U.S. patent number 3,928,245 [Application Number 05/377,218] was granted by the patent office on 1975-12-23 for metal oxide voltage-variable resistor composition.
This patent grant is currently assigned to General Electric Company. Invention is credited to Herbert Fishman, James S. Kresge.
United States Patent |
3,928,245 |
Fishman , et al. |
December 23, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Metal oxide voltage-variable resistor composition
Abstract
A metal oxide resistor of the type consisting essentially of
zinc oxide and containing significant amounts of the impurities
bismuth trioxide, cobalt trioxide, manganese dioxide, antimony
oxide, chromic oxide, and silicon dioxide contains also significant
amounts of the impurities barium oxide and boron oxide.
Inventors: |
Fishman; Herbert (Pittsfield,
MA), Kresge; James S. (Pittsfield, MA) |
Assignee: |
General Electric Company
(Pittsfield, MA)
|
Family
ID: |
23488228 |
Appl.
No.: |
05/377,218 |
Filed: |
July 9, 1973 |
Current U.S.
Class: |
252/519.52;
252/519.54; 338/21 |
Current CPC
Class: |
H01C
7/112 (20130101) |
Current International
Class: |
H01C
7/105 (20060101); H01C 7/112 (20060101); H01B
001/08 () |
Field of
Search: |
;252/518,521 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Sebastian; Leland A.
Attorney, Agent or Firm: Ulbrich; Volker R.
Claims
We claim:
1. A voltage-variable sintered body resistor composition of the
type consisting mostly of zinc oxide and comprising a significant
amount of silicon dioxide, wherein the improvement comprises that
said composition also contains significant amounts of at least one
of the impurities chosen from the group consisting of barium oxide
and boron oxide.
2. The composition defined in claim 1 wherein the barium oxide is
present to a concentration of on the order of 0.1 molar
percent.
3. The composition defined in claim 1 wherein the boron oxide is
present to a concentration of on the order of about 0.1 molar
percent.
4. The composition defined in claim 1 and comprising additionally
at least one impurity chosen from the group consisting of bismuth
trioxide, cobaltic trioxide, manganese dioxide, antimony oxide, and
chromic oxide.
5. The composition defined in claim 4 and comprising:
about 96.3 molar percent zinc oxide,
about 0.5 molar percent bismuth trioxide,
about 0.5 molar percent cobaltic trioxide,
about 0.5 molar percent manganese dioxide,
about 1.0 molar percent antimony trioxide,
about 0.5 molar percent chromic oxide,
about 0.1 molar percent barium oxide,
about 0.1 molar percent boron oxide, and
about 0.25 molar percent silicon dioxide.
Description
BACKGROUND OF THE INVENTION
The invention relates generally to metal oxide non-linear
voltage-variable resistors, and is particularly applicable to, but
not limited to, zinc oxide resistors for overvoltage surge
protection devices.
Various overvoltage surge protective devices include as an
essential element a non-linear voltage-variable resistor. The
resistor may be made of silicon carbide, which is commonly used for
such a purpose, or it may also be made of a metal oxide
composition, such as zinc oxide. Overvoltage surge protection
devices and their function are discussed in, for example, the
following:
U.s. pat. Nos.
3,671,800 issued 20 June 1972 to E. W. Stetson
3,586,913 issued 22 June 1971 to A. A. Olsen et al.
2,529,144 issued 7 Nov. 1950 to E. A. Evans et al.
Technical Publications
"Electrical Transmission & Distribution Reference Book" 4th
Edition, Westinghouse Electric Corporation, Pittsburg, Pa., 1950
pp. 621 to 627.
Metal oxide compositions for non-linear resistors are described in
some detail in, for example, the following:
U.s. pat. Nos.
3,689,863 issued 5 Sept. 1972 to M. Matsuoka et al.
3,670,216 issued 13 June 1972 to T. Masuyama et al.
3,670,221 issued 13 June 1972 to K. Hamamoto et al.
3,663,458 issued 16 May 1972 to T. Masuyama et al.
3,642,664 issued 15 Feb. 1972 to T. Masuyama et al.
3,634,337 issued 11 Jan. 1972 to M. Matsuoka et al.
3,632,529 issued 4 Jan. 1972 to M. Matsuoka et al.
3,632,528 issued 4 Jan. 1972 to M. Matsuoka et al.
3,611,073 issued 5 Oct. 1971 to K. Hamamoto et al.
3,598,763 issued 10 Aug. 1971 to M. Matsuoka et al.
3,570,002 issued 24 Apr. 1968 to T. Masuyama et al.
3,503,029 issued 24 Mar. 1970 to M. Matsuoka
3,496,512 issued 17 Feb. 1970 to M. Matsuoka et al.
Technical Publications
Ichonose, Noboru "TNR High Performance Ceramic Varistor Element",
in Japan Electronic Engineering, Toyko Shibaura Electric Company,
Ltd, July 1972 pp. 32 - 36.
"Metal Oxide Varistors For Power-Surge Protection", in Electrical
World, Vol. 177, Feb. 1, 1972 p. 109.
"Unique Variable Resistor Bypasses High Voltage Spikes" in Product
Engineering, Vol. 43, Feb. 1972 p. 40.
"Defeating Power Surges", in Research & Development Review 1972
by General Electric Company, Corporate Research & Development,
Schenectady, New York, pp. 6 - 7.
While zinc oxide resistors consist substantially of zinc oxide,
certain impurities added to the zinc oxide in minute quantities are
necessary to give the resistor the characteristics which are
desired for a given application. These characteristics are termed
the strength, the exponent, and the stability.
The strength of surge arrester valve element is a measure of its
ability to resist current channeling in the bulk material under
severe loading conditions. The phenomenon by which such channeling
occurs is not presently fully understood, and the strength of a
given valve element material is thus determined on a relative basis
by empirical methods.
The exponent of a valve element material is, in effect, the degree
of non-linearity of the resistance relative to the applied voltage.
Thus, a high exponent material is more likely to be suitable as
surge arrester valve than is a low exponent material, as it will
provide a more distinct switching operation.
Stability refers to the ability of the valve element to retain its
initial current-voltage characteristics after a period of operation
under typical operating conditions.
One composition of zinc oxide which has shown considerable promise
as a surge arrester valve material has added to it, in addition to
a number of other impurities, some silicon dioxide. The silicon
dioxide increases the exponent and the resistance of the material.
However, the composition does not have the stability needed to make
it truly successful commercially for high voltage surge arrester
applications. Even under normal operating conditions, its
electrical characteristics change after a relatively short time.
Such a change can, in the case of a high voltage surge arrester,
result in a catastrophic failure causing extensive damage to other
components in the system, which the arrester is designed to
protect.
SUMMARY OF THE INVENTION
In the present invention a metal oxide non-linear voltage-variable
resistor of the type comprising silicon dioxide as an impurity
comprises in addition thereto, the impurities barium oxide and
boron oxide. The addition of the impurities barium oxide and boron
oxide results in improved stability of the resistor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a sectioned perspective of an arrester valve element
of sintered material having a composition in accordance with a
preferred embodiment of the invention.
FIG. 2 shows the relative stabilities of prior art valve elements
as compared to the valve element of FIG. 1.
PREFERRED EMBODIMENT OF THE INVENTION
A preferred embodiment of the envention is the surge arrester valve
element disc 10 shown in FIG. 1. The disc 10 is a sintered body of
zinc oxide compound provided on both faces with a contact layer 12
of silver, and also provided about the perimeter with an insulating
coating 14 to prevent flashover.
The disc 10 is pressed from a powder having the following
composition, in mole percent:
96.53 percent, ZnO (zinc oxide)
0.5 percent, Bi.sub.2 O.sub.3 (bismuth trioxide)
0.5 percent, Co.sub.2 O.sub.3 (cobalt trioxide)
0.5 percent, MnO.sub.2 (manganese dioxide)
1.0 percent, Sb.sub.2 O.sub.3 (antimony trioxide)
0.5 percent, Cr.sub.2 O.sub.3 (chromic oxide)
0.1 percent, BaCO.sub.3 (barium carbonate)
0.1 percent, B.sub.2 O.sub.3 (boron oxide)
0.25 percent, SiO.sub.2 (silicon dioxide)
After the disc 10 is pressed into shape, it is sintered in
generally the same way as are the more commonly used silicon
carbide discs. The silver layers 12 and the anti-flashover collar
14 are applied in later steps. After sintering, the disc 10 is
about 0.9 inch thick and about 23/4 inches in diameter. One or more
of such discs 10 may then be incorporated in a surge arrester
assembly, such as for instance in a surge arrester of the type
rated at 258 kilovolts.
General Considerations
During the sintering process, the impurities are believed to form
various reaction products. The precise nature and molar
concentration of such products in the sintered disc is not
presently fully understood. It does seem likely, for instance, that
the barium carbonate reacts at the sintering temperature to form
barium oxide. If this does in fact occur, then it seems also likely
that the molar precentage of the barium oxide is nearly the same as
that of the barium carbonate, from which it was formed. For this
reason, the composition of the final sintered disc is given here in
terms of the composition of the powder from which it was pressed,
though it is recognized that conceivably the actual composition may
vary slightly therefrom in molar percentages due to this formation
of the reaction products. Also, some elements with a relatively low
boiling temperature, such as bismuth, may well be partly lost by
evaporation in the heating process so that the final composition
after sintering can have as much as 25 percent less bismuth in
it.
A rough indication of the degree of improved stability that can be
obtained by the addition of the impurities barium oxide and boron
oxide to silicon oxide containing compositions as compared to their
addition to compositions that do not contain silicon dioxide is
given in the FIG. 2. The graph of FIG. 2 represents the percentage
change in current of four different disc samples in a time interval
during which they were subjected to conditions designed to
approximate those under which they would operate in a surge
arrester. The curves indicate only rough approximations of the
actual valves of current during the time intervals.
Referring now to FIG. 2, the curve 16 shows generally the stability
of a first sample disc pressed from a powder containing no silicon
dioxide and having the following composition:
97.0 molar percent zinc oxide
0.5 molar percent bismuth trioxide
0.5 molar percent cobalt trioxide
0.5 molar percent manganese dioxide
1.0 molar percent antimony trioxide
0.5 molar percent chromic oxide
For testing, the disc was placed in an oven in circulated air at
65.degree.C. An alternating voltage of sufficient magnitude was
applied across the disc to result in a relatively low initial
current of 0.04 milliamperes per square centimeter through the
disc, and this voltage was then held constant. The current was read
as a function of time to determine the stability. It is seen from
the curve 16 that the current rapidly increased during the first
100 hours, thus indicating rather poor stability.
The curve 18 in FIG. 2 shows generally the stability of a second
disc sample made from a powder having the same composition as the
sample for the curve 16, but in which a corresponding portion of
the zinc oxide has been replaced by 0.1 molar percent of each of
the impurities barium carbonate and boron oxide. It contains about
0.1 molar percent of each of the impurities barium oxide and boron
oxide after sintering. This second sample was tested with an
initial current of 0.12 milliampere per square centimeter under
generally the same conditions as the first sample of curve 16. It
can be seen from the curve 18 that the stability of the second
sample was somewhat improved over the first sample, in that the
current rose to a lower level during the first 100 hours, despite
the higher initial current.
The curve 20 of FIG. 2 shows generally the stability of a third
sample disc pressed from a powder having a composition which is the
same as that for the first sample, except that 0.25 molar percent
of the zinc oxide has been replaced by silicon dioxide. While this
composition with silicon dioxide has a higher exponent than does
the composition of the first sample, the stability of the third
sample composition is not nearly as good. In fact, the stability of
the third sample is so poor that in order to yield meaningful data,
the initial current for it could only be brought to 0.03 millampere
per square contimeters. It can be seen from the curve 20 that even
at this low current, the stability of the third sample was very
poor, the current rapidly increasing to over 150 percent during
just the first 25 hours.
The curve 22 of FIG. 2 shows generally the stability of a fourth
sample disc pressed from a powder having the same composition as
the third sample, except that a corresponding portion of the zinc
oxide has been replaced by 0.1 molar percent barium carbonate and
0.1 molar percent boron oxide. The sample was tested at the same
initial current of 0.12 milliampere per square centimeters, as was
the second sample. It is seen from the curve 22 that the
improvement in the stability for the fourth sample, as compared to
the third sample, is much greater than would be expected from the
improvement that resulted in the second sample when the same
impurities were added to the first sample composition. The reasons
for the dramatic nature of the improved stability when barium
carbonate and boron oxide are added to a silicon dioxide-containing
zinc oxide powder for a sintered disc are not at this time fully
understood.
It should be noted that the data on which the above curves are
based is at this time necessarily limited, and the curves shown in
the FIG. 2 are by no means presented as necessarily completely
accurate for a large number of samples. However, the data is
thought to be sufficiently representative to give a reasonable
approximation of the stabilities of the various compositions for
describing the present invention.
The addition of the impurities barium carbonate and boron oxide has
been known to result in some improvement in stability when added to
various other zinc oxide compositions. However, it has been assumed
heretofore by those skilled in the art of zinc oxide resistor
compositions for surge arrester valve elements that these
impurities should not be added to a composition which contains
silicon dioxide, as that would result in impaired electrical
strength as well as degradation of other electrical
characteristics. It has been found, however, that the addition of
barium carbonate and boron oxide to a silicon dioxide-containing
zinc oxide composition does not, in fact, necessarily result in
significantly degraded characteristics, and at the same time does
result in a surprising degree of improved stability. The degree of
improved stability is much greater than that which results when the
impurities barium carbonate and boron oxide are added to the other
zinc oxide compositions.
While the disc of the preferred embodiment has a given specific
composition, it is to be understood that the individual impurity
contents of the disc may be varied to degrees known to those
skilled in the art without departing from the spirit of the
invention. The silicon dioxide may, for example, be only half of
the concentration as given in the preferred embodiment.
The precise limits of concentration within which the amounts of
barium carbonate and boron oxide may be varied are not presently
determined, since rather extensive experimentation would be
required to establish the limits with precision. However, at
present it appears that one or both of these impurities may be
present in a considerably lower concentration than that given in
the preferred embodiment and still result in improved stability.
There are some indications that if one or both of the barium
carbonate and boron oxide are present in a concentration on the
order of more than about 0.3 molar percent, the characteristics are
likely to be degraded.
While the invention had been discussed herein in terms of a
composition in which the metal oxide is zinc oxide, there is some
reason to think that other metal oxides of somewhat similar nature,
such as for example magnesium oxide, may also have improved
stability under such operating conditions by the addition of the
impurities as described herein. However, other metal oxides are not
at this time being intensively investigated for such an
application, and therefore not sufficient data is available at this
time to indicate with certainty just how applicable the invention
is to such other metal oxides for surge arrester uses.
* * * * *