U.S. patent number 3,758,705 [Application Number 05/289,193] was granted by the patent office on 1973-09-11 for coaxially conducting element and process for manufacture.
This patent grant is currently assigned to Owens-Illinois, Inc.. Invention is credited to Anthony P. Schmid.
United States Patent |
3,758,705 |
Schmid |
September 11, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
COAXIALLY CONDUCTING ELEMENT AND PROCESS FOR MANUFACTURE
Abstract
Disclosed is a method for forming an array of conductive
crystalline dendrites of reduced rutile in a glass-ceramic
insulating matrix by crystallizing certain compositions containing
titania and silica in a non-oxidizing atmosphere under the
influence of a thermal gradient to form a parallel array of
conductive reduced rutile dendrites.
Inventors: |
Schmid; Anthony P. (Riga,
MI) |
Assignee: |
Owens-Illinois, Inc. (Toledo,
OH)
|
Family
ID: |
23110445 |
Appl.
No.: |
05/289,193 |
Filed: |
September 14, 1972 |
Current U.S.
Class: |
174/113R; 23/300;
264/345; 313/523; 29/592.1; 313/329 |
Current CPC
Class: |
H01B
1/00 (20130101); C03C 10/0009 (20130101); H01J
31/065 (20130101); C03C 10/0036 (20130101); Y10T
29/49002 (20150115) |
Current International
Class: |
H01B
1/00 (20060101); H01J 31/00 (20060101); H01J
31/06 (20060101); C03C 10/00 (20060101); H01b
007/00 () |
Field of
Search: |
;174/113R,11R,151
;313/95 ;23/296,300 ;264/345,348 ;29/592 ;317/258 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Goldberg; E. A.
Claims
Having thus described the invention, what is claimed is:
1. The method for forming an electrically conductive element
comprising an array of coaxial, mutually insulated, crystalline
conductors through an insulating matrix, comprising the steps
of:
forming a molten mass of a thermally crystallizable glass
composition consisting essentially of:
under reducing or neutral conditions,
removing gaseous materials from said molten mass,
cooling a first cross-sectional portion of said molten mass to
establish a temperature gradient within the melt to nucleate and
initiate crystallization of an array of discrete, conductive,
dendrites of reduced rutile within said first cross sectional
portion, said reduced rutile being represented by the structural
formula Ti.sub.x O.sub.2x.sub.+1 wherein x is an integer of at
least one,
cooling cross sectional portions of said molten mass adjoining said
first cross sectional portion to advance the temperature gradient
throughout said mass thereby growing said dendrites within said
adjoining cross sectional portions in a substantially parallel
array with said dendrites being axially aligned in the direction of
said temperature gradient,
further cooling the resulting mass to terminate dendrite growth and
form an insulating matrix around said array of conductive
dendrites.
2. The method of claim 1 further including the steps of exposing
terminal points of individual conductive dendrites on the surface
of said matrix to establish electrical conductivity through said
dendrites.
3. The method of claim 1 wherein a reducing agent is present in
said molten mass.
4. The method of claim 3 wherein said reducing agent is carbon or a
metal.
5. The method of claim 1 wherein said crystallizable composition
consists essentially of:
6. The method of claim 1 wherein said crystallizable composition
consists essentially of:
7. The method of claim 1 wherein the resulting matrix is a glass
ceramic.
8. The method of claim 1 wherein the resulting matrix is
glassy.
9. An electrically conductive element comprising a coaxial array of
discrete, conductive, crystalline dendrites of reduced rutile in an
insulating matrix, said reduced rutile being represented by the
structural formula Ti.sub.x O.sub.2x.sub.+1 wherein x is an integer
of at least one, said dendrites having been formed by in-situ
crystallization and growth in said insulating matrix.
10. The element of claim 9 wherein the distribution of dendrites is
at least about 50,000 per square inch.
11. The element of claim 9 wherein the diameter of said dendrites
are in the range of about 0.1 to about 1.5 mil.
12. The element of claim 9 wherein the resistance of said dendrites
is in the range of about 300 to about 1,000 ohms per linear
inch.
13. The element of claim 9 wherein the resistivity of the matrix is
at least about 10.sup.10 ohm-cm.
Description
There is a need in the electronics industry for a device comprising
an insulating plate having embedded therein and passing
therethrough an array of mutually insulated conductors. Such
devices are used in the faceplates of cathode ray tubes and other
electronic transmission systems where an interaction between an
electronic charge generated in vacuum and processing equipment
located in air is desired. General background for such applications
is provided in U. S. Pat. Nos. 3,321,657; 3,193,364; 3,220,012;
3,424,932; 2,952,796; 3,140,528; and 3,366,817.
For such applications the device must be vacuum tight and this
requirement has resulted in severe fabrication difficulties when
conventional manufacturing techniques are employed. For instance
when metal filaments are embedded in a glassy matrix the devices
often have structural defects due to the difference in thermal
expansion coefficients between the glassy matrix and the metal
filaments. Moreover it is often difficult to achieve a vacuum-tight
seal between the glassy matrix and the individual conductors.
One particularly important application of the present invention is
an electron image transfer device as in the face plate of a
cathode-ray tube. In such a device the coaxially conducting element
is sealed in the faceplate of a cathode-ray tube so that the ends
of the conductors present a mosaic pattern upon which electronic
information is imposed by means of the electron gun within the
tube. The conductor ends which are in the cathode-ray tube each
receive an electronic charge which is then transmitted outside the
face plate and can be used for reproduction or display
purposes.
An image transfer device of this type must incorporate a very large
number of relatively small diameter conductors which are spaced and
insulated from one another, in order to provide adequate optical
resolution for electron charge information thus transmitted.
Furthermore, the device must have sufficient strength so that a
relatively thin section can serve as a cathode-ray tube faceplate
and the individual conductors must be vacuum tight within the
insulating matrix to provide for the maintenance of a prolonged
vacuum.
To accomplish these objective the prior art has proposed various
methods of binding as assemblage of short wires or other conductors
together with an insulating matrix. This has often proven to be
unreliable or economically impractical for many commercial
applications.
The present invention provides a unique and novel solution to the
problem of preparing such coaxially conducting element by the
controlled crystallization of conducting crystalline dendrites
orientated along an axis of the element and growing through an
insulating glassy or glass-ceramic matrix. This approach obviates
the problems associated with handling and physically installing
several thousand conductors into a single insulating matrix.
Accordingly it is a primary object of the present invention to
provide an efficient and practical coaxially conductive element
comprising an array of mutually insulated electrical conductors
passing through an insulating matrix.
In attaining the objects of this invention one feature resides in
forming a molten mass of thermally crystallizable glass composition
comprising silica, at least one alkaline earth oxide, and titania,
removing gaseous materials from said molten mass under
non-oxidizing conditions (i.e., reducing or neutral conditions)
cooling a first cross-sectional portion of said molten mass to
establish a temperature gradient in said molten mass, and
selectively crystallize an array of discrete, conductive
needle-like dendrites of titanium oxide or dendrites of stuffed
titanium oxide represented by the structural formula Ti.sub.x
O.sub.2x.sub.+1 wherein x is an integer of at least one, cooling
cross-sectional portions of said molten mass adjoining said first
cross-sectional portion to advance the temperature gradient
throughout said mass thereby crystallizing said dendrites in a
substantially parallel coaxial array with said dendrites being
axially aligned in the direction of said temperature gradient, and
cooling the resulting mass to form an insulating matrix around said
array of conductive dendrites. The term dendrites of stuffed
titanium oxide has been used above and refers to dendrites having a
crystalline structure which is stabilized with inclusions of matrix
constituents. The resulting body is then formed into the desired
configuration by conventional glass and ceramic forming techniques
such as cutting, drawing, grinding and so on, to form the desired
coaxially conducting element. The terminal points of individual
conductive dendrites are exposed on surfaces of the element to
establish electrical conductivity through the dendrites.
For convenience in reference the titanium oxides represented by the
formula Ti.sub.x O.sub.2x.sub.+1 wherein x is an integer of at
least one will be hereinafter called "reduced rutile."
In the drawings, which will be discussed in relation to the
examples,
FIG. 1 illustrates an idealized time-temperature profile for
crystallizing conductive reduced rutile in a preferred composition
range;
FIG. 2 illustrates an actual time-temperature profile employed in
example 2;
FIG. 3 is a partial sectional view of a coaxially conductive
element of invention; and
FIG. 4 is an enlarged view of the cross section of FIG. 3.
U. S. Pat. No. 3,065,091 to Russell discloses a process for growing
crystalline fibers of titania, zirconia or zircon in a sodium
borosilicate flux. According to this patent, titania, zircon or
zirconia is melted in the borosilicate flux at a sufficiently high
temperature to cause all of the crystal-forming materials to go
into solution and form a homogeneous melt. This resulting melt is
then cooled to cause the crystals to precipitate and form a
reinforced ceramic structure. In the Russell Patent the crystals
are shown to be growing as a ball of needles from a point
nucleation source (see FIGS. 2 and 3) and a parallel array of
needles is not disclosed. Conduction in reduced rutile is mentioned
by Russell at column 6 although there is no mention of coaxially
conducting elements or methods for manufacture of same.
In commonly assigned U.S. Pat. No. 2,484,248 the disclosure of
which is incorporated by reference, are disclosed crystalline glass
ceramics having a high dielectric constant which are formed from a
melt of thermally crystallizable glass compositions containing
silica, and titania under reducing or neutral conditions. The glass
composition is crystallized to obtain a conductive phase of reduced
rutile by a random nucleation and crystallization process. The
crystallized glass-ceramic is thereafter surface-oxidized at an
elevated temperature under oxidizing conditions to obtain a
non-conductive surface on the desired dielectric body.
The present invention utilizes a specific range of thermally
crystallizable glass compositions within the broad range of
3,484,258 which, when subjected to a specifically defined thermal
treatment, will form a parallel array of conducting dendrites of
reduced rutile in an insulating matrix.
Compositions suitable for practicing the present invention consist
essentially of alkaline earth-titania-silicate within the weight
range of about:
Broad Preferred Preferred CaO-TiO .sub.2 -SiO.sMgO-TiO .sub.2
iO.sub.2 Compositions Compositions % % % SiO 25 .sub.2 -60 25 -50
30 -60 TiO 10 .sub.2 -40 20 -40 10 -35 0aO -30 10 -25 -- 0gO -30 --
10 -30 Wherein MgO 10 +CaO -30 Al 0 .sub.2 O.sub.3 -30 0-30 0-30 B
0.sub.2 O.sub.3 -15 0-10 0-10
other conventional glass forming ingredients such as Na.sub.2 O,
K.sub.2 O, P.sub.2 O.sub.5, ZnO, PbO, and BaO can be added if
desired in combined proportion of up to about 10 percent by weight
of the above composition so long as such addition does not prevent
the formation of the reduced rutile phase.
In the preferred CaO-TiO.sub.2 -SiO.sub.2 system, reduced rutile
and sphene can exist as the crystalline phases. Due to the
mechanics of crystallization, reduced rutile will always form as
conductive needle-like dendrites while the non-conductive sphene
(if it crystallizes at all) will crystallize in the matrix. Whether
or not sphene crystallizes in the matrix is of no importance to the
present invention because the matrix is non-conductive in either
case. For some applications it may be desirable to have a glassy
matrix and for these applications the crystallization conditions
will be selected to avoid the formation of sphene. When a
glass-ceramic matrix is desired, the crystallization conditions
will be selected to promote this formation of sphene in the
matrix.
The batch compositions can be selected from conventional fritted or
unfritted glass making materials such as feldspar, oxides,
carbonates, aluminates and so forth. Impurities can also enter the
compositions, depending on the source of starting materials
provided they do not adversely affect the desired properties of the
final element.
In preparing the melt, the batch material are placed in a refractor
container and brought to a temperature where the molten state is
achieved. For most of the compositions described above this
temperature is about 1400.degree.C - 1600.degree.C. When the
conductive element to be formed must be vacuum tight, the
prevention of the formation of bubbles during crystallization of
the reduced rutile phase is of great importance. The source of
these bubbles appears to be the release of gases dissolved or
occluded in the melt during the nromal process of melting the
glass. This results in the formation of an elongated bubbles in the
vicinity of the reduced rutile dendrite.
The present invention provides for minimizing the formation of such
elongated bubbles by out-gassing the melt. One of these outgassing
methods is vacuum melting wherein the entire melt is processed
under a total pressure of less than 1mm of Hg or less and often as
low as 10.sup.-.sup.3 mm of Hg. While this method is efficient, it
requires specialized vacuuming melting equipment. Accordingly,
other methods such as purging or sparging the melt with an inert
gas such as nitrogen, argon, neon or carbon dioxide can be
employed. This sparging can be accomplished by bubbling the purging
gas through this melt or by employing a batch material which
releases a purging gas upon decomposition during melting.
Carbonates as raw materials release carbon dioxide during melting
which has the effect of purging the melt and sweeping away
dissolved and occluded gaseous components. The amount of purging
required varies from application to application. In most
applications the melt should be purged so that no visible bubbles
are observed by visually examining the finished element with the
naked eye.
In the inert gas sparging technique the inert gas is bubbled
through the melt at a temperature sufficiently far above the
melting temperature that the glass is fluid enough so that a
reasonable rate of gas flow through the melt can be achieved, while
at the same time the bubbles formed are sufficiently small to have
a high ratio of surface to volume. Both of these factors are
functions of melt viscosity. It has been found that sufficient
outgassing to practically eliminate the formation of bubbles and
voids from the finish element can be achieved by bubbling argon gas
through the melt at the rate of about 0.1 to 0.5 SCFH at a
temperature of about 1400.degree.-1500.degree.C for a period of 3
and 1/2 hours for melts having a volume of about 10 cubic
inches.
In the preparation of electrically conducting elements according to
the present invention a glass composition as described above is
melted in an essentially neutral atmosphere or a reducing
atmosphere. Thereafter the desired article is shaped and
crystallized while still in the same atmosphere.
The effect of the neutral or reducing atmosphere is to reduce some
of the potentially conductive titania present in the composition to
the lower member of the homologous series Ti.sub.x O.sub.2x.sub.]1
where x is an integer with a value of at least one (i.e., reduced
rutile). This provides the mixture of valence states in the
titanium which is necessary to achieve electrical conductivity.
Many crystalline species other than the reduced rutile species can
be present in the resultant element in addition to the reduced
rutile without materially effecting the conductivity
characteristics.
Example of neutral and reducing atmospheres for use in this
invention are argon, argon-hydrogen, nitrogen, nitrogen-hydrogen,
carbon monoxide, and nitrogen-oxygen gas mixtures. These
atmospheres function to form reduced rutile phase by the exclusion
of the required amount of oxygen necessary to convert all of the
titanium compounds present to TiO.sub.2.
In another embodiment invention a metal or reducing agent is added
to the melt in an amount sufficient to reduce the titanium oxide
present to the conductive reduced rutile state. Suitable reducing
agents for this purpose include carbon and titanium titanium-oxide.
Carbon (i.e., graphite) melting vessels are often employed in which
case the reducing agent is available by reaction of the melt with
its containing vessel.
The heat treatment required to crystallize the reduced rutile
dendrites is more complicated than is usually encountered in
crystallization processes. A first cross-sectional portion of the
melt, after it has been purged to remove dissolved and occluded
gases and while still in a neutral or reducing atmosphere, is
cooled so as to initiate the crystallization of reduced rutile
dendrites therein while maintaining the balance of the melt at a
temperature above the crystallization temperature of reduced
rutile. The cross section portion so cooled is essentially planar
in cross sectional area so that reduced rutile dendrites are
randomly crystallized throughout the cross sectional portion rather
that at a point as a "ball of dendrites." For most compositions
described above, this crystallization temperature is in the range
of about 1050.degree.C to 1150.degree.C.
Once the reduced rutile dendrites have been randomly crystallized
throughout the first cross sectional portion, cross sectional
portions adjoining the first cross sectional portions are cooled to
within the crystallizing temperature range to cause the dendrites
to grow through such adjoining cross sectional portions. This
process is repeated until the dendrites have achieved the desired
length at which time the resulting mass is cooled to form an
insulating glass or glass-ceramic matrix around the array of
conductive dendrites.
The technique of advancing a planar temperature gradient through
the melt usually forms a substantially parallel array of conductive
dendrites of reduced rutile is an insulating matrix having the
following characteristics:
1. a conductive dendrite distribution of at least about 50,000 per
sq. in. although conductive dendrites of 200,000 to 3,000,000 per
square inch are not uncommon, with about 1,000,000 per square inch
being typical;
2. a conductive dendrite diameter in the range of about 0.1 to 1.5
mil;
3. a conductive dendrite resistance of about 300 to 1,000 ohms per
linear inch;
4. essentially all of the dendrites in parallel alignment;
5. matrix resistivity of at least about 10.sup.10 ohm-cm;
6. essentially void free elements;
7. high mechanical strength.
The present invention will be illustrated in the follwoing examples
wherein all parts are by weight, all percentages are weight
percentages and all temperatures are in .degree.C unless stated
otherwise.
EXAMPLE 1
The following batch materials are placed in a refractor
crucible:
Titania 23 parts Silica 37.2 parts Alumina 7.5 parts Calcium
Carbonate 32 parts Aluminum 0.5 parts (reducing agent)
The charged crucible is placed in a furnace and the temperature is
raised to 1,350.degree.C while the contents of the crucible are
melted and stirred. During this melting procedure, a forming gas
(10 percent hydrogen--90 percent nitrogen) atmosphere is maintained
in the furnace. After melting for 4 hours under the above
conditions, a homogeneous molten mass of approximately 1 inch in
thickness is achieved. The prolonged heating effectively removes
the gaseous materials from the melt. The composition of the molten
mass is:
Mole % Weight % SiO .sub.2 47.5 43.2 TiO .sub.2 22.0 26.8 CaO 24.5
20.8 Al .sub.2 O.sub.3 6 9.2
at the end of this 4 hour period, a stream of forming gas at room
temperature is directed against the bottom of the crucible to
establish a thermal gradient of about 60.degree.C from top to
bottom of the molten mass. Thus, the temperature at the top of the
molten mass is about 1,350.degree.C while the temperature at the
bottom of the molten mass is about 1,290.degree.C. The cooling with
forming gas is continued over a 5 hour period to maintain the
60.degree.C temperature gradient from top to bottom while gradually
lowering the bottom temperature of the mass to about 980.degree.C
and the top temperature of the melt to about 1,040.degree.C. This
thermal treatment results in the nucleation and growth of an array
of axially aligned, conductive dendrites of reduced rutile in a
glass-ceramic matrix containing sphene as the crystalline
phase.
The element thus formed is then held at 1,250.degree.F for about 10
hours to anneal and remove strains. After this annealing period
sample is cooled to room temperature over a 24 hour period while
the forming gas atmosphere is maintained in the furnace.
The element thus is removed from the crucible and the top and
bottom faces are ground and polished to clearly expose the
dendrites. The ground and polished faces are observed to contain
conductive, black, reduced rutile dendrites in the proportion of
about 700,000 to 1,000,000 dendrites per square inch.
About 80-90 percent of the dendrites are in a parallel array and
axially aligned from bottom to top of the element. The dendrites
are about one mil in diameter and are spaced at about 1.5 mils
center line to center line. About 30 percent of the element
comprises conductive dendrites and the remaining 70 percent
comprised the insulating glass-ceramic matrix. The dendrites have a
resistance of about 500 to 1,000 ohms as determined by placing the
leads of the ohmmeter on terminal points of the individual
dendrites on opposing faces of the element.
The element thus formed is designated generally as reference
numbered 10 in FIGS. 3 and 4. In these figures the insulating
matrix is designated by reference numeral 11 and the conductive
dendrites of reduced rutile are designated by number 12. 10a
represents that portion of the element derived from the bottom of
melt and 10b represents that portion of the element derived from
near to top of the melts so that the dendrites 12 grew in the
direction from 10a to 10b.
The element is suitable for use in transmitting electronic
information.
EXAMPLE 2
In this example glass frits of the following weight percent are
used as the batch materials:
Frit A Frit B % % SiO .sub.2 46.4 38 TiO .sub.2 23.6 35 CaO 19.9 18
A1 .sub.2 O.sub.3 9.5 9
a melt is prepared by melting 200 parts of Frit A, 200 parts of
Frit B, together with one part of silicon, 1 part of titanium, 0.3
parts of aluminum as reducing agents in a refractory crucible at
about 1,450.degree.C to 1,500.degree.C for 4 hours. Because of the
furnace construction the temperature at the bottom of the melt is
1,520.degree.C while the temperature at the top of the melt is
measured to be 1,430.degree.C. During this melting period a flow
rate of 0.2 SCFH of argon gas is bubbled through the molten mass,
and argon is maintained in the furnace atmosphere. The composition
of the molten mass is:
Mole % Weight % SiO .sub.2 47.0 42.2 TiO .sub.2 24.3 29.3 CaO 22.0
19.0 Al .sub.2 O.sub.3 6.0 9.3
at the end of this melting period the mass is subjected to a time
temperature crystallization profile as illustrated in FIG. 2. To
achieve this profile the temperature at the bottom of the mass is
cooled over a 20 minute period to 1,030.degree.C by directing a
stream of argon gas at room temperature against the bottom of the
crucible. The temperature at the top of the mass is maintained at
about 1,430.degree.C. The top of the melt is then cooled with a
stream of argon gas to a temperature of 1,030.degree.C over a
period of about three-quarters of an hour while the temperature at
the bottom is maintained at 1,030.degree.C. Conductive coaxially
aligned dendrites of reduced rutile grow through the mass during
this three-quarters of an hour period as described in Example 1.
The entire mass was then held at 1,030.degree.C for an additional
hour to relieve thermal stresses and then slowly cooled to room
temperature.
When the element thus formed has cooled, it is removed from the
mold and the top and bottom faces are ground and polished. The
element is observed to be an array of substantially parallel,
substantially 100 percent axially aligned conductive dendrites of
reduced rutile of about 1 1/2 inch to 2 inches in length and
passing through a glass-ceramic matrix containing sphene as the
crystalline phase. The dendrites extend in the bottom to top
direction of the original melt. The ends of the conductive
dendrites are identified on either face of the sample with the
leads of an ohmmeter. The resistance of the dendrites is measured
to be 300to 1,000 ohms. The dendrites are about 1 mil in diameter
and are spaced at about one-half to 2 mils center line to center
line. The dendrites are present in the proportion of 700,000 to
1,000,000 dendrites per square inch. The element is suitable for
use in transmitting electronic information. The element is
substantially as illustrated in FIG. 3 and 4 and is suitable for
transmission of electronic information.
EXAMPLE 3
To further demonstrate the principles of the present invention in
the MgO-SiO.sub.2 system, 0.74 parts of titania, 0.67 parts of
silica, 0.68 parts of magnesium carbonate and 0.34 parts of alumina
(all material being minus 40 mesh screen size) are melted under
neutral conditions in a refractory crucible at 1,450.degree.C for a
10 hour period. The resulting molten mass has the weight
composition 36.3 percent TiO.sub.2 ; 32.8 percent SiO.sub.2 ; 16.7
percent Al.sub.2 O.sub.3 ; and 14.1 percent MgO.
After the 10 hour melting period a thermal gradient is established
across the molten mass as in Example 1 with a flow of argon gas.
The mass is then cooled as in Example 1 and an array of coaxial,
conductive dendrites of reduced rutile is observed in the resulting
solidified mass. The composition of the residual matrix is not
determined although it appears to be glass-ceramic in nature. This
conductivity of the dendrites is established by means of an
ohmmeter. The resulting element is substantially as shown in FIGS.
3 and 4.
Substantially similar results are obtained when the compositions
listed below are employed in the procedures of Example 3.
##SPC1##
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