sheet piece of 9 mm.times.9 mm and a green sheet piece of 6 mm.times.9 mm.
As shown in FIG. 1, printed on the aforesaid green sheet 1 piece 1 of 9 mm.times.9 mm was a conductive material paste by means of screen printing, which was obtained by adding as the organic vehicle 20 parts by weight of butyl carbitol and 5 parts by weight of ethyl cellulose to 95 parts by weight of copper powders and 5 parts by weight of glass frit, followed by three-roll milling. The conductive paste printed ceramic green sheet piece 1 was dried at 125.degree. C. for 10 minutes to form a conductive material film 2. Next, each of the aforesaid respective resistive material pastes was similarly screen-printed on the aforesaid green sheet piece 1 by the screen process, and was dried at 125.degree. C. for 10 minutes to form a resistor material film 3 for a thick-film resistor.
Then, the aforesaid green sheet piece 4 of 6 mm.times.9 mm was laminated upon the green sheet piece 1, as shown by a chain dash, at 100.degree. C. and 150 Kg/cm.sup.2. Subsequently, the laminated product was heated at 400.degree. to 500.degree. C. in an oxidizing atmosphere of, e.g., air to decompose and burn off the organics remaining in the green sheet pieces 1,4, the conductive film 2 and the resistive film 3.
After decomposing the organics in this manner, they were fired at 950.degree. C. for 1 hour in a gaseous mixture consisting of 98.5% by volume of N.sub.2 and 1.5% by volume of H.sub.2 to obtain an integral multilayered ceramic board having a porcelain 1a formed of the sintered body of the green sheet piece 1, a porcelain layer 4a formed of the sintered body of the green sheet piece 4, a thick-film conductor 2a formed of the sintered body of the conductive film 2 and a thick-film resistor 3a formed of the sintered resistive film 3 located between the layers 1 and 4, as illustrated in FIG. 3. With regard to this multilayered ceramic board, such warping or swelling as shown in FIGS. 4 and 5 were not found, as will be described later.
The thus obtained multilayered ceramic board was polished in its layer direction to expose the resistor layer to view, which was then analized by X-ray diffraction (Cu K alpha rays). The results of Sample No. 1 obtained are shown in FIG. 6, from which the presence of the molybdate of the corresponding element could be ascertained. FIG. 7 is also a TEM photograph taken of said sample, which shows the acicular particles that are the reduction product of the molybdate of magnesium. In the photograph, the molybdate of magnesium is shown by a black portion on the left side, and the glass is indicated by a gray portion on the upper side. It is to be noted that the sample, of which a TEM photograph was taken, was prepared by cutting the multilayered ceramic board in the sectional direction to a band of 200 .mu.m in width, and polishing the band to a thickness of about 20 .mu.m, followed by thinning with an ion milling device. Although not illustrated and described, similar results could also be confirmed with respect to other samples.
Next, the resistance values (R.sub.25) and (R.sub.125) of the thick-film resistor 3a at 25.degree. C. and at the time when heated to 125.degree. C. were measured with a digital multimeter, and the temperature coefficient of resistance (TCR) was calculated from the following equation: ##EQU1##
The measured resistance values R.sub.25 and calculated values TCR are shown in Table 10 for the compositions of Table 2 and, similarly, in Tables 11 to 17 for the compositions of Tables 3 to 9.
After the obtained multilayered ceramic board had been permitted to stand at 60.degree. C. and a relative humidity of 95% for 1000 hours, its resistance at 25.degree. C. was measured to determine the rate of change with respect to the resistance at 25.degree. C. Just as mentioned above, the results are shown in the tables.
With resistor material samples obtained by removing the carbonates and fluorides of alkaline earth metals, and by removing the former only from the aforesaid respective resistor material samples, multilayered ceramic boards were prepared and measured in the same manner as mentioned above. The results are set forth in Tables 10 to 17 with the sample numbers corresponding to the sample numbers of the 1st column in the 2nd and 3rd columns of Tables 10 to 17.
TABLE 10__________________________________________________________________________(Characteristic values corresponding to the sample in Table 2)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value at Change in value at Change in value at Change in 25.degree. C. R.sub.25 TCR Resistance 25.degree. C. R.sub.25 TCR Resistance 25.degree. C. TCRub.25 ResistanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 8.35 .times. 10.sup.3 -286 <.+-.2 22.6 .times. 10.sup.3 -511 <.+-.2 18.5 .times. 10.sup.3 -831 <.+-.2 2 5.28 .times. 10.sup.3 -252 " 14.9 .times. 10.sup.3 -496 " 9.24 .times. 10.sup.3 -529 " 3 2.15 .times. 10.sup.3 -192 " 72.3 .times. 10.sup.3 -424 " 4.11 .times. 10.sup.3 -508 " 4 1.02 .times. 10.sup.3 -161 " 4.55 .times. 10.sup.3 -326 " 2.36 .times. 10.sup.3 -456 " 5 6.49 .times. 10.sup.3 -274 " 13.8 .times. 10.sup.3 -405 " 9.21 .times. 10.sup.3 -530 " 6 1.58 .times. 10.sup.3 -173 " 6.98 .times. 10.sup.3 -369 " 4.07 .times. 10.sup.3 -511 " 7 3.58 .times. 10.sup.3 -248 " 10.2 .times. 10.sup.3 -502 " 12.6 .times. 10.sup.3 -542 " 8 2.73 .times. 10.sup.3 -205 " 8.24 .times. 10.sup.3 -498 " 2.03 .times. 10.sup.3 -501 " 9 1.03 .times. 10.sup.3 -168 " 7.44 .times. 10.sup.3 -472 " 1.99 .times. 10.sup.3 -499 " 10 1.18 .times. 10.sup.3 -177 " 8.34 .times. 10.sup.3 -499 " 4.07 .times. -511up.3 " 11 899 -89 " 5.21 .times. 10.sup.3 -470 " 2.03 .times. 10.sup.3 -501 " 12 925 -97 " 4.49 .times. 10.sup.3 -462 " 1.97 .times. 10.sup.3 -498 " 13 676 -25 " 3.32 .times. 10.sup.3 -454 " 3.12 .times. 10.sup.3 -505 " 14 4.03 .times. 10.sup.3 -270 " 11.5 .times. 10.sup.3 -504 " 12.6 .times. 10.sup.3 -542 " 15 2.88 .times. 10.sup.3 -211 " 8.27 .times. 10.sup.3 -498 " 2.03 .times. 10.sup.3 -501 " 16 2.91 .times. 10.sup.3 -218 " 7.98 .times. 10.sup.3 -483 " 1.99 .times. 10.sup.3 -499 " 17 3.10 .times. 10.sup.3 -229 " 8.20 .times. 10.sup.3 -497 " 4.07 .times. 10.sup.3 -511 " 18 1.03 .times. 10.sup.3 -159 " 7.52 .times. 10.sup.3 -474 " 2.03 .times. 10.sup.3 -501 " 19 1.57 .times. 10.sup.3 -198 " 8.01 .times. 10.sup.3 -487 " 1.97 .times. 10.sup.3 -498 " 20 755 -71 " 8.13 .times. 10.sup.3 -492 " 3.12 .times. 10.sup.3 -505 " 21 980 -135 " 8.28 .times. 10.sup.3 -498 " 4.07 .times. 10.sup.3 -511 " 22 805 -75 " 7.73 .times. 10.sup.3 -482 " 1.97 .times. 10.sup.3 -498 " 23 953 -109 " 7.99 .times. 10.sup.3 -494 " 4.07 .times. 10.sup.3 -511 " 24 785 -70 " 7.66 .times. 10.sup.3 -475 " 1.97 .times. 10.sup.3 -498 " 25 1.09 .times. 10.sup.3 -171 " 11.9 .times. 10.sup.3 -510 " 4.07 .times. 10.sup.3 -511 " 26 867 -81 " 7.92 .times. 10.sup.3 -482 " 1.97 .times. 10.sup.3 -498 " 27 4.73 .times. 10.sup.3 -281 " 8.10 .times. 10.sup.3 -491 " 2.42 .times. 10.sup.3 -503 " 28 1.13 .times. 10.sup.3 -125 " 7.50 .times. 10.sup.3 -472 " 2.03 .times. 10.sup.3 -501 " 29 3.00 .times. 10.sup.3 -229 " 8.06 .times. 10.sup.3 -488 " 2.42 .times. 10.sup.3 -503 " 30 854 -77 " 7.14 .times. 10.sup.3 -452 " 2.03 .times. 10.sup.3 -501 " 31 3.95 .times. 10.sup.3 -248 " 8.09 .times. 10.sup.3 -489 " 2.42 .times. 10.sup.3 -503 " 32 953 -98 " 7.21 .times. 10.sup.3 -463 " 2.03 .times. 10.sup.3 -501 " 33 3.02 .times. 10.sup.3 -221 " 7.75 .times. 10.sup.3 -484 " 2.03 .times. 10.sup.3 -507 " 34 3.77 .times. 10.sup.3 -248 " 8.15 .times. 10.sup.3 -492 " 4.07 .times. 10.sup.3 -511 " 35 9.34 .times. 10.sup.3 233 " 14.6 .times. 10.sup.3 502 " 12.9 .times. 10.sup.3 -744 " 36 5.68 .times. 10.sup.3 164 " 9.28 .times. 10.sup.3 321 " 7.11 .times. 10.sup.3 -516 " 37 1.04 .times. 10.sup.3 98 " 4.67 .times. 10.sup.3 216 " 2.07 .times. 10.sup.3 -440 " 38 923 87 " 3.34 .times. 10.sup.3 173 " 1.09 .times. 10.sup.3 -395 " 39 3.24 .times. 10.sup.3 121 " 8.89 .times. 10.sup.3 288 " 7.14 .times. 10.sup.3 -512 " 40 1.89 .times. 10.sup.3 113 " 5.11 .times. 10.sup.3 244 " 2.06 .times. 10.sup.3 -438 " 41 2.05 .times. 10.sup.3 -153 " 5.14 .times. 10.sup.3 -478 " 5.23 .times. 10.sup.3 -482 " 42 1.03 .times. 10.sup.3 -108 " 2.05 .times. 10.sup.3 -418 " 1.52 .times. 10.sup.3 -421 " 43 847 -83 " 1.23 .times. 10.sup.3 -384 " 1.14 .times. 10.sup.3 -397 " 44 980 -89 " 1.62 .times. 10.sup.3 -392 " 2.07 .times. 10.sup.3 -440 " 45 658 -41 " 1.54 .times. 10.sup.3 -388 " 1.48 .times. 10.sup.3 -420 " 46 723 -37 " 1.47 .times. 10.sup.3 -384 " 1.21 .times. 10.sup.3 -399 " 47 521 -5 " 1.14 .times. 10.sup.3 -381 " 1.10 .times. 10.sup.3 -395 " 48 1.23 .times. 10.sup.3 -98 " 2.09 .times. 10.sup.3 -436 " 2.07 .times. 10.sup.3 -440 " 49 705 -59 " 1.32 .times. 10.sup.3 -383 " 1.21 .times. 10.sup.3 -399 " 50 915 -78 " 2.10 .times. 10.sup.3 -434 " 2.07 .times. 10.sup.3 -440 " 51 625 -38 " 1.25 .times. 10.sup.3 -382 " 1.21 .times. 10.sup.3 -399 " 52 1.01 .times. 10.sup.3 -95 " 2.13 .times. 10.sup.3 -438 " 2.07 .times. 10.sup.3 -440 " 53 688 -50 " 1.82 .times. 10.sup.3 -401 " 1.21 .times. 10.sup.3 -399 " 54 3.77 .times. 10.sup.3 - 230 " 4.05 .times. 10.sup.3 -444 " 1.54 .times. 10.sup.3 -422 " 55 991 -100 " 2.03 .times. 10.sup.3 -417 " 1.48 .times. 10.sup.3 -420 " 56 2.01 .times. 10.sup.3 -131 " 3.49 .times. 10.sup.3 -421 " 1.54 .times. 10.sup.3 -422 " 57 795 -50 " 2.09 .times. 10.sup.3 -418 " 1.48 .times. 10.sup.3 -420 " 58 2.95 .times. 10.sup.3 -185 " 3.63 .times. 10.sup.3 -423 " 1.54 .times. 10.sup.3 -422 " 59 888 -55 " 2.02 .times. 10.sup.3 -417 " 1.48 .times. 10.sup.3 -420 " 60 1.45 .times. 10.sup.3 -129 " 3.51 .times. 10.sup.3 -421 " 1.48 .times. 10.sup.3 -420 " 61 1.01 .times. 10.sup.3 -120 " 4.25 .times. 10.sup. 3 -445 " 2.07 .times. 10.sup.3 -440 " 62 1.63 .times. 10.sup.3 -136 " 4.50 .times. 10.sup.3 369 " 2.22 .times. 10.sup.3 -451 " 63 2.49 .times. 10.sup.3 -203 " 4.82 .times. 10.sup.3 -458 " 4.08 .times. 10.sup.3 -462 " 64 30.2 .times. 10.sup.3 +32 " 70.5 .times. 10.sup.3 -321 " 97.5 .times. 10.sup.3 -829 " 65 27.9 .times. 10.sup.3 +49 " 59.7 .times. 10.sup.3 -286 " 25.6 .times. 10.sup.3 -519 " 66 18.4 .times. 10.sup.3 +116 " 36.5 .times. 10.sup.3 -224 " 12.3 .times. 10.sup.3 -268 " 67 2.54 .times. 10.sup.3 +223 " 4.39 .times. 10.sup.3 -63 " 1.86 .times. 10.sup.3 -85 " 68 26.8 .times. 10.sup.3 +52 " 49.3 .times. 10.sup.3 -218 " 27.4 .times. 10.sup.3 -436 " 69 22.4 .times. 10.sup.3 +73 " 37.2 .times. 10.sup.3 -163 " 12.4 .times. 10.sup.3 -270 " 70 40.5 .times. 10.sup.3 +52 " 62.7 .times. 10.sup.3 -462 " 42.3 .times. 10.sup.3 -639 " 71 32.5 .times. 10.sup.3 +80 " 45.6 .times. 10.sup.3 -233 " 8.26 .times. 10.sup.3 -248 " 72 14.8 .times. 10.sup.3 +125 " 32.8 .times. 10.sup.3 -196 " 7.42 .times. 10.sup.3 -236 " 73 17.3 .times. 10.sup.3 +103 " 40.5 .times. 10.sup.3 -214 " 12.4 .times. 10.sup.3 -270 " 74 7.25 .times. 10.sup.3 +178 " 47.6 .times. 10.sup.3 -240 " 8.26 .times. 10.sup.3 -248 " 75 9.00 .times. 10.sup.3 +175 " 42.1 .times. 10.sup.3 -221 " 6.98 .times. 10.sup.3 -230 " 76 856 +255 " 2.04 .times. 10.sup.3 -99 " 2.23 .times. 10.sup.3 -103 " 77 43.1 .times. 10.sup.3 +26 " 59.4 .times. 10.sup.3 -398 " 42.3 .times. 10.sup.3 -639 " 78 35.1 .times. 10.sup.3 +62 " 41.8 .times. 10.sup.3 -218 " 8.26 .times. 10.sup.3 -248 " 79 19.4 .times. 10.sup.3 +79 " 34.5 .times. 10.sup.3 -199 " 7.42 .times. 10.sup.3 -236 " 80 21.7 .times. 10.sup.3 +88 " 43.2 .times. 10.sup.3 -224 " 12.4 .times. 10.sup.3 -270 " 81 9.85 .times. 10.sup.3 +102 " 32.9 .times. 10.sup.3 -198 " 8.26 .times. 10.sup.3 -248 " 82 10.6 .times. 10.sup.3 +105 " 30.5 .times. 10.sup.3 -186 " 6.98 .times. 10.sup.3 -230 " 83 1.03 .times. 10.sup.3 +205 " 1.85 .times. 10.sup.3 -87 " 2.23 .times. 10.sup.3 -103 " 84 20.5 .times. 10.sup.3 +95 " 44.6 .times. 10.sup.3 -225 " 12.4 .times. 10.sup.3 -270 " 85 12.3 .times. 10.sup.3 +120 " 31.2 .times. 10.sup.3 -196 " 6.98 .times. 10.sup.3 -230 " 86 16.1 .times. 10.sup.3 +111 " 38.7 .times. 10.sup.3 -210 " 12.4 .times. 10.sup.3 -270 " 87 6.99 .times. 10.sup.3 +181 " 30.9 .times. 10.sup.3 -187 " 6.98 .times. 10.sup.3 -230 " 88 19.7 .times. 10.sup.3 +98 " 50.2 .times. 10.sup.3 -246 " 12.4 .times. 10.sup.3 -270 " 89 10.8 .times. 10.sup.3 +179 " 29.6 .times. 10.sup.3 -185 " 6.98 .times. 10.sup.3 -230 " 90 4.27 .times. 10.sup.3 -55 " 51.3 .times. 10.sup.3 -248 " 8.82 .times. 10.sup.3 -252 " 91 10.3 .times. 10.sup.3 +149 " 21.6 .times. 10.sup.3 -152 " 8.26 .times. 10.sup.3 -248 " 92 39.5 .times. 10.sup.3 -60 " 54.9 .times. 10.sup.3 -250 " 8.82 .times. 10.sup.3 -252 " 93 8.08 .times. 10.sup.3 +153 " 27.4 .times. 10.sup.3 -172 " 8.26 .times. 10.sup.3 -248 " 94 40.9 .times. 10.sup.3 -39 " 48.6 .times. 10.sup.3 -245 " 8.82 .times. 10.sup.3 -252 " 95 8.91 .times. 10.sup.3 +160 " 28.2 .times. 10.sup. 3 -180 " 8.26 .times. 10.sup.3 -248 " 96 34.4 .times. 10.sup.3 +71 " 42.5 .times. 10.sup.3 -222 " 8.26 .times. 10.sup.3 -248 " 97 20.9 .times. 10.sup.3 +95 " 50.0 .times. 10.sup.3 -246 " 12.4 .times. 10.sup.3 -270 " 98 68.2 .times. 10.sup.3 -234 " 97.6 .times. 10.sup.3 -463 " 100.6 .times. 10.sup.3 -957 " 99 27.3 .times. 10.sup.3 -92 " 46.5 .times. 10.sup.3 -413 " 32.4 .times. 10.sup.3 -607 "100 20.8 .times. 10.sup.3 -74 " 34.8 .times. 10.sup.3 -296 " 21.4 .times. 10.sup.3 -483 "101 6.24 .times. 10.sup.3 -25 " 10.7 .times. 10.sup.3 -152 " 5.37 .times. 10.sup.3 -195 "102 27.6 .times. 10.sup.3 - 96 " 35.2 .times. 10.sup.3 -274 " 32.9 .times. 10.sup.3 -436 "103 18.8 .times. 10.sup.3 -48 " 29.6 .times. 10.sup.3 -304 " 21.1 .times. 10.sup.3 -490 "104 45.4 .times. 10.sup.3 -127 " 63.2 .times. 10.sup.3 -512 " 68.2 .times. 10.sup.3 -802 "105 36.6 .times. 10.sup.3 -83 " 45.2 .times. 10.sup.3 -262 " 12.5 .times. 10.sup.3 -271 "106 19.6 .times. 10.sup.3 -18 " 30.4 .times. 10.sup.3 -241 " 7.24 .times. 10.sup.3 -243 "107 22.1 .times. 10.sup.3 -77 " 51.3 .times. 10.sup.3 -462 " 21.4 .times. 10.sup.3 -483 "108 9.90 .times. 10.sup.3 -55 " 30.3 .times. 10.sup.3 -241 " 6.96 .times. 10.sup.3 -338 "109 12.3 .times. 10.sup.3 -37 " 17.7 .times. 10.sup.3 -200 " 6.12 .times. 10.sup.3 -219 "110 1.87 .times. 10.sup.3 -60 " 32.8 .times. 10.sup.3 -254 " 8.63 .times. 10.sup.3 -262 "111 20.8 .times. 10.sup.3 -75 " 54.2 .times. 10.sup.3 -472 " 21.1 .times. 10.sup.3 -490 "112 9.85 .times. 10.sup.3 -28 " 45.3 .times. 10.sup.3 -264 " 12.3 .times. 10.sup.3 -270 "113 18.6 .times. 10.sup.3 -60 " 56.3 .times. 10.sup.3 -481 " 21.1 .times. 10.sup.3 -490 "114 9.12 .times. 10.sup.3 -29 " 17.4 .times. 10.sup.3 -198 " 6.12 .times. 10.sup.3 -219 "115 21.2 .times. 10.sup.3 -68 " 54.3 .times. 10.sup.3 -472 " 21.4 .times. 10.sup.3 -483 "116 11.5 .times. 10.sup.3 -35 " 18.6 .times. 10.sup.3 -209 " 6.12 .times. 10.sup.3 -219 "117 43.6 .times. 10.sup.3 -188 " 47.9 .times. 10.sup.3 -306 " 14.6 .times. 10.sup.3 -302 "118 11.5 .times. 10.sup.3 -58 " 28.9 .times. 10.sup.3 -225 " 6.96 .times. 10.sup.3 -233 "119 38.5 .times. 10.sup.3 -107 " 44.6 .times. 10.sup.3 -292 " 14.6 .times. 10.sup.3 -302 "120 9.05 .times. 10.sup.3 -51 " 29.3 .times. 10.sup.3 -230 " 6.96 .times. 10.sup.3 -233 "121 34.5 .times. 10.sup.3 -95 " 42.3 .times. 10.sup.3 -290 " 14.6 .times. 10.sup.3 -302 "122 7.88 .times. 10.sup.3 -50 " 29.5 .times. 10.sup.3 -231 " 6.96 .times. 10.sup.3 -233 "123 38.3 .times. 10.sup.3 -107 " 30.2 .times. 10.sup.3 -236 " 6.96 .times. 10.sup.3 -233 "124 22.5 .times. 10.sup.3 -89 " 55.4 .times. 10.sup.3 -472 " 21.4 .times. 10.sup.3 -483 "125 4.73 .times. 10.sup.3 -42 " 48.6 .times. 10.sup.3 -321 " 3.62 .times. 10.sup.3 -138 "126 21.9 .times. 10.sup.3 -55 " 48.6 .times. 10.sup.3 -321 " 16.9 .times. 10.sup.3 -324 "127 2.22 .times. 10.sup.3 -126 " 3.48 .times. 10.sup.3 -324 " 2.36 .times. 10.sup.3 -626 "128 1.76 .times. 10.sup.3 -83 " 2.32 .times. 10.sup.3 -302 " 1.90 .times. 10.sup.3 -490 "129 893 +64 " 1.26 .times. 10.sup.3 -236 " 619 -251 "130 562 +52 " 763 - 103 " 488 +55 "131 2.04 .times. 10.sup.3 -109 " 2.88 .times. 10.sup.3 -318 " 1.92 .times. 10.sup.3 -505 "132 724 -63 " 846 -193 " 621 -250 "133 841 -216 " 1.25 .times. 10.sup.3 -493 " 2.35 .times. 10.sup.3 -732 "134 803 -185 " 1.09 .times. 10.sup.3 -240 " 492 -241 "135 596 -107 " 954 -236 " 468 -238 "136 608 -106 " 1.12 .times. 10.sup.3 -248 " 621 -250 "137 442 +56 " 974 -238 " 492 -241 "138 438 +58 " 968 -237 " 474 -239 "139 396 +95 " 942 -232 " 442 -235 "140 839 -238 " 1.22 .times. 10.sup.3 -487 " 2.35 .times. 10.sup.3 -732 "141 798 -198 " 1.10 .times. 10.sup.3 -242 " 492 -241 "142 597 -115 " 969 -237 " 468 -238 "143 603 -118 " 1.14 .times. 10.sup.3 -248 " 621 -250 "144 438 +5 " 975 -238 " 492 -241 "145 441 -15 " 965 -237 " 474 -239 "146 390 +21 " 948 -233 " 442 -235 "147 705 -159 " 1.16 .times. 10.sup.3 -249 " 621 -250 "148 509 -56 " 964 -236 " 474 -239 "149 617 -111 " 1.13 .times. 10.sup.3 -248 " 621 -250 "150 459 +41 " 968 -237 " 474 -239 "151 668 -140 " 1.18 .times. 10.sup.3 -252 " 621 -250 "152 481 +36 " 970 -237 " 474 -239 "153 636 -119 " 973 -237 " 470 -238 "154 481 -5 " 976 -238 " 492 -241 "155 578 -106 " 975 -239 " 470 -238 "156 425 -9 " 977 -238 " 492 -241 "157 615 -120 " 982 -240 " 470 -238 "158 469 -20 " 974 -239 " 492 -241 "159 846 -221 " 1.01 .times. 10.sup.3 -243 " 492 -241 "160 641 -152 " 977 -239 " 621 -239 "161 3.95 .times. 10.sup.3 -212 " 8.94 .times. 10.sup.3 -324 " 4.66 .times. 10.sup.3 -677 "162 3.23 .times. 10.sup.3 -186 " 6.62 .times. 10.sup.3 -295 " 3.51 .times. 10.sup.3 -525 "163 1.24 .times. 10.sup.3 -152 " 4.63 .times. 10.sup.3 -251 " 1.19 .times. 10.sup.3 -400 "164 886 -82 " 1.64 .times. 10.sup.3 -183 " 728 -305 "165 3.65 .times. 10.sup.3 -205 " 6.49 .times. 10.sup.3 -294 " 3.54 .times. 10.sup.3 -520 "166 2.02 .times. 10.sup.3 -163 " 3.28 .times. 10.sup.3 -198 " 1.22 .times. 10.sup.3 -398 "167 852 -235 " 2.62 .times. 10.sup.3 -498 " 4.12 .times. 10.sup.3 -612 "168 814 -204 " 2.18 .times. 10.sup.3 -352 " 983 -354 "169 605 -113 " 1.94 .times. 10.sup.3 -331 " 842 -332 "170 619 -119 " 2.25 .times. 10.sup.3 -397 " 1.19 .times. 10.sup.3 -400 "171 453 -55 " 2.10 .times. 10.sup.3 -357 " 983 -354 "172 449 -51 " 1.65 .times. 10.sup.3 -321 " 815 -324 "173 407 -32 " 1.42 .times. 10.sup.3 -304 " 734 -307 "174 634 -124 " 2.24 .times. 10.sup.3 -397 " 1.19 .times. 10.sup.3 -400 "175 463 -60 " 1.70 .times. 10.sup.3 -322 " 815 -324 "176 594 -108 " 2.21 .times. 10.sup.3 -396 " 1.19 .times. 10.sup.3 -400 "177 426 -49 " 1.51 .times. 10.sup.3 -320 " 815 -324 "178 581 -94 " 2.28 .times. 10.sup.3 -399 " 1.19 .times. 10.sup.3 -400 "179 407 -35 " 1.60 .times. 10.sup.3 -321 " 815 -324 "180 664 -185 " 2.18 .times. 10.sup.3 -369 " 997 -400 "181 499 -115 " 1.99 .times. 10.sup.3 -353 " 983 -324 "182 617 -124 " 2.12 .times. 10.sup.3 -367 " 997 -368 "183 469 -100 " 2.10 .times. 10.sup.3 -352 " 983 -354 "184 631 -153 " 2.21 .times. 10.sup.3 -370 " 997 -368 "185 481 -85 " 2.09 .times. 10.sup.3 -352 " 983 -354 "186 837 -236 " 2.07 .times. 10.sup.3 -356 " 983 -354 "187 639 -169 " 2.30 .times. 10.sup.3 -398 " 1.19 .times. 10.sup.3 -400 "188 592 -83 " 1.03 .times. 10.sup.3 -203 " 608 -252 "189 453 -40 " 1.99 .times. 10.sup.3 -338 " 906 -341 "190 875 -109 " 1.58 .times. 10.sup.3 -163 " 706 +148 "191 652 -17 " 1.36 .times. 10.sup.3 -124 " 518 +287 "192 426 +74 " 924 +320 " 270 +401 "193 349 +108 " 763 +263 " 196 +428 "194 775 -28 " 1.40 .times. 10.sup.3 +318 " 520 +290 "195 328 +107 " 863 +318 " 270 +505 "196 525 +55 " 682 +184 " 652 +182 "197 490 +83 " 820 +428 " 235 +582 "198 321 +105 " 852 +462 " 213 +589 "199 285 +118 " 802 +412 " 270 +505 "200 141 +267 " 830 +445 " 224 +584 "201 94 +300 " 860 +482 " 202 +598 "202 341 +108 " 801 +410 " 270 +505 "203 310 +111 " 802 +411 " 270 +505 "204 335 +105 " 801 +409 " 270 +505 "205 182 +250 " 835 +452 " 224 +584 "206 131 +273 " 854 +463 " 224 +584 "207 115 +295 " 857 +471 " 224 +505 "208 503 +90 " 822 +430 " 232 +584 "209 495 +88 " 818 +425 " 232 +582 "210 508 +97 " 824 +438 " 232 +582 "211 932 -83 " 1.65 .times. 10.sup.3 -164 " 761 +108 "212 729 -65 " 1.29 .times. 10.sup.3 -142 " 588 +144 "213 544 +86 " 962 +242 " 380 +273 "214 428 +132 " 743 +264 " 254 +326 "215 583 +25 " 721 +124 " 675 +126 "216 512 +28 " 542 +300 " 289 +302 "217 351 +100 " 628 +272 " 380 +273 "218 296 +233 " 423 +316 " 265 +318 "219 181 +279 " 446 +313 " 274 +314 "220 120 +286 " 404 +318 " 260 +320 "221 329 +109 " 635 +271 " 380 +273 "222 318 +96 " 648 +270 " 380 +273 "223 342 +108 " 672 +272 " 380 +273 "224 245 +240 " 405 +310 " 274 +314 "225 195 +268 " 453 +312 " 274 +314 "226 212 +259 " 398 +311 " 274 +314 "227 325 +218 " 436 +315 " 265 +318 "228 331 +245 " 425 +316 " 265 +318 "229 319 +250 " 411 +317 " 265 +318 "230 824 -120 " 1.32 .times. 10.sup.3 -216 " 645 +107 "231 536 +31 " 824 +103 " 415 +209 "232 743 -21 " 1.28 .times. 10.sup.3 +183 " 645 +106 "233 526 +40 " 832 +149 " 410 +211 "234 721 -23 " 1.42 .times. 10.sup.3 +156 " 528 +158 "235 605 +12 " 868 +360 " 239 +362 "236 433 +183 " 1.02 .times. 10.sup.3 +212 " 410 +211 "237 380 +209 " 675 +500 " 203 +502 "238 350 +221 " 623 +701 " 191 +702 "239 211 +266 " 543 +974 " 182 +982 "240 505 +50 " 1.32 .times. 10.sup.3 +208 " 410 +211 "241 450 +61 " 1.14 .times. 10.sup.3 +210 " 410 +211 "242 475 +63 " 1.06 .times. 10.sup.3 +211 " 410 +211 "243 405 +179 " 652 +698 " 191 +702 "244 386 +205 " 620 +701 " 191 +702 "245 421 +185 " 640 +699 " 191 +702 "246 383 +207 " 682 +484 " 208 +486 "247 422 + 199 " 924 +302 " 396 +304 "248 639 -161 " 583 +105 " 354 +294 "249 17.5 .times. 10.sup.3 -124 " 25.8 .times. 10.sup.3 -321 " 18.6 .times. 10.sup.3 -448 "250 10.5 .times. 10.sup.3 -79 " 16.7 .times. 10.sup.3 -212 " 11.9 .times. 10.sup.3 -507 "251 5.29 .times. 10.sup.3 -36 " 9.24 .times. 10.sup.3 -143 " 4.88 .times. 10.sup.3 -487 "252 21.6 .times. 10.sup.3 -144 " 32.3 .times. 10.sup.3 -365 " 20.6 .times. 10.sup.3 -449 "253 1.98 .times. 10.sup.3 +28 " 7.62 .times. 10.sup.3 -62 " 2.30 .times. 10.sup.3 -87 "254 12.4 .times. 10.sup.3 -106 " 15.6 .times. 10.sup.3 -203 " 7.08 .times. 10.sup.3 -328 "255 17.9 .times. 10.sup.3 -131 " 24.8 .times. 10.sup.3 -272 " 16.6 .times. 10.sup.3 -308 "256 16.8 .times. 10.sup.3 -129 " 22.9 .times. 10.sup.3 -264 " 14.5 .times. 10.sup.3 -381 "257 6.88 .times. 10.sup.3 -54 " 13.9 .times. 10.sup.3 -179 " 6.21 .times. 10.sup.3 -422 "258 6.02 .times. 10.sup.3 -42 " 11.2 .times. 10.sup.3 -158 " 5.49 .times. 10.sup.3 -456 "259 13.2 .times. 10.sup.3 -109 " 22.4 .times. 10.sup.3 -252 " 12.2 .times. 10.sup.3 -470 "260 16.4 .times. 10.sup.3 -120 " 23.8 .times. 10.sup.3 -270 " 14.6 .times. 10.sup.3 -485 "261 18.6 .times. 10.sup.3 -128 " 42.6 .times. 10.sup.3 -391 " 27.4 .times. 10.sup.3 -641 "262 9.64 .times. 10.sup.3 -94 " 17.9 .times. 10.sup.3 -224 " 8.61 .times. 10.sup.3 -588 "263 2.39 .times. 10.sup.3 +15 " 6.93 .times. 10.sup.3 -891 " 2.19 .times. 10.sup.3 -501 "264 1.68 .times. 10.sup.3 +32 " 4.83 .times. 10.sup.3 -521 " 1.55 .times. 10.sup.3 +57 "265 -18.7 .times. 10.sup.3 -222 " 24.5 .times. 10.sup.3 -342 " 16.3 .times. 10.sup.3 -342 "266 8.38 .times. 10.sup.3 -124 - 10.6 .times. 10.sup.3 -296 " 7.35 .times. 10.sup.3 -296 "267 624 +10 " 928 -42 " 483 -42 "268 921 +35 " 1.03 .times. 10.sup.3 -28 " 826 -28 "269 3.21 .times. 10.sup.3 -89 " 4.28 .times. 10.sup.3 -251 " 2.38 .times. 10.sup.3 -251 "270 3.3 .times. 10.sup.3 -98 " 4.93 .times. 10.sup.3 -124 " 2.88 .times. 10.sup.3 -256 "271 7.46 .times. 10.sup.3 -169 " 18.3 .times. 10.sup.3 -405 " 16.6 .times. 10.sup.3 -546 "272 1.39 .times. 10.sup.3 -132 " 8.11 .times. 10.sup.3 -216 " 14.5 .times. 10.sup.3 -367 "273 342 +23 " 560 -51 " 6.21 .times. 10.sup.3 -44 "274 694 -41 " 925 -88 " 5.49 .times. 10.sup.3 -109 "275 1.54 .times. 10.sup.3 -142 " 3.00 .times. 10.sup.3 -295 " 12.2 .times. 10.sup.3 -381 "276 1.03 .times. 10.sup.3 -95 " 3.49 .times. 10.sup.3 -186 " 14.6 .times. 10.sup.3 - 242 "__________________________________________________________________________
TABLE 11__________________________________________________________________________(Characteristic values corresponding to the sample in Table 3)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value Change value Change value Change at 25.degree. C. in Re- at 25.degree. C. in Re- at 25.degree. C. in Re- R.sub.25 TCR sistance R.sub.25 TCR sistance R.sub.25 TCR sistanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 9.23 .times. 10.sup.3 -48 <.+-.2 15.2 .times. 10.sup.3 -268 <.+-.2 8.78 .times. 10.sup.3 -916 <.+-.2 2 5.69 .times. 10.sup.3 +21 " 7.94 .times. 10.sup.3 -196 " 5.10 .times. 10.sup.3 -522 " 3 3.48 .times. 10.sup.3 +163 " 4.22 .times. 10.sup.3 -154 " 3.16 .times. 10.sup.3 -398 " 4 3.16 .times. 10.sup.3 +125 " 4.09 .times. 10.sup.3 -150 " 3.05 .times. 10.sup.3 -216 " 5 5.74 .times. 10.sup.3 +12 " 8.26 .times. 10.sup.3 -214 " 5.17 .times. 10.sup.3 -529 " 6 3.52 .times. 10.sup.3 +174 " 6.13 .times. 10.sup.3 -189 " 3.22 .times. 10.sup.3 -402 " 7 5.48 .times. 10.sup.3 +36 " 5.63 .times. 10.sup.3 -171 " 5.01 .times. 10.sup.3 -516 " 8 5.16 .times. 10.sup.3 +38 " 5.49 .times. 10.sup.3 -170 " 2.82 .times. 10.sup.3 -201 " 9 3.15 .times. 10.sup.3 +126 " 4.98 .times. 10.sup.3 -166 " 2.73 .times. 10.sup.3 -185 "10 3.23 .times. 10.sup.3 +150 " 5.16 .times. 10.sup.3 -167 " 3.04 .times. 10.sup.3 -215 "11 2.84 .times. 10.sup.3 +195 " 4.62 .times. 10.sup.3 -162 " 2.65 .times. 10.sup.3 -177 "12 2.46 .times. 10.sup.3 +242 " 4.41 .times. 10.sup.3 -161 " 2.62 .times. 10.sup.3 -175 "13 5.88 .times. 10.sup.3 +7 " 6.02 .times. 10.sup.3 -191 " 2.82 .times. 10.sup.3 -201 "14 4.21 .times. 10.sup.3 +108 " 5.81 .times. 10.sup.3 -172 " 3.04 .times. 10.sup.3 -215 "15 4.92 .times. 10.sup.3 +43 " 6.11 .times. 10.sup.3 -198 " 2.82 .times. 10.sup.3 -201 "16 3.00 .times. 10.sup.3 +161 " 5.99 .times. 10.sup.3 -182 " 3.04 .times. 10.sup.3 -215 "17 5.38 .times. 10.sup.3 +34 " 6.15 .times. 10.sup.3 -199 " 2.82 .times. 10.sup.3 -201 "18 3.81 .times. 10.sup.3 +136 " 6.01 .times. 10.sup.3 -188 " 3.04 .times. 10.sup.3 -215 "19 2.84 .times. 10.sup.3 +167 " 5.85 .times. 10.sup.3 -180 " 2.73 .times. 10.sup.3 -185 "20 2.40 .times. 10.sup.3 +193 " 5.65 .times. 10.sup.3 -173 " 2.65 .times. 10.sup.3 -177 "21 2.69 .times. 10.sup.3 +181 " 5.84 .times. 10.sup.3 -178 " 2.73 .times. 10.sup.3 -185 "22 2.18 .times. 10.sup.3 +180 " 5.62 .times. 10.sup.3 -171 " 2.65 .times. 10.sup.3 -177 "23 3.08 .times. 10.sup.3 +130 " 5.88 .times. 10.sup.3 -181 " 2.73 .times. 10.sup.3 -185 "24 2.61 .times. 10.sup.3 +185 " 5.67 .times. 10.sup.3 -174 " 2.65 .times. 10.sup.3 -177 "25 3.40 .times. 10.sup.3 +151 " 6.19 .times. 10.sup.3 -209 " 3.04 .times. 10.sup.3 -215 "26 2.99 .times. 10.sup.3 +203 " 6.22 .times. 10.sup.3 -211 " 3.04 .times. 10.sup.3 -215 "27 3.08 .times. 10.sup.3 +176 " 6.25 .times. 10.sup.3 -214 " 3.04 .times. 10.sup.3 -215 "28 8.72 .times. 10.sup.3 -62 " 14.3 .times. 10.sup.3 -278 " 8.55 .times. 10.sup.3 -859 "29 5.11 .times. 10.sup.3 +119 " 11.2 .times. 10.sup.3 -257 " 5.03 .times. 10.sup.3 -545 "30 2.92 .times. 10.sup.3 +267 " 8.92 .times. 10.sup.3 -148 " 3.02 .times. 10.sup.3 -349 "31 2.89 .times. 10.sup.3 +246 " 5.71 .times. 10.sup.3 -92 " 2.88 .times. 10.sup.3 -207 "32 4.94 .times. 10.sup.3 +205 " 9.96 .times. 10.sup.3 -246 " 5.00 .times. 10.sup.3 -550 "33 3.09 .times. 10.sup.3 +167 " 7.23 .times. 10.sup.3 -104 " 3.07 .times. 10.sup.3 -389 "34 4.89 .times. 10.sup.3 +103 " 6.21 .times. 10.sup.3 -490 " 4.98 .times. 10.sup.3 -531 "35 4.57 .times. 10.sup.3 +96 " 5.31 .times. 10.sup.3 -243 " 2.91 .times. 10.sup.3 -241 "36 2.66 .times. 10.sup.3 +145 " 3.68 .times. 10.sup.3 -216 " 2.89 .times. 10.sup.3 -223 "37 2.74 .times. 10.sup.3 +149 " 5.52 .times. 10.sup.3 -258 " 2.95 .times. 10.sup.3 -262 "38 2.33 .times. 10.sup.3 +189 " 4.86 .times. 10.sup.3 -234 " 2.90 .times. 10.sup. -236 "39 1.97 .times. 10.sup.3 +240 " 3.32 .times. 10.sup.3 -207 " 2.88 .times. 10.sup.3 -209 "40 5.03 .times. 10.sup.3 +65 " 5.21 .times. 10.sup.3 -239 " 2.91 .times. 10.sup.3 -241 "41 3.23 .times. 10.sup.3 +128 " 5.83 .times. 10.sup.3 -264 " 2.95 .times. 10.sup.3 -262 "42 4.71 .times. 10.sup.3 +95 " 5.25 .times. 10.sup.3 -240 " 2.91 .times. 10.sup.3 -241 "43 2.89 .times. 10.sup.3 +139 " 5.75 .times. 10.sup.3 -261 " 2.95 .times. 10.sup.3 -262 "44 4.88 .times. 10.sup.3 +81 " 4.98 .times. 10.sup.3 -238 " 2.91 .times. 10.sup.3 -241 "45 3.05 .times. 10.sup.3 +129 " 5.67 .times. 10.sup.3 -259 " 2.95 .times. 10.sup.3 -262 "46 3.20 .times. 10.sup.3 +103 " 4.65 .times. 10.sup.3 -225 " 2.89 .times. 10.sup.3 -223 "47 2.87 .times. 10.sup.3 +151 " 4.61 .times. 10.sup.3 -235 " 2.90 .times. 10.sup.3 -236 "48 2.44 .times. 10.sup.3 +140 " 3.81 .times. 10.sup.3 -220 " 2.89 .times. 10.sup.3 -223 "49 2.08 .times. 10.sup.3 +183 " 4.77 .times. 10.sup.3 -233 " 2.90 .times. 10.sup.3 -236 "50 2.85 .times. 10.sup.3 +160 " 4.68 .times. 10.sup.3 -227 " 2.89 .times. 10.sup.3 -223 "51 2.54 .times. 10.sup.3 +179 " 4.87 .times. 10.sup.3 -234 " 2.90 .times. 10.sup.3 -236 "52 4.68 .times. 10.sup.3 +89 " 5.30 .times. 10.sup.3 -243 " 2.91 .times. 10.sup.3 -241 "53 4.70 .times. 10.sup.3 +95 " 5.32 .times. 10.sup.3 -245 " 2.91 .times. 10.sup.3 -241 "54 4.77 .times. 10.sup.3 +78 " 5.46 .times. 10.sup.3 -261 " 2.91 .times. 10.sup.3 -241 "55 7.16 .times. 10.sup.3 -163 " 9.33 .times. 10.sup.3 -462 " 7.28 .times. 10.sup.3 -928 "56 4.81 .times. 10.sup.3 -82 " 6.42 .times. 10.sup.3 -419 " 4.99 .times. 10.sup.3 -636 "57 7.22 .times. 10.sup.3 -184 " 10.2 .times. 10.sup.3 -497 " 7.30 .times. 10.sup.3 -936 "58 4.93 .times. 10.sup.3 -93 " 7.21 .times. 10.sup.3 -444 " 5.05 .times. 10.sup.3 -640 "59 6.13 .times. 10.sup.3 -121 " 8.25 .times. 10.sup.3 -498 " 7.02 .times. 10.sup.3 -887 "60 6.01 .times. 10.sup.3 -105 " 8.43 .times. 10.sup.3 -499 " 3.42 .times. 10.sup.3 -524 "61 3.87 .times. 10.sup.3 +53 " 7.91 .times. 10.sup.3 -497 " 3.21 .times. 10.sup.3 -502 "62 3.62 .times. 10.sup.3 +77 " 7.62 .times. 10.sup.3 -496 " 4.67 .times. 10.sup.3 -611 "63 3.14 .times. 10.sup.3 +68 " 6.41 .times. 10.sup.3 -490 " 3.33 .times. 10.sup.3 -512 "64 3.00 .times. 10.sup.3 +85 " 6.15 .times. 10.sup.3 -489 " 2.64 .times. 10.sup.3 -499 "65 6.24 .times. 10.sup.3 -135 " 7.32 .times. 10.sup.3 -495 " 3.42 .times. 10.sup.3 -524 "66 4.07 .times. 10.sup.3 +5 " 7.04 .times. 10.sup.3 -494 " 4.67 .times. 10.sup.3 -611 "67 5.85 .times. 10.sup.3 -85 " 6.02 .times. 10.sup.3 -488 " 3.42 .times. 10.sup.3 -524 "68 3.41 .times. 10.sup.3 +58 " 6.52 .times. 10.sup.3 -491 " 4.67 .times. 10.sup.3 -611 "69 5.67 .times. 10.sup.3 -18 " 5.88 .times. 10.sup.3 -487 " 3.42 .times. 10.sup.3 -524 "70 3.29 .times. 10.sup.3 +60 " 6.72 .times. 10.sup.3 -429 " 4.67 .times. 10.sup.3 -611 "71 4.33 .times. 10.sup.3 -52 " 6.83 .times. 10.sup.3 -493 " 3.21 .times. 10.sup.3 -502 "72 3.68 .times. 10.sup.3 +21 " 6.39 .times. 10.sup.3 -490 " 3.33 .times. 10.sup.3 -512 "73 3.99 .times. 10.sup.3 +18 " 4.86 .times. 10.sup.3 -468 " 3.21 .times. 10.sup. -468 "74 3.31 .times. 10.sup.3 +28 " 5.25 .times. 10.sup.3 -478 " 3.33 .times. 10.sup.3 -478 "75 4.18 .times. 10.sup.3 -20 " 5.06 .times. 10.sup.3 -472 " 3.21 .times. 10.sup.3 -472 "76 3.54 .times. 10.sup.3 +40 " 5.45 .times. 10.sup.3 -479 " 3.33 .times. 10.sup.3 -479 "77 3.08 .times. 10.sup.3 +72 " 5.61 .times. 10.sup.3 -481 " 3.33 .times. 10.sup.3 -481 "78 3.20 .times. 10.sup.3 +70 " 5.24 .times. 10.sup.3 -478 " 3.33 .times. 10.sup.3 -478 "79 3.49 .times. 10.sup.3 +20 " 5.16 .times. 10.sup.3 -476 " 3.33 .times. 10.sup.3 -476 "80 3.10 .times. 10.sup.3 +166 " 4.74 .times. 10.sup.3 -467 " 3.00 .times. 10.sup.3 -467 "81 4.02 .times. 10.sup.3 +172 " 6.14 .times. 10.sup.3 -492 " 3.82 .times. 10.sup.3 -477 "82 3.48 .times. 10.sup.3 +159 " 3.98 .times. 10.sup.3 -398 " 3.04 .times. 10.sup.3 -501 "83 3.84 .times. 10.sup.3 +144 " 4.52 .times. 10.sup.3 -456 " 3.16 .times. 10.sup.3 -504 "__________________________________________________________________________
TABLE 12__________________________________________________________________________(Characteristic values corresponding to the sample in Table 4)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value Change value Change value Change at 25.degree. C. in Re- at 25.degree. C. in Re- at 25.degree. C. in Re- R.sub.25 TCR sistance R.sub.25 TCR sistance R.sub.25 TCR sistanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 20.3 .times. 10.sup.3 -289 <.+-.2 26.3 .times. 10.sup.3 -986 <.+-.2 25.4 .times. 10.sup.3 -986 <.+-.2 2 17.5 .times. 10.sup.3 -278 " 22.5 .times. 10.sup.3 -877 " 21.7 .times. 10.sup.3 -877 " 3 13.2 .times. 10.sup.3 -252 " 19.3 .times. 10.sup.3 -805 " 18.4 .times. 10.sup.3 -805 " 4 5.34 .times. 10.sup.3 -190 " 10.3 .times. 10.sup.3 -681 " 9.26 .times. 10.sup.3 -681 " 5 21.5 .times. 10.sup.3 -285 " 27.5 .times. 10.sup.3 -995 " 26.4 .times. 10.sup.3 -995 " 6 18.4 .times. 10.sup.3 -275 " 23.1 .times. 10.sup.3 -880 " 22.3 .times. 10.sup.3 -880 " 7 14.9 .times. 10.sup.3 -250 " 19.8 .times. 10.sup.3 -803 " 19.0 .times. 10.sup.3 -803 " 8 4.25 .times. 10.sup.3 -187 " 10.1 .times. 10.sup.3 -684 " 9.77 .times. 10.sup.3 -684 " 9 15.3 .times. 10.sup.3 -265 " 19.2 .times. 10.sup.3 -804 " 18.8 .times. 10.sup.3 -804 "10 15.1 .times. 10.sup.3 -285 " 23.6 .times. 10.sup.3 -418 " 21.4 .times. 10.sup.3 -842 "11 13.9 .times. 10.sup.3 -249 " 16.4 .times. 10.sup.3 -376 " 17.3 .times. 10.sup.3 -794 "12 11.5 .times. 10.sup.3 -218 " 15.2 .times. 10.sup.3 -351 " 14.6 .times. 10.sup.3 -693 "13 9.84 .times. 10.sup.3 -205 " 17.6 .times. 10.sup.3 -402 " 16.9 .times. 10.sup.3 -761 "14 8.07 .times. 10.sup.3 -188 " 9.31 .times. 10.sup.3 -598 " 9.48 .times. 10.sup.3 -652 "15 16.3 .times. 10.sup.3 -297 " 20.3 .times. 10.sup.3 -783 " 21.4 .times. 10.sup.3 -842 "16 14.7 .times. 10.sup.3 -259 " 16.8 .times. 10.sup.3 -428 " 17.3 .times. 10.sup.3 -794 "17 12.7 .times. 10.sup.3 -231 " 15.4 .times. 10.sup.3 -398 " 14.6 .times. 10.sup.3 -693 "18 10.4 .times. 10.sup.3 -227 " 14.9 .times. 10.sup.3 -372 " 16.9 .times. 10.sup.3 -761 "19 8.65 .times. 10.sup.3 -205 " 9.72 .times. 10.sup.3 -481 " 9.48 .times. 10.sup.3 -652 "20 13.9 .times. 10.sup.3 -261 " 15.2 .times. 10.sup.3 -384 " 14.6 .times. 10.sup.3 -693 "21 13.4 .times. 10.sup.3 -268 " 15.8 .times. 10.sup.3 -402 " 16.9 .times. 10.sup.3 -761 "22 12.3 .times. 10.sup.3 -242 " 14.4 .times. 10.sup.3 -369 " 14.6 .times. 10.sup.3 -693 "23 10.7 .times. 10.sup.3 -225 " 15.5 .times. 10.sup.3 -401 " 16.9 .times. 10.sup.3 -761 "24 12.9 .times. 10.sup.3 -243 " 13.9 .times. 10.sup.3 -340 " 14.6 .times. 10.sup. -693 "25 11.8 .times. 10.sup.3 -236 " 15.1 .times. 10.sup.3 -377 " 16.9 .times. 10.sup.3 -761 "26 12.7 .times. 10.sup.3 -240 " 14.2 .times. 10.sup.3 -358 " 14.6 .times. 10.sup.3 -693 "27 10.7 .times. 10.sup.3 -235 " 14.9 .times. 10.sup.3 -373 " 16.9 .times. 10.sup.3 -761 "28 10.4 .times. 10.sup.3 -205 " 14.3 .times. 10.sup.3 -364 " 14.6 .times. 10.sup.3 -693 "29 9.12 .times. 10.sup.3 -207 " 15.9 .times. 10.sup.3 -418 " 16.9 .times. 10.sup.3 -761 "30 9.03 .times. 10.sup.3 -198 " 14.5 .times. 10.sup.3 -370 " 14.6 .times. 10.sup.3 -693 "31 8.88 .times. 10.sup.3 -191 " 13.4 .times. 10.sup.3 -314 " 16.9 .times. 10.sup.3 -761 "32 12.6 .times. 10.sup.3 -243 " 15.8 .times. 10.sup.3 -404 " 14.6 .times. 10.sup.3 -693 "33 11.4 .times. 10.sup.3 -222 " 13.6 .times. 10.sup.3 -318 " 14.6 .times. 10.sup.3 -693 "34 13.8 .times. 10.sup.3 -261 " 14.9 .times. 10.sup.3 -382 " 14.6 .times. 10.sup.3 -693 "35 9.73 .times. 10.sup.3 -209 " 15.2 .times. 10.sup.3 -383 " 16.9 .times. 10.sup.3 -761 "__________________________________________________________________________
TABLE 13__________________________________________________________________________(Characteristic values corresponding to the sample in Table 5)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value Change value Change value Change at 25.degree. C. in Re- at 25.degree. C. in Re- at 25.degree. C. in Re- R.sub.25 TCR sistance R.sub.25 TCR sistance R.sub.25 TCR sistanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 48.3 .times. 10.sup.3 -298 <.+-.2 53.8 .times. 10.sup.3 -483 <.+-.2 52.5 .times. 10.sup.3 -877 <.+-.2 2 14.8 .times. 10.sup.3 -273 " 19.5 .times. 10.sup.3 -395 " 18.9 .times. 10.sup.3 -580 " 3 2.54 .times. 10.sup.3 -93 " 6.23 .times. 10.sup.3 - 315 " 5.81 .times. 10.sup.3 -416 " 4 2.19 .times. 10.sup.3 -90 " 3.15 .times. 10.sup.3 -310 " 2.30 .times. 10.sup.3 -304 " 5 16.2 .times. 10.sup.3 -279 " 20.5 .times. 10.sup.3 -403 " 19.3 .times. 10.sup.3 -576 " 6 2.80 .times. 10.sup.3 -95 " 6.34 .times. 10.sup.3 -392 " 5.79 .times. 10.sup.3 -415 " 7 20.1 .times. 10.sup.3 -292 " 26.3 .times. 10.sup.3 -425 " 25.3 .times. 10.sup.3 -685 " 8 18.5 .times. 10.sup.3 -281 " 22.1 .times. 10.sup.3 -410 " 21.6 .times. 10.sup.3 -675 " 9 8.78 .times. 10.sup.3 -195 " 9.56 .times. 10.sup.3 -380 " 9.26 .times. 10.sup.3 -525 "10 7.96 .times. 10.sup.3 -197 " 9.02 .times. 10.sup.3 -378 " 8.92 .times. 10.sup.3 -518 "11 2.01 .times. 10.sup.3 -105 " 3.25 .times. 10.sup.3 -309 " 3.03 .times. 10.sup.3 -403 "12 2.00 .times. 10.sup.3 -98 " 2.89 .times. 10.sup.3 -305 " 2.84 .times. 10.sup.3 -398 "13 1.12 .times. 10.sup.3 -45 " 2.18 .times. 10.sup.3 -303 " 2.13 .times. 10.sup.3 -387 "14 24.3 .times. 10.sup.3 -298 " 26.9 .times. 10.sup.3 -432 " 25.3 .times. 10.sup.3 -685 "15 21.8 .times. 10.sup.3 -290 " 23.0 .times. 10.sup.3 -415 " 21.6 .times. 10.sup.3 -675 "16 9.95 .times. 10.sup.3 -225 " 9.82 .times. 10.sup.3 -392 " 9.26 .times. 10.sup.3 -525 "17 9.03 .times. 10.sup.3 -221 " 9.03 .times. 10.sup. 3 -381 " 8.92 .times. 10.sup.3 -518 "18 4.68 .times. 10.sup.3 -185 " 3.25 .times. 10.sup.3 -363 " 3.03 .times. 10.sup.3 -403 "19 4.41 .times. 10.sup.3 -168 " 3.01 .times. 10.sup.3 -314 " 2.84 .times. 10.sup.3 -398 "20 1.85 .times. 10.sup.3 -62 " 2.21 .times. 10.sup.3 -309 " 2.13 .times. 10.sup.3 -387 "21 10.08 10.sup.3 -223 " 9.83 .times. 10.sup.3 -392 " 9.26 .times. 10.sup.3 -525 "22 2.38 .times. 10.sup.3 -114 " 3.21 .times. 10.sup.3 -365 " 3.03 .times. 10.sup.3 -403 "23 8.14 .times. 10.sup.3 -186 " 9.56 .times. 10.sup.3 -353 " 9.26 .times. 10.sup.3 -525 "24 1.95 .times. 10.sup.3 -106 " 3.14 .times. 10.sup.3 -358 " 3.03 .times. 10.sup.3 -403 "25 7.68 .times. 10.sup.3 -181 " 9.54 .times. 10.sup.3 -393 " 9.26 .times. 10.sup.3 -525 "26 1.88 .times. 10.sup.3 -99 " 3.17 .times. 10.sup.3 -374 " 3.03 .times. 10.sup.3 -403 "27 9.84 .times. 10.sup.3 -200 " 9.02 .times. 10.sup.3 -362 " 8.92 .times. 10.sup.3 -518 "28 3.01 .times. 10.sup.3 -141 " 2.92 .times. 10.sup.3 -316 " 2.84 .times. 10.sup.3 -398 "29 8.16 .times. 10.sup.3 -184 " 9.21 .times. 10.sup.3 -321 " 8.92 .times. 10.sup.3 -518 "30 2.18 .times. 10.sup.3 -120 " 2.90 .times. 10.sup.3 -316 " 2.84 .times. 10.sup.3 -398 "31 8.78 .times. 10.sup.3 -188 " 8.98 .times. 10.sup.3 -321 " 8.92 .times. 10.sup.3 -518 "32 2.54 .times. 10.sup.3 -121 " 2.96 .times. 10.sup.3 -319 " 2.84 .times. 10.sup.3 -398 "33 17.4 .times. 10.sup.3 -277 " 21.9 .times. 10.sup.3 -403 " 21.6 .times. 10.sup.3 -675 "34 18.9 .times. 10.sup.3 -289 " 22.0 .times. 10.sup.3 -410 " 21.6 .times. 10.sup.3 -675 "35 43.9 .times. 10.sup.3 -297 " 45.6 .times. 10.sup.3 -463 " 44.8 .times. 10.sup.3 -857 "36 14.8 .times. 10.sup.3 -261 " 16.3 .times. 10.sup.3 -405 " 15.0 .times. 10.sup.3 -521 "37 4.13 .times. 10.sup.3 -180 " 5.34 .times. 10.sup.3 -362 " 4.77 .times. 10.sup.3 -408 "38 1.93 .times. 10.sup.3 -120 " 3.51 .times. 10.sup.3 -354 " 2.07 .times. 10.sup.3 -311 "39 14.8 .times. 10.sup.3 -273 " 17.5 .times. 10.sup.3 -413 " 15.3 .times. 10.sup.3 -527 "40 4.24 .times. 10.sup.3 -186 " 5.83 .times. 10.sup.3 -372 " 4.80 .times. 10.sup.3 -411 "41 18.2 .times. 10.sup.3 -271 " 19.8 .times. 10.sup.3 -412 " 19.4 .times. 10.sup.3 -621 "42 16.4 .times. 10.sup.3 -254 " 18.6 .times. 10.sup.3 -408 " 18.2 .times. 10.sup.3 -613 "43 6.85 .times. 10.sup.3 -186 " 7.82 .times. 10.sup.3 -395 " 7.32 .times. 10.sup.3 -480 "44 6.18 .times. 10.sup.3 -184 " 7.53 .times. 10.sup.3 -389 " 7.01 .times. 10.sup.3 -478 "45 2.81 .times. 10.sup.3 -125 " 3.43 .times. 10.sup.3 -325 " 3.24 .times. 10.sup.3 -411 "46 2.16 .times. 10.sup.3 -118 " 3.21 .times. 10.sup.3 -320 " 3.02 .times. 10.sup.3 -408 "47 985 -15 " 1.53 .times. 10.sup.3 -302 " 1.21 .times. 10.sup.3 -398 "48 7.90 .times. 10.sup.3 -197 " 7.42 .times. 10.sup.3 -380 " 7.32 .times. 10.sup.3 -480 "49 4.11 .times. 10.sup.3 -174 " 3.28 .times. 10.sup.3 -328 " 3.24 .times. 10.sup.3 -411 "50 6.99 .times. 10.sup.3 -181 " 7.38 .times. 10.sup.3 -375 " 7.32 .times. 10.sup.3 -480 "51 3.05 .times. 10.sup.3 -155 " 3.80 .times. 10.sup.3 -331 " 3.24 .times. 10.sup.3 -411 "52 7.41 .times. 10.sup.3 -192 " 7.36 .times. 10.sup.3 -375 " 7.32 .times. 10.sup.3 -480 "53 3.40 .times. 10.sup.3 -148 " 3.92 .times. 10.sup.3 -380 " 3.24 .times. 10.sup.3 -411 "54 7.10 .times. 10.sup.3 -189 " 7.21 .times. 10.sup.3 -369 " 7.01 .times. 10.sup.3 -478 "55 2.99 .times. 10.sup.3 -133 " 3.56 .times. 10.sup.3 -345 " 3.02 .times. 10.sup.3 -408 "56 5.84 .times. 10.sup.3 -170 " 7.26 .times. 10.sup.3 -361 " 7.01 .times. 10.sup.3 -478 "57 1.95 .times. 10.sup.3 -119 " 3.21 .times. 10.sup.3 -353 " 3.02 .times. 10.sup.3 -408 "58 6.65 .times. 10.sup.3 -179 " 7.36 .times. 10.sup.3 -372 " 7.01 .times. 10.sup.3 -478 "59 2.45 .times. 10.sup.3 -130 " 3.25 .times. 10.sup.3 -350 " 3.02 .times. 10.sup.3 -408 "60 18.6 .times. 10.sup.3 -283 " 19.3 .times. 10.sup.3 -403 " 18.2 .times. 10.sup.3 -613 "61 19.1 .times. 10.sup.3 -290 " 18.6 .times. 10.sup.3 -410 " 18.2 .times. 10.sup.3 -613 "62 1.66 .times. 10.sup.3 -105 " 2.10 .times. 10.sup.3 -380 " 2.06 .times. 10.sup.3 -487 "63 1.59 .times. 10.sup.3 -100 " 2.24 .times. 10.sup.3 -383 " 2.15 .times. 10.sup.3 -498 "64 1.76 .times. 10.sup.3 -109 " 1.98 .times. 10.sup.3 -375 " 1.92 .times. 10.sup.3 -478 "__________________________________________________________________________
TABLE 14__________________________________________________________________________(Characteristic values corresponding to the sample in Table 6)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value Change value Change value Change at 25.sub.5 .degree. C. in Re- at 25.sub.5 .degree. C. in Re- at 25.sub.5 .degree. C. in Re- R.sub.25 TCR sistance R.sub.25 TCR sistance R.sub.25 TCR sistanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 83.6 .times. 10.sup.3 -300 <.+-.2 87.5 .times. 10.sup.3 -493 <.+-.2 84.3 .times. 10.sup.3 -989 <.+-.2 2 38.5 .times. 10.sup.3 -285 " 41.5 .times. 10.sup.3 -423 " 39.4 .times. 10.sup.3 -720 " 3 19.8 .times. 10.sup.3 -120 " 21.6 .times. 10.sup.3 -401 " 20.4 .times. 10.sup.3 -378 " 4 4.83 .times. 10.sup.3 +12 " 4.92 .times. 10.sup.3 -263 " 4.05 .times. 10.sup.3 -185 " 5 38.7 .times. 10.sup.3 -214 " 40.5 .times. 10.sup.3 -418 " 39.2 .times. 10.sup.3 -723 " 6 19.6 .times. 10.sup.3 -118 " 21.4 .times. 10.sup.3 -409 " 20.6 .times. 10.sup.3 -380 " 7 52.5 .times. 10.sup.3 -298 " 53.8 .times. 10.sup.3 -454 " 53.2 .times. 10.sup.3 -830 " 8 45.3 .times. 10.sup.3 -295 " 46.5 .times. 10.sup.3 -438 " 46.3 .times. 10.sup.3 -810 " 9 48.7 .times. 10.sup.3 -267 " 49.3 .times. 10.sup.3 -437 " 49.1 .times. 10.sup.3 -812 "10 27.4 .times. 10.sup.3 -205 " 28.9 .times. 10.sup.3 -407 " 28.5 .times. 10.sup.3 -750 "11 33.0 .times. 10.sup.3 -198 " 34.0 .times. 10.sup.3 -198 " 33.8 .times. 10.sup.3 -780 "12 8.31 .times. 10.sup.3 +23 " 9.60 .times. 10.sup.3 -283 " 9.25 .times. 10.sup.3 -520 "13 7.20 .times. 10.sup.3 +31 " 8.03 .times. 10.sup.3 -265 " 7.80 .times. 10.sup.3 -490 "14 2.38 .times. 10.sup.3 +89 " 3.08 .times. 10.sup.3 -250 " 3.04 .times. 10.sup.3 -353 "15 59.6 .times. 10.sup.3 -289 " 53.6 .times. 10.sup.3 -449 " 53.2 .times. 10.sup.3 -830 "16 51.2 .times. 10.sup.3 -274 " 46.8 .times. 10.sup.3 -424 " 46.3 .times. 10.sup.3 -810 "17 57.7 .times. 10.sup.3 -283 " 49.0 .times. 10.sup.3 -430 " 49.1 .times. 10.sup.3 -812 "18 30.1 .times. 10.sup.3 -245 " 29.1 .times. 10.sup.3 -380 " 28.5 .times. 10.sup.3 -750 "19 35.2 .times. 10.sup.3 -201 " 34.1 .times. 10.sup.3 -415 " 33.8 .times. 10.sup.3 -780 "20 10.1 .times. 10.sup.3 -15 " 9.34 .times. 10.sup.3 -350 " 9.25 .times. 10.sup.3 -520 "21 9.08 .times. 10.sup.3 -50 " 7.89 .times. 10.sup.3 -314 " 7.80 .times. 10.sup.3 -490 "22 4.01 .times. 10.sup.3 +3 " 3.21 .times. 10.sup.3 -289 " 3.04 .times. 10.sup.3 -353 "23 54.9 .times. 10.sup.3 -283 " 46.8 .times. 10.sup.3 -438 " 46.3 .times. 10.sup.3 -830 "24 15.6 .times. 10.sup.3 -95 " 9.36 .times. 10.sup.3 -352 " 9.25 .times. 10.sup.3 -520 "25 32.7 .times. 10.sup.3 -254 " 46.5 .times. 10.sup.3 -423 " 46.3 .times. 10.sup.3 -810 "26 5.23 .times. 10.sup.3 -18 " 9.30 .times. 10.sup.3 -273 " 9.25 .times. 10.sup.3 -520 "27 47.4 .times. 10.sup.3 -270 " 46.5 .times. 10.sup.3 -430 " 46.3 .times. 10.sup.3 -830 "28 9.98 .times. 10.sup.3 -78 " 9.31 .times. 10.sup.3 -360 " 9.25 .times. 10.sup.3 -520 "29 47.3 .times. 10.sup.3 -272 " 33.9 .times. 10.sup.3 -416 " 33.8 .times. 10.sup.3 -780 "30 18.0 .times. 10.sup.3 -105 " 9.35 .times. 10.sup.3 -370 " 9.25 .times. 10.sup.3 -520 "31 35.2 .times. 10.sup.3 -187 " 33.2 .times. 10.sup.3 -421 " 33.8 .times. 10.sup.3 -780 "32 9.51 .times. 10.sup.3 -5 " 8.93 .times. 10.sup.3 -320 " 9.25 .times. 10.sup.3 -520 "33 37.0 .times. 10.sup.3 -201 " 34.1 .times. 10.sup.3 -431 " 33.8 .times. 10.sup.3 -780 "34 11.3 .times. 10.sup.3 -11 " 9.25 .times. 10.sup.3 -368 " 9.25 .times. 10.sup.3 -520 "35 46.8 .times. 10.sup.3 -300 " 45.9 .times. 10.sup.3 -433 " 46.3 .times. 10.sup.3 -810 "36 48.5 .times. 10.sup.3 -295 " 46.4 .times. 10.sup.3 -430 " 46.3 .times. 10.sup.3 -810 "37 43.3 .times. 10.sup.3 -280 " 46.8 .times. 10.sup.3 -435 " 46.3 .times. 10.sup.3 -810 "38 42.9 .times. 10.sup.3 -283 " 45.8 .times. 10.sup.3 -429 " 46.3 .times. 10.sup.3 -810 "39 67.1 .times. 10.sup.3 -299 " 71.2 .times. 10.sup.3 -498 " 70.1 .times. 10.sup.3 -995 "40 25.6 .times. 10.sup.3 -154 " 29.3 .times. 10.sup.3 -408 " 28.4 .times. 10.sup.3 -788 "41 16.8 .times. 10.sup.3 -121 " 18.1 .times. 10.sup.3 -374 " 17.7 .times. 10.sup.3 -385 "42 2.13 .times. 10.sup.3 -62 " 3.21 .times. 10.sup.3 -270 " 2.95 .times. 10.sup.3 -207 "43 27.1 .times. 10.sup.3 -156 " 29.5 .times. 10.sup.3 -412 " 28.2 .times. 10.sup.3 -790 "44 16.4 .times. 10.sup.3 -128 " 18.4 .times. 10.sup.3 -368 " 17.6 .times. 10.sup.3 -381 "45 45.5 .times. 10.sup.3 -284 " 48.9 .times. 10.sup.3 - 425 " 48.6 .times. 10.sup.3 -825 "46 37.9 .times. 10.sup.3 -217 " 39.0 .times. 10.sup.3 -416 " 38.2 .times. 10.sup.3 -810 "47 41.5 .times. 10.sup.3 -254 " 42.8 .times. 10.sup.3 -421 " 42.1 .times. 10.sup.3 -819 "48 19.8 .times. 10.sup.3 -101 " 20.8 .times. 10.sup.3 -382 " 20.3 .times. 10.sup.3 -780 "49 25.5 .times. 10.sup.3 -137 " 26.5 .times. 10.sup.3 -393 " 26.3 .times. 10.sup.3 -789 "50 5.11 .times. 10.sup.3 -95 " 6.23 .times. 10.sup.3 -283 " 6.03 .times. 10.sup.3 -310 "51 4.78 .times. 10.sup.3 -73 " 5.34 .times. 10.sup.3 -279 " 5.05 .times. 10.sup.3 -308 "52 1.09 .times. 10.sup.3 -25 " 2.10 .times. 10.sup.3 -268 " 2.09 .times. 10.sup.3 -280 "53 6.95 .times. 10.sup.3 -105 " 5.21 .times. 10.sup.3 -280 " 5.05 .times. 10.sup.3 -310 "54 39.4 .times. 10.sup.3 -219 " 38.4 .times. 10.sup.3 -420 " 38.2 .times. 10.sup.3 -815 "55 38.1 .times. 10.sup.3 -183 " 38.6 .times. 10.sup.3 -425 " 38.2 .times. 10.sup.3 -804 "56 36.8 .times. 10.sup.3 -195 " 37.9 .times. 10.sup.3 -418 " 38.2 .times. 10.sup.3 -809 "57 26.5 .times. 10.sup.3 -295 " 28.8 .times. 10.sup.3 -489 " 27.1 .times. 10.sup.3 -849 "58 16.2 .times. 10.sup.3 -286 " 18.2 .times. 10.sup.3 -465 " 17.1 .times. 10.sup.3 -452 "59 6.81 .times. 10.sup.3 -267 " 7.43 .times. 10.sup.3 -378 " 7.34 .times. 10.sup.3 -424 "60 22.4 .times. 10.sup.3 -284 " 24.8 .times. 10.sup.3 -412 " 23.7 .times. 10.sup.3 -784 "61 13.8 .times. 10.sup.3 -253 " 15.4 .times. 10.sup.3 -324 " 14.6 .times. 10.sup.3 -382 "62 5.32 .times. 10.sup.3 -218 " 5.92 .times. 10.sup.3 -295 " 5.82 .times. 10.sup.3 -316 "63 41.6 .times. 10.sup.3 -254 " 43.8 .times. 10.sup.3 -454 " 42.5 .times. 10.sup.3 -573 "64 27.2 .times. 10.sup.3 -180 " 29.6 .times. 10.sup.3 -398 " 28.8 .times. 10.sup.3 -375 "65 9.53 .times. 10.sup.3 +88 " 8.95 .times. 10.sup.3 -314 " 9.82 .times. 10.sup.3 -306 "66 23.4 .times. 10.sup.3 -263 " 25.3 .times. 10.sup.3 -263 " 24.0 .times. 10.sup.3 -501 "67 14.1 .times. 10.sup.3 -201 " 15.9 .times. 10.sup.3 -201 " 15.4 .times. 10.sup.3 -328 "68 5.73 .times. 10.sup.3 -83 " 6.25 .times. 10.sup.3 -254 " 6.15 .times. 10.sup.3 -287 "69 24.1 .times. 10.sup.3 -526 " 26.4 .times. 10.sup.3 -526 " 25.7 .times. 10.sup.3 -526 "70 15.2 .times. 10.sup.3 -349 " 15.2 .times. 10.sup.3 -349 " 16.6 .times. 10.sup.3 -349 "71 6.69 .times. 10.sup.3 -104 " 7.41 .times. 10.sup.3 -295 " 7.32 .times. 10.sup.3 -324 "72 38.6 .times. 10.sup.3 -253 " 40.3 .times. 10.sup.3 -418 " 39.4 .times. 10.sup.3 -485 "73 27.5 .times. 10.sup.3 -180 " 29.5 .times. 10.sup.3 -384 " 28.4 .times. 10.sup.3 -366 "74 8.32 .times. 10.sup.3 +91 " 9.14 .times. 10.sup.3 -214 " 9.03 .times. 10.sup.3 -343 "75 30.4 .times. 10.sup.3 -284 " 32.4 .times. 10.sup.3 -462 " 31.0 .times. 10.sup.3 -796 "76 18.6 .times. 10.sup.3 -235 " 20.5 .times. 10.sup.3 -390 " 19.5 .times. 10.sup.3 -391 "77 7.71 .times. 10.sup.3 -203 " 8.21 .times. 10.sup.3 -283 " 8.64 .times. 10.sup.3 -312 "78 39.6 .times. 10.sup.3 -180 " 41.6 .times. 10.sup.3 -254 " 40.8 .times. 10.sup.3 -299 "79 31.5 .times. 10.sup.3 -174 " 33.5 .times. 10.sup.3 -209 " 32.2 .times. 10.sup.3 -284 "80 8.54 .times. 10.sup.3 +95 " 9.15 .times. 10.sup.3 -196 " 9.03 .times. 10.sup.3 -254 "81 33.4 .times. 10.sup.3 -263 " 35.3 .times. 10.sup.3 -435 " 34.3 .times. 10.sup.3 -511 "82 19.6 .times. 10.sup.3 -242 " 21.9 .times. 10.sup.3 -353 " 20.8 .times. 10.sup.3 -360 "83 7.51 .times. 10.sup.3 -195 " 8.24 .times. 10.sup.3 -286 " 8.20 .times. 10.sup.3 -313 "84 44.8 .times. 10.sup.3 -294 " 46.8 .times. 10.sup.3 -463 " 45.5 .times. 10.sup.3 -775 "85 32.8 .times. 10.sup.3 -281 " 34.3 .times. 10.sup.3 -401 " 33.1 .times. 10.sup.3 -381 "86 9.11 .times. 10.sup.3 -240 " 9.8 .times. 10.sup.3 -2931 " 10.3 .times. 10.sup.3 -329 "87 34.3 .times. 10.sup.3 -285 " 36.5 .times. 10.sup.3 -459 " 35.1 .times. 10.sup.3 -769 "88 24.5 .times. 10.sup.3 -239 " 26.8 .times. 10.sup.3 -375 " 25.4 .times. 10.sup.3 -375 "89 7.87 .times. 10.sup.3 -176 " 8.14 .times. 10.sup.3 -275 " 8.03 .times. 10.sup.3 -352 "90 28.4 .times. 10.sup.3 -287 " 30.5 .times. 10.sup.3 -469 " 29.6 .times. 10.sup.3 -789 "91 18.5 .times. 10.sup.3 -453 " 20.9 .times. 10.sup.3 -353 " 19.8 .times. 10.sup.3 -384 "92 5.43 .times. 10.sup.3 -224 " 6.12 .times. 10.sup.3 -302 " 6.25 .times. 10.sup.3 -363 "93 26.3 .times. 10.sup.3 -282 " 28.6 .times. 10.sup.3 -434 " 27.0 .times. 10.sup.3 -600 "94 15.2 .times. 10.sup.3 -253 " 17.8 .times. 10.sup.3 -319 " 16.4 .times. 10.sup.3 -321 "95 5.43 .times. 10.sup.3 - 224 " 5.58 .times. 10.sup.3 -264 " 5.63 .times. 10.sup.3 -302 "96 28.3 .times. 10.sup.3 -186 " 31.5 .times. 10.sup.3 -353 " 18.4 .times. 10.sup.3 -441 "97 26.5 .times. 10.sup.3 -215 " 24.6 .times. 10.sup.3 -321 " 15.3 .times. 10.sup.3 -425 "98 32.8 .times. 10.sup.3 -255 " 33.1 .times. 10.sup.3 -189 " 29.5 .times. 10.sup.3 -295 "99 31.1 .times. 10.sup.3 -281 " 30.5 .times. 10.sup.3 -340 " 30.0 .times. 10.sup.3 -518 "100 32.5 .times. 10.sup.3 -296 " 31.1 .times. 10.sup.3 -290 " 23.4 .times. 10.sup.3 -399 "101 7.35 .times. 10.sup.3 -58 " 8.44 .times. 10.sup.3 -159 " 4.90 .times. 10.sup.3 -365 "102 8.03 .times. 10.sup.3 - 103 " 8.33 .times. 10.sup.3 -353 " 4.62 .times. 10.sup.3 -521 "103 9.46 .times. 10.sup.3 -59 " 11.5 .times. 10.sup.3 -197 " 5.51 .times. 10.sup.3 -403 "104 11.5 .times. 10.sup.3 -206 " 13.0 .times. 10.sup.3 -395 " 7.70 .times. 10.sup.3 -530 "105 7.48 .times. 10.sup.3 -251 " 8.15 .times. 10.sup.3 -420 " 4.80 .times. 10.sup.3 -565 "__________________________________________________________________________
TABLE 15__________________________________________________________________________(Characteristic values corresponding to the sample in Table 7)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resistance Rate of Resistance Rate of Resistance Rate of value Change value Change value Change at 25.degree. C. in Re- at 25.degree. C. in Re- at 25.degree. C. in Re- R.sub.25 TCR sistance R.sub.25 TCR sistance R.sub.25 TCR sistance (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________ 1 2.03 .times. 10.sup.3 +193 <.+-.2 3.01 .times. 10.sup.3 +304 <.+-.2 2.87 .times. 10.sup.3 +307 <.+-.2 2 923 +210 " 1.53 .times. 10.sup.3 +318 " 1.09 .times. 10.sup.3 +395 " 3 710 +235 " 811 +412 " 781 +480 " 4 493 +280 " 583 +431 " 527 +545 " 5 963 +205 " 1.23 .times. 10.sup.3 +320 " 1.05 .times. 10.sup.3 +400 " 6 720 +215 " 803 +390 " 780 +475 " 7 893 +203 " 1.99 .times. 10.sup.3 +315 " 1.96 .times. 10.sup.3 +348 " 8 818 +218 " 556 +426 " 545 +529 " 9 625 +244 " 701 +405 " 703 +503 "10 631 +241 " 707 +401 " 703 +503 "11 321 +285 " 572 +4161 " 566 +5141 "12 218 +299 " 503 +386 " 524 +541 "13 595 +275 " 701 +405 " 703 +503 "14 308 +281 " 572 +416 " 566 +514 "15 583 +276 " 701 +405 " 703 +503 "16 300 +280 " 572 +416 " 566 +514 "17 610 +279 " 701 +405 " 703 +503 "18 318 +286 " 572 +416 " 566 +514 "19 925 +203 " 580 +422 " 545 +529 "20 781 +218 " 699 +403 " 703 +503 "21 785 +228 " 571 +425 " 545 +529 "22 523 +248 " 678 +409 " 703 +503 "23 712 +251 " 559 +414 " 545 +529 "24 455 +263 " 650 +400 " 703 +503 "25 585 +269 " 685 +410 " 703 +503 "26 564 +268 " 671 +405 " 703 +503 "27 5.85 .times. 10.sup.3 -298 " 7.25 .times. 10.sup.3 -483 " 6.14 .times. 10.sup.3 -705 "28 3.23 .times. 10.sup.3 -284 " 4.26 .times. 10.sup.3 -448 " 3.88 .times. 10.sup.3 -509 "29 1.84 .times. 10.sup.3 -283 " 2.62 .times. 10.sup.3 -431 " 2.17 .times. 10.sup.3 -417 "30 814 -163 " 893 -285 " 866 -284 "31 3.10 .times. 10.sup.3 -276 " 4.21 .times. 10.sup.3 -451 " 3.90 .times. 10.sup.3 -515 "32 1.94 .times. 10.sup.3 -284 " 2.85 .times. 10.sup.3 -436 " 2.18 .times. 10.sup.3 -421 "33 2.03 .times. 10.sup.3 -299 " 5.07 .times. 10.sup.3 -452 " 5.14 .times. 10.sup.3 -618 "34 1.86 .times. 10.sup.3 -286 " 1.48 .times. 10.sup.3 -303 " 1.02 .times. 10.sup.3 -326 "35 1.03 .times. 10.sup.3 -251 " 1.52 .times. 10.sup.3 -301 " 1.50 .times. 10.sup.3 -347 "36 1.02 .times. 10.sup.3 -233 " 1.47 .times. 10.sup.3 -316 " 1.50 .times. 10.sup.3 -347 "37 985 -185 " 1.14 .times. 10.sup.3 -281 " 1.07 .times. 10.sup.3 -334 "38 818 -135 " 886 -251 " 9.02 -295 "39 1.48 .times. 10.sup.3 -281 " 1.52 .times. 10.sup.3 -301 " 1.50 .times. 10.sup.3 -347 "40 1.25 .times. 10.sup.3 -220 " 1.14 .times. 10.sup.3 -281 " 1.07 .times. 10.sup.3 -334 "41 1.11 .times. 10.sup.3 -256 " 1.52 .times. 10.sup.3 -301 " 1.50 .times. 10.sup.3 -347 "42 1.03 .times. 10.sup.3 -188 " 1.14 .times. 10.sup.3 -281 " 1.07 .times. 10.sup.3 -334 "43 1.23 .times. 10.sup.3 -248 " 1.52 .times. 10.sup.3 -301 " 1.50 .times. 10.sup.3 -347 "44 1.09 .times. 10.sup.3 -195 " 1.14 .times. 10.sup.3 -281 " 1.07 .times. 10.sup.3 -334 "45 1.90 .times. 10.sup.3 -299 " 1.55 .times. 10.sup.3 -314 " 1.02 .times. 10.sup.3 -326 "46 2.54 .times. 10.sup.3 -273 " 1.86 .times. 10.sup.3 -295 " 1.50 .times. 10.sup.3 -314 "47 1.28 .times. 10.sup.3 -249 " 1.35 .times. 10.sup.3 -288 " 1.02 .times. 10.sup.3 -326 "48 980 -203 " 1.38 .times. 10.sup.3 -256 " 1.50 .times. 10.sup.3 -341 "49 2.05 .times. 10.sup.3 -285 " 1.56 .times. 10.sup.3 -311 " 1.02 .times. 10.sup.3 -326 "50 1.76 .times. 10.sup.3 -251 " 1.67 .times. 10.sup.3 -285 " 1.50 .times. 10.sup.3 -341 "51 1.24 .times. 10.sup.3 -240 " 1.58 .times. 10.sup.3 -295 " 1.50 .times. 10.sup.3 -341 "52 1.48 .times. 10.sup.3 -259 " 1.55 .times. 10.sup.3 -336 " 1.50 .times. 10.sup.3 -341 "53 703 +112 " 884 +162 " 830 +261 "54 625 +101 " 878 +156 " 816 +258 "__________________________________________________________________________
TABLE 16__________________________________________________________________________(Characteristic value corresponding to the sample in Table 8)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resis- Rate of Resis- Rate of Resis- Rate of tance value Change tance value Change tance value Change at 25.degree. C. in Resis- at 25.degree. C. in Resis- at 25.degree. C. in Resis- R.sub.25 TCR tance R.sub.25 TCR tance R.sub.25 TCR tanceNO (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________1 2.92 .times. 10.sup.3 +118 <.+-.2 3.46 .times. 10.sup.3 +321 <.+-.2 3.14 .times. 10.sup.3 +357 <.+-.22 1.16 .times. 10.sup.3 +124 " 2.03 .times. 10.sup.3 +403 " 1.77 .times. 10.sup.3 +421 "3 983 +159 " 1.65 .times. 10.sup.3 +463 " 1.05 .times. 10.sup.3 +480 "4 786 +214 " 892 +494 " 828 +676 "5 2.98 .times. 10.sup.3 +120 " 3.84 .times. 10.sup.3 +360 " 3.13 .times. 10.sup.3 +362 "6 1.26 .times. 10.sup.3 +123 " 2.35 .times. 10.sup.3 +420 " 1.81 .times. 10.sup.3 +427 "7 965 +160 " 2.14 .times. 10.sup.3 +430 " 1.09 .times. 10.sup.3 +480 "8 789 +223 " 874 +490 " 831 +675 "9 963 +163 " 1.92 .times. 10.sup.3 +453 " 1.07 .times. 10.sup.3 +485 "10 1.03 .times. 10.sup.3 +123 " 1.86 .times. 10.sup.3 +314 " 1.78 .times. 10.sup.3 +512 "11 925 +155 " 1.02 .times. 10.sup.3 +368 " 1.13 .times. 10.sup.3 +567 "12 833 +202 " 983 +480 " 925 +624 "13 805 +248 " 854 +475 " 835 +675 "14 744 +249 " 821 +485 " 815 +685 "15 635 +255 " 735 +492 " 740 +702 "16 2.00 .times. 10.sup.3 +89 " 1.96 .times. 10.sup.3 +303 " 1.78 .times. 10.sup.3 +512 "17 1.51 .times. 10.sup.3 +115 " 1.82 .times. 10.sup.3 +343 " 1.13 .times. 10.sup.3 +567 "18 1.14 .times. 10.sup.3 +126 " 1.72 .times. 10.sup.3 +392 " 925 +624 "19 1.02 .times. 10.sup.3 +180 " 1.68 .times. 10.sup.3 +403 " 835 +675 "20 921 +205 " 956 +424 " 815 +685 "21 829 +238 " 912 +490 " 740 +702 "22 1.05 .times. 10.sup.3 +105 " 1.12 .times. 10.sup.3 +390 " 925 +624 "23 921 +150 " 985 +436 " 815 +685 "24 884 +136 " 925 +453 " 925 +624 "25 795 +181 " 894 +483 " 815 +685 "26 935 +161 " 913 +409 " 925 +624 "27 880 +180 " 862 +490 " 815 +685 "28 706 +223 " 752 +493 " 835 +675 "29 641 +244 " 680 +496 " 815 +685 "30 654 +249 " 672 +495 " 835 +675 "31 606 +250 " 632 +480 " 815 +685 "32 753 +195 " 690 +476 " 835 +675 "33 706 +203 " 683 +481 " 815 +685 "34 1.08 .times. 10.sup.3 +123 " 1.12 .times. 10.sup.3 +373 " 1.13 .times. 10.sup.3 +567 "35 1.14 .times. 10.sup.3 +106 " 1.14 .times. 10.sup.3 +359 " 1.13 .times. 10.sup.3 +567 "36 929 +192 " 953 +393 " 956 +634 "__________________________________________________________________________
TABLE 17__________________________________________________________________________(Characteristic value corresponding to the sample in Table 9)Example 1 Carbonate-Free Carbonate & Fluoride-Free Resis- Rate of Resis- Rate of Resis- Rate of tance value Change tance value Change tance value Change at 25.degree. C. in Resis- at 25.degree. C. in Resis- at 25.degree. C. in Resis- R.sub.25 TCR tance R.sub.25 TCR tance R.sub.25 TCR tanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________1 9.07 .times. 10.sup.3 -276 <.+-.2 9.56 .times. 10.sup.3 -483 <.+-.2 9.13 .times. 10.sup.3 -528 <.+-.22 20.2 .times. 10.sup.3 -278 " 23.1 .times. 10.sup.3 -495 " 21.4 .times. 10.sup.3 -676 "3 16.5 .times. 10.sup.3 -289 " 19.4 .times. 10.sup.3 -496 " 17.6 .times. 10.sup.3 -805 "4 2.45 .times. 10.sup.3 -216 " 3.77 .times. 10.sup.3 -350 " 2.86 .times. 10.sup.3 -396 "5 825 +222 " 1.01 .times. 10.sup.3 +362 " 888 +380 "6 4.01 .times. 10.sup.3 -152 " 4.22 .times. 10.sup.3 -249 " 4.18 .times. 10.sup.3 -256 "7 31.6 .times. 10.sup.3 -292 " 34.0 .times. 10.sup.3 -486 " 32.1 .times. 10.sup.3 -929 "8 18.5 .times. 10.sup.3 -296 " 24.1 .times. 10.sup.3 -493 " 20.0 .times. 10.sup.3 -956 "9 6.88 .times. 10.sup.3 -277 " 8.03 .times. 10.sup.3 -446 " 7.14 .times. 10.sup.3 -530 "10 2.55 .times. 10.sup.3 -242 " 3.96 .times. 10.sup.3 -387 " 3.04 .times. 10.sup.3 -407 "11 4.29 .times. 10.sup.3 -269 " 4.93 .times. 10.sup.3 -477 " 4.80 .times. 10.sup.3 -628 "12 7.68 .times. 10.sup.3 -275 " 8.95 .times. 10.sup.3 -467 " 8.11 .times. 10.sup.3 -607 "13 25.4 .times. 10.sup.3 -293 " 29.4 .times. 10.sup.3 -480 " 26.4 .times. 10.sup.3 -814 "14 27.9 .times. 10.sup.3 -261 " 34.9 .times. 10.sup.3 -417 " 29.6 .times. 10.sup.3 -505 "15 10.6 .times. 10.sup.3 -116 " 16.9 .times. 10.sup.3 -290 " 11.4 .times. 10.sup.3 -334 "16 13.9 .times. 10.sup.3 -288 " 14.7 .times. 10.sup.3 -491 " 14.1 .times. 10.sup.3 -769 "17 9.21 .times. 10.sup.3 -287 " 11.9 .times. 10.sup.3 -465 " 10.6 .times. 10.sup.3 -582 "18 3.85 .times. 10.sup. 3 -249 " 4.95 .times. 10.sup.3 -425 " 4.18 .times. 10.sup.3 -520 "19 12.6 .times. 10.sup.3 -234 " 16.6 .times. 10.sup.3 -392 " 12.8 .times. 10.sup.3 -477 "20 9.44 .times. 10.sup.3 -216 " 14.3 .times. 10.sup.3 -401 " 10.0 .times. 10.sup.3 -500 "21 924 -169 " 1.18 .times. 10.sup.3 -373 " 1.01 .times. 10.sup.3 -423 "22 8.05 .times. 10.sup.3 -264 " 9.02 .times. 10.sup.3 -495 " 8.18 .times. 10.sup.3 -677 "23 4.02 .times. 10.sup.3 -250 " 5.13 .times. 10.sup.3 -388 " 4.43 .times. 10.sup.3 -459 "24 1.21 .times. 10.sup.3 -234 " 2.07 .times. 10.sup.3 -379 " 1.52 .times. 10.sup.3 -533 "25 5.09 .times. 10.sup.3 -262 " 7.09 .times. 10.sup.3 -416 " 5.24 .times. 10.sup.3 -540 "26 5.49 .times. 10.sup.3 -270 " 5.92 .times. 10.sup.3 -433 " 5.84 .times. 10.sup.3 -574 "27 18.4 .times. 10.sup.3 -298 " 22.2 .times. 10.sup.3 -482 " 20.5 .times. 10.sup.3 -865 "28 12.6 .times. 10.sup.3 -186 " 15.6 .times. 10.sup.3 -316 " 13.3 .times. 10.sup.3 -414 "29 4.11 .times. 10.sup.3 -107 " 5.20 .times. 10.sup.3 -222 " 4.46 .times. 10.sup.3 -295 "30 28.4 .times. 10.sup.3 -284 " 36.3 .times. 10.sup.3 -492 " 31.1 .times. 10.sup.3 -639 "31 16.0 .times. 10.sup.3 -292 " 16.9 .times. 10.sup.3 -499 " 16.5 .times. 10.sup.3 -821 "32 925 -106 " 995 -232 " 990 -259 "33 7.96 .times. 10.sup.3 -295 " 10.3 .times. 10.sup.3 -486 " 8.24 .times. 10.sup.3 -795 "34 3.82 .times. 10.sup.3 -264 " 5.28 .times. 10.sup.3 -378 " 4.33 .times. 10.sup.3 -496 "35 1.02 .times. 10.sup.3 +96 " 2.05 .times. 10.sup.3 +89 " 1.14 .times. 10.sup.3 +125 "36 524 +250 " 647 +370 " 628 +482 "37 36.0 .times. 10.sup.3 -289 " 37.7 .times. 10.sup.3 -485 " 36.3 .times. 10.sup.3 -992 "38 15.5 .times. 10.sup.3 -275 " 19.0 .times. 10.sup.3 -466 " 16.4 .times. 10.sup.3 -584 "39 8.00 .times. 10.sup.3 -270 " 9.93 .times. 10.sup.3 -447 " 8.14 .times. 10.sup.3 -534 "40 4.05 .times. 10.sup.3 -206 " 6.01 .times. 10.sup.3 -250 " 4.27 .times. 10.sup.3 -317 "41 5.09 .times. 10.sup.3 -219 " 5.70 .times. 10.sup.3 -365 " 5.45 .times. 10.sup.3 -487 "42 2.26 .times. 10.sup.3 -244 " 3.07 .times. 10.sup.3 -430 " 2.87 .times. 10.sup.3 -521 "43 12.0 .times. 10.sup.3 -289 " 14.9 .times. 10.sup.3 -477 " 12.4 .times. 10.sup.3 -855 "44 7.03 .times. 10.sup.3 -294 " 10.2 .times. 10.sup.3 -411 " 7.14 .times. 10.sup.3 -505 "45 5.49 .times. 10.sup.3 -233 " 9.05 .times. 10.sup.3 -395 " 6.23 .times. 10.sup.3 -480 "46 980 +204 " 1.30 .times. 10.sup.3 +285 " 1.19 .times. 10.sup.3 +329 "47 6.97 .times. 10.sup.3 -288 " 9.66 .times. 10.sup.3 -483 " 8.11 .times. 10.sup. -683 "48 2.79 .times. 10.sup.3 -195 " 5.11 .times. 10.sup.3 -303 " 3.18 .times. 10.sup.3 -359 "49 20.6 .times. 10.sup.3 -289 " 24.7 .times. 10.sup.3 -480 " 22.4 .times. 10.sup.3 -805 "50 15.4 .times. 10.sup.3 -221 " 21.3 .times. 10.sup.3 -419 " 17.7 .times. 10.sup.3 -551 "51 5.82 .times. 10.sup.3 -125 " 7.10 .times. 10.sup.3 -344 " 7.01 .times. 10.sup.3 -384 "52 4.02 .times. 10.sup.3 -128 " 6.09 .times. 10.sup.3 -285 " 4.98 .times. 10.sup.3 -399 "53 2.77 .times. 10.sup.3 -105 " 4.95 .times. 10.sup.3 -216 " 3.03 .times. 10.sup.3 -304 "54 5.29 .times. 10.sup.3 -212 " 9.22 .times. 10.sup.3 -382 " 6.18 .times. 10.sup.3 -454 "55 10.5 .times. 10.sup.3 -277 " 15.6 .times. 10.sup.3 -495 " 11.4 .times. 10.sup.3 -882 "56 3.00 .times. 10.sup.3 -212 " 3.18 .times. 10.sup.3 -212 " 3.05 .times. 10.sup.3 -309 "57 13.6 .times. 10.sup.3 -266 " 16.2 .times. 10.sup.3 -423 " 14.9 .times. 10.sup.3 -529 "58 11.2 .times. 10.sup.3 -221 " 14.5 .times. 10.sup.3 -326 " 13.4 .times. 10.sup.3 -418 "59 2.01 .times. 10.sup.3 -106 " 4.22 .times. 10.sup.3 -210 " 2.16 .times. 10.sup.3 -293 "60 3.12 .times. 10.sup.3 -121 " 5.67 .times. 10.sup.3 -199 " 3.39 .times. 10.sup.3 -305 "61 15.7 .times. 10.sup.3 -296 " 16.9 .times. 10.sup.3 -491 " 16.3 .times. 10.sup.3 -867 "62 10.7 .times. 10.sup.3 -291 " 12.6 .times. 10.sup.3 -482 " 11.0 .times. 10.sup.3 -797 "63 1.04 .times. 10.sup.3 -200 " 2.09 .times. 10.sup.3 -275 " 1.19 .times. 10.sup.3 -312 "64 2.55 .times. 10.sup.3 -212 " 4.11 .times. 10.sup.3 -346 " 2.76 .times. 10.sup.3 -425 "65 2.84 .times. 10.sup.3 -209 " 5.71 .times. 10.sup.3 -315 " 3.19 .times. 10.sup.3 -404 "66 21.9 .times. 10.sup.3 -225 " 2.18 .times. 10.sup.3 -303 " 2.05 .times. 10.sup.3 -377 "67 6.05 .times. 10.sup.3 -234 " 24.9 .times. 10.sup.3 -473 " 22.8 .times. 10.sup.3 -676 "68 5.79 .times. 10.sup.3 -277 " 8.07 .times. 10.sup.3 -493 " 6.39 .times. 10.sup.3 -820 "69 13.5 .times. 10.sup.3 - 280 " 18.8 .times. 10.sup.3 -469 " 15.7 .times. 10.sup.3 -796 "70 10.1 .times. 10.sup.3 -225 " 14.7 .times. 10.sup.3 -407 " 11.6 .times. 10.sup.3 -491 "71 1.85 .times. 10.sup.3 -174 " 2.41 .times. 10.sup.3 -312 " 2.35 .times. 10.sup.3 -353 "72 94.8 .times. 10.sup.3 -88 " 1.80 .times. 10.sup.3 -243 " 1.07 .times. 10.sup.3 -307 "73 15.2 .times. 10.sup.3 -285 " 20.3 .times. 10.sup.3 -469 " 16.2 .times. 10.sup.3 -751 "74 17.9 .times. 10.sup.3 -290 " 24.9 .times. 10.sup.3 -473 " 20.5 .times. 10.sup.3 -787 "75 1.85 .times. 10.sup.3 -192 " 4.85 .times. 10.sup.3 -315 " 2.16 .times. 10.sup.3 -356 "76 1.44 .times. 10.sup.3 +221 " 2.03 .times. 10.sup.3 +357 " 1.99 .times. 10.sup.3 +420 "77 3.79 .times. 10.sup.3 -236 " 5.96 .times. 10.sup.3 -405 " 4.24 .times. 10.sup.3 -485 "78 7.00 .times. 10.sup.3 -250 " 9.53 .times. 10.sup.3 -436 " 7.14 .times. 10.sup.3 -652 "79 7.89 .times. 10.sup.3 -262 " 10.2 .times. 10.sup.3 -449 " 8.53 .times. 10.sup.3 -645 "80 13.4 .times. 10.sup.3 -249 " 17.9 .times. 10.sup.3 -415 " 15.3 .times. 10.sup.3 -577 "81 6.03 .times. 10.sup.3 -260 " 6.33 .times. 10.sup.3 -382 " 6.21 .times. 10.sup.3 -514 "82 3.09 .times. 10.sup.3 -263 " 5.11 .times. 10.sup.3 -425 " 4.02 .times. 10.sup.3 -520 "83 1.72 .times. 10.sup.3 -187 " 4.07 .times. 10.sup. 3 -249 " 2.00 .times. 10.sup.3 -348 "84 3.85 .times. 10.sup.3 -179 " 7.35 .times. 10.sup.3 -235 " 4.11 .times. 10.sup.3 -380 "85 9.11 .times. 10.sup.3 -296 " 14.5 .times. 10.sup.3 -489 " 10.6 .times. 10.sup.3 -925 "86 6.04 .times. 10.sup.3 -236 " 6.41 .times. 10.sup.3 -415 " 6.22 .times. 10.sup.3 -545 "87 10.5 .times. 10.sup.3 -277 " 14.2 .times. 10.sup.3 -495 " 12.9 .times. 10.sup.3 -889 "88 17.7 .times. 10.sup.3 -281 " 23.4 .times. 10.sup.3 -479 " 19.5 .times. 10.sup.3 -826 "89 6.75 .times. 10.sup.3 -267 " 10.7 .times. 10.sup.3 -452 " 8.19 .times. 10.sup.3 -695 "90 2.29 .times. 10.sup.3 -216 " 5.33 .times. 10.sup.3 -326 " 3.14 .times. 10.sup.3 -459 "91 16.5 .times. 10.sup.3 -241 " 17.9 .times. 10.sup.3 -473 " 17.4 .times. 10.sup.3 -626 "92 15.6 .times. 10.sup.3 -270 " 21.4 .times. 10.sup.3 -470 " 18.6 .times. 10.sup.3 -893 "93 18.3 .times. 10.sup.3 -281 " 24.0 .times. 10.sup.3 -475 " 21.5 .times. 10.sup.3 -884 "94 15.4 .times. 10.sup.3 -290 " 23.6 .times. 10.sup.3 -468 " 19.9 .times. 10.sup.3 -834 "95 4.02 .times. 10.sup.3 -287 " 7.12 .times. 10.sup.3 -356 " 4.15 .times. 10.sup.3 -477 "96 1.89 .times. 10.sup.3 -162 " 3.01 .times. 10.sup.3 -250 " 2.90 .times. 10.sup.3 -299 "97 20.3 .times. 10.sup.3 -273 " 24.7 .times. 10.sup.3 -493 " 22.4 .times. 10.sup.3 -805 "98 10.1 .times. 10.sup.3 -269 " 13.3 .times. 10.sup.3 -452 " 11.5 .times. 10.sup.3 -603 "99 6.25 .times. 10.sup.3 -216 " 9.69 .times. 10.sup.3 -395 " 7.18 .times. 10.sup.3 -525 "100 3.80 .times. 10.sup.3 -207 " 6.18 .times. 10.sup.3 -376 " 3.87 .times. 10.sup.3 -489 "101 1.15 .times. 10.sup.3 -149 " 1.82 .times. 10.sup.3 -288 " 1.72 .times. 10.sup.3 -360 "102 12.8 .times. 10.sup.3 -280 " 16.7 .times. 10.sup.3 -481 " 14.4 .times. 10.sup.3 -863 "103 18.3 .times. 10.sup.3 -226 " 23.0 .times. 10.sup.3 -432 " 19.1 .times. 10.sup.3 -590 "104 21.4 .times. 10.sup.3 -280 " 29.2 .times. 10.sup.3 -476 " 25.6 .times. 10.sup.3 -842 "105 7.03 .times. 10.sup.3 -216 " 12.6 .times. 10.sup.3 -358 " 9.02 .times. 10.sup.3 -492 "106 969 +70 " 992 +148 " 983 +196 "107 3.00 .times. 10.sup.3 -201 " 3.56 .times. 10.sup.3 -388 " 3.14 .times. 10.sup.3 -502 "108 4.17 .times. 10.sup.3 -212 " 7.23 .times. 10.sup.3 -365 " 5.01 .times. 10.sup.3 -483 "109 5.84 .times. 10.sup.3 -182 " 9.44 .times. 10.sup.3 -250 " 6.24 .times. 10.sup.3 -314 "110 5.99 .times. 10.sup.3 -209 " 10.1 .times. 10.sup.3 -371 " 6.92 .times. 10.sup.3 -505 "111 7.03 .times. 10.sup.3 -220 " 7.51 .times. 10.sup.3 -428 " 7.44 .times. 10.sup.3 -521 "112 9.76 .times. 10.sup.3 -254 " 13.4 .times. 10.sup.3 -452 " 11.0 .times. 10.sup.3 -647 "113 4.01 .times. 10.sup.3 -172 " 6.33 .times. 10.sup.3 -333 " 4.56 .times. 10.sup.3 -424 "114 4.70 .times. 10.sup.3 -225 " 6.49 .times. 10.sup.3 -329 " 4.73 .times. 10.sup.3 -412 "115 9.54 .times. 10.sup.3 -185 " 15.4 .times. 10.sup.3 -376 " 10.2 .times. 10.sup.3 -509 "116 9.09 .times. 10.sup.3 -196 " 9.29 .times. 10.sup.3 -395 " 9.18 .times. 10.sup.3 -518 "117 6.19 .times. 10.sup.3 -200 " 8.81 .times. 10.sup.3 -400 " 7.02 .times. 10.sup.3 -540 "118 6.25 .times. 10.sup.3 -225 " 9.24 .times. 10.sup.3 -416 " 6.88 .times. 10.sup.3 -523 "119 5.87 .times. 10.sup.3 -230 " 10.1 .times. 10.sup.3 -420 " 6.90 .times. 10.sup.3 -520 "120 5.14 .times. 10.sup.3 -209 " 9.91 .times. 10.sup.3 -405 " 5.89 .times. 10.sup.3 -509 "__________________________________________________________________________
EXAMPLE 2
In accordance with Example 1, multilayered ceramic substrates were prepared, except that the molybdates, fluorides and glass powders having the compositions specified in Table 18 were used without any heat treatment, and their R.sub.25, TCR and rate of changes in resistance were measured. The results are indicated in Table 19 with the corresponding sample numbers.
TABLE 18__________________________________________________________________________(Ex. 2 - Composition in the case without heattreating Molybdates withothers)Composition Glass Fluorides Carbonates Molybdate B (wt. %) (wt. %)NOs (wt. %) (wt. %) SrF.sub.2 BaF.sub.2 MgF.sub.2 CaF.sub.2 SrCO.sub.3 BaCO.sub.3 MgCO.sub.3 CaCO.sub.3__________________________________________________________________________1 MgMoO.sub.4 40 59 0.5 0.52 CaMoO.sub.4 40 59 0.5 0.53 SrMoO.sub.4 40 59 0.5 0.54 BaMoO.sub.4 40 59 0.5 0.55 (Mg.sub.0.3 Ca.sub.0.7)MoO.sub.4 60 20 10 106 MgMoO.sub.4 30 20 10 10 Ca.sub.3 MoO.sub.6 307 ZnMoO.sub.4 65 34 0.5 0.58 Al.sub.2 Mo.sub.3 O.sub.12 60 39 0.5 0.59 ZrMo.sub.2 O.sub.8 45 54 0.5 0.510 HfMo.sub.2 O.sub.8 45 54 0.5 0.511 Y.sub.6 MoO.sub.12 80 5 7.5 7.512 La.sub.6 MoO.sub.12 80 5 7.5 7.513 Ce.sub.6 MoO.sub.12 80 5 7.5 7.514 Pr.sub.6 MoO.sub.12 80 5 7.5 7.515 Nd.sub.6 MoO.sub.12 80 5 7.5 7.516 Sm.sub.6 MoO.sub.12 80 5 7.5 7.517 Eu.sub.6 MoO.sub.12 80 5 7.5 7.518 Gd.sub.6 MoO.sub.12 80 5 7.5 7.519 Tb.sub.6 MoO.sub.12 80 5 7.5 7.520 Dy.sub.6 MoO.sub.12 80 5 7.5 7.521 Ho.sub.6 MoO.sub.12 80 5 7.5 7.522 Er.sub.6 MoO.sub.12 80 5 7.5 7.523 Tm.sub. 6 MoO.sub.12 80 5 7.5 7.524 Yb.sub.6 MoO.sub.12 80 5 7.5 7.525 Lu.sub.6 MoO.sub.12 80 5 7.5 7.526 Nb.sub.6 Mo.sub.3 O.sub.14 55 44 0.5 0.527 Ta.sub.2 Mo.sub.3 O.sub.14 55 44 0.5 0.528 MnMoO.sub.4 65 34 0.5 0.5__________________________________________________________________________
TABLE 19__________________________________________________________________________(Characteristic value corresponding to the sample in Table 18)Example 2 Fluoride Free Resistance Rate of Resistance Rate of value at Change value at Change 25.degree. C. in Resis- 25.degree. C. in Resis- R.sub.25 TCR tance R.sub.25 TCR tanceNos (.OMEGA.) (ppm/.degree.C.) (%) (.OMEGA.) (ppm/.degree.C.) (%)__________________________________________________________________________1 3.04 .times. 10.sup.3 -1316 <.+-.2 4.35 .times. 10.sup.3 -1356 <.+-.22 29.8 .times. 10.sup.3 -1435 " 35.2 .times. 10.sup.3 -1483 "3 674 -1385 " 823 -1411 "4 388 +1156 " 524 +1192 "5 8.44 .times. 10.sup.3 -1384 " 9.83 .times. 10.sup.3 -1401 "6 6.24 .times. 10.sup.3 -1309 " 7.29 .times. 10.sup.3 -1328 "7 4.80 .times. 10.sup.3 -1370 " 5.63 .times. 10.sup.3 -1412 "8 11.6 .times. 10.sup.3 -1462 " 12.5 .times. 10.sup.3 -1489 "9 17.4 .times. 10.sup.3 -1615 " 18.9 .times. 10.sup.3 -1676 "10 15.4 .times. 10.sup.3 -1468 " 16.2 .times. 10.sup.3 +1498 "11 5.95 .times. 10.sup.3 -1216 " 6.82 .times. 10.sup.3 -1273 "12 5.03 .times. 10.sup.3 -1206 " 6.23 .times. 10.sup.3 -1256 "13 3.95 .times. 10.sup.3 -1195 " 4.36 .times. 10.sup.3 +1232 "14 3.88 .times. 10.sup.3 -1192 " 4.21 .times. 10.sup.3 -1213 "15 4.99 .times. 10.sup.3 -1312 " 5.36 .times. 10.sup.3 -1363 "19 7.18 .times. 10.sup.3 -1269 " 8.05 .times. 10.sup.3 -1272 "20 7.33 .times. 10.sup.3 -1050 " 8.65 .times. 10.sup.3 -1080 "21 7.18 .times. 10.sup.3 -1182 " 8.23 .times. 10.sup.3 -1210 "22 7.85 .times. 10.sup.3 -1324 " 8.41 .times. 10.sup.3 -1363 "23 6.94 .times. 10.sup.3 -1306 " 7.81 .times. 10.sup.3 +1353 "24 6.03 .times. 10.sup.3 -1244 " 7.03 .times. 10.sup.3 -1286 "25 4.67 .times. 10.sup.3 -1195 " 5.63 .times. 10.sup.3 -1215 "26 625 +1059 " 725 +1080 "27 1.45 .times. 10.sup.3 -1345 " 2.03 .times. 10.sup.3 -1376 "28 905 +1230 " 1.06 .times. 10.sup.3 -1271 "__________________________________________________________________________
COMPARISON EXAMPLE 1
MoSi.sub.2 -TaSi.sub.2 Glass Base Resistor Material
A mixture of 16 parts by weight of MoSi.sub.2 with 9 parts by weight of TaSi.sub.2 was heated at 1400.degree. C. in vacuum. The resulting product was pulverized together with ethanol by alumina balls in a pot mill for 24 hours, and was dried to obtain fine powders having a particle size of 10 .mu.m or lower. Seventy five (75) parts by weight of glass frit consisting of BaO, B.sub.2 O.sub.3, MgO, CaO and SiO.sub.2 and 25 parts by weight of the organic vehicle (20 parts by weight of butyl carbitol plus 5 parts by weight of ethyl cellulose) were added to 25 parts by weight of the thus obtained fine powders, and were roll-milled to obtain a resistive paste.
Except that this resistive paste was used, a multilayered ceramic board was obtained in the same manner as in the foregoing examples.
As a result, the product obtained by forming the resistive film produced from said paste on a ceramic green sheet, heat-treating them for the decomposition of the organics and, thereafter, simultaneously sintering them could not be put to practical use, since it warped due to differences in the coefficients of expansion and shrinkage between both the sintered bodies, as illustrated in FIG. 4, and swelled due to the evolution of a gas by the decomposing reaction of MoSi.sub.2 and TaSi.sub.2, as illustrated in FIG. 5. It is to be noted that 11a, 14a and 13a are a layer corresponding to the aforesaid layer 1a, a layer corresponding to the aforesaid layer 4a and a thick-film resistor corresponding to the aforesaid thick-film resistor 3a, respectively.
COMPARISON EXAMPLE 2
MoSi.sub.2 -BaF.sub.2 Glass Base Resistor Material
Seventy (70) parts by weight of MoSi.sub.2 and 20 parts by weight of BaF.sub.2 were mixed with 10 parts by weight of glass frit comprising SiO.sub.2, ZnO, ZrO.sub.2, CaO and Al.sub.2 O.sub.3 by ball-milling, and the resulting powders were heat-treated at 1200.degree. C. in an argon (Ar) gas atmosphere. Thereafter, the product was pulverized together with ethanol for 24 hours by alumina balls in a pot mill, and was dried to obtain fine powders having a particle size of 10 .mu.m or lower.
Except that this resistive paste was used, a multilayered ceramic board was obtained in the same manner as in Example 1. Shown in Table 20 are the results of the R.sub.25, TCR and rate of change in resistance value of the thick-film resistor of the multilayered ceramic substrate, which were measured in the same manner as in Example 1.
TABLE 20______________________________________Resistance Value TCR Rate of Change inR.sub.25 at 25.degree. C., Ohms ppm/.degree.C. Resistance Value, %______________________________________Comp. Ex. 124.5 +1120 9.7% increase______________________________________
From the above results, it has been found that the multilayered ceramic boards according to the examples all undergo neither warping nor swelling, and their rate of change in resistance value is within .+-.2%, and that, in particular, the TCR of those having the resistor material heat-treated does not exceed .+-.500 ppm/.degree.C. in the case where the fluorides of alkaline earth metals are used and .+-.300 ppm/.degree.C. in the case where the carbonates of alkaline earth metals are used. It has been noted, on the other hand, that the multilayered ceramic board of Comp. Ex. 1 undergoes warping, whereas the multilayered ceramic board of Comp. Ex. 2 has its resistor showing a rate of change in resistance value that is four times higher and a TCR that is one order of magnitude higher.
EFFECTS OF THE INVENTION
According to the present invention, there can be provided a sintered body containing at least one molybdate selected from at least one molybdate group selected from the groups (A) to (G) defined in the foregoing, with or without the flurodie of an alkaline earth metal, and an electrical resistor paste containing a resistive material for said sintered body and the carbonate of an alkaline earth metal. Accordingly, if the resistor material or paste for this sintered body is used and sintered along with a conductor material based on, e.g., a base metal and a ceramic green sheet in a nonoxidizing atmosphere to form a resistor, it is very unlikely that the sintered body may either warp or swell due to sintering. It is further possible not only to decrease a change-with-time of the resistance value esp. at a high humidity but also to reduce the temperature dependence coefficient of the resistance value of the resistor not to exceed .+-.300 ppm/.degree.C., for instance.
Hence, it is possible to meet both the demands for reductions in the size and cost of circuit boards having resistors incorporated thereinto and to provide excellent electronic parts to electronic equipment needing precise work.
Further, if the molybdate belonging to the aforesaid groups (A) to (G), preferably with the fluoride of an alkaline earth metal are heat-treated with glass, it is then possible to decrease the absolute value of the temperature dependent coefficient of the resistor and add excellent capabilities to electronic circuits needing precise performance, compared with the case where such any heat-treatment is not carried out.

Number	Date	Country
62-45615	Feb 1987	JPX
62-45619	Feb 1987	JPX
62-104415	Apr 1987	JPX
62-104416	Apr 1987	JPX

Number	Name	Date	Kind
4891158	Hatu	Jan 1990
4940849	Monis et al.	Jul 1990

Electrical resistors, electrical resistor paste and method for making the same

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