U.S. patent number 3,858,144 [Application Number 05/319,492] was granted by the patent office on 1974-12-31 for voltage stress-resistant conductive articles.
This patent grant is currently assigned to Raychem Corporation. Invention is credited to Ronald L. Bedard, Andrew J. Kampe.
United States Patent |
3,858,144 |
Bedard , et al. |
December 31, 1974 |
VOLTAGE STRESS-RESISTANT CONDUCTIVE ARTICLES
Abstract
Described herein are methods and means by which conductive
carbon black-containing resistive heaters which are
self-temperature limiting by reason of their positive temperature
coefficient of resistance are stabilized against long-term
resistance variation under high voltage stress, variously by (a)
increasing the proportion of carbon black at the electrode
interface relative to that of the remainder of the semi-conductive
material of which the article is comprised; and (b) providing at
the electrode interface a material selected from the group
consisting of carboxylic acid group-containing polymers of acid
number greater than 3, their ammonium, alkali or alkaline earth
metal salts, or a polymeric amine of amine number greater than
3.
Inventors: |
Bedard; Ronald L. (San Leandro,
CA), Kampe; Andrew J. (Half Moon Bay, CA) |
Assignee: |
Raychem Corporation (Menlo
Park, CA)
|
Family
ID: |
23242462 |
Appl.
No.: |
05/319,492 |
Filed: |
December 29, 1972 |
Current U.S.
Class: |
338/22R; 219/549;
252/511; 219/505; 252/502 |
Current CPC
Class: |
H01B
3/44 (20130101); H05B 3/06 (20130101); H01C
7/027 (20130101); H05B 3/146 (20130101) |
Current International
Class: |
H01C
7/02 (20060101); H01B 3/44 (20060101); H05B
3/06 (20060101); H05B 3/14 (20060101); H01c
007/04 () |
Field of
Search: |
;338/22R,22SD
;252/502,511 ;219/553 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Albritton; C. L.
Attorney, Agent or Firm: Lyon & Lyon
Claims
We claim:
1. In an electrically conductive self-regulating article comprised
of at least two spaced-apart metallic electrodes electrically
interconnected by a composition containing conductive carbon black
dispersed in a crystalline polymeric matrix, the improvement
wherein voltage-induced resistance variance is diminished which
comprises providing at the electrode surface an effective
resistance-stabilizing amount of a material selected from the group
consisting of carboxylic acid group-containing polymers of acid
number greater than about 3 and the ammonium, alkali or alkaline
earth metal salts of such polymers.
2. The article of claim 1 wherein said material is selected from
the group consisting of zinc and sodium salts of an
ethylene-acrylic acid copolymer.
3. The article of claim 2 wherein said material is uniformly
dispersed throughout said matrix in the amount of from about 2 to 8
percent by weight based on total weight of the material-containing
matrix.
4. The article of claim 1 wherein said material is a terpolymer of
ethylene, vinyl acetate and .alpha.-.beta. ethylenically
unsaturated carboxylic acid.
5. The composition of claim 4 wherein said material is uniformly
dispersed throughout said matrix in the amount of from about 2 to 8
percent by weight based on total weight of the material-containing
matrix.
6. The article of claim 4 wherein said material is uniformly
dispersed throughout said matrix in the amount of from about 0.1 to
2 percent by weight based on the total weight of the
material-containing matrix.
7. In an electrically conductive self-regulating article comprised
of at least two spaced-apart metallic electrodes electrically
interconnected by a composition containing conductive carbon black
dispersed in a crystalline matrix, the improvement wherein
voltage-induced resistance variance is diminished which comprises
providing that the percent by weight conductive black at the
electrode surface is at least about 1.5 times that contained in
said matrix at the midpoint between adjoining electrodes, the
latter constituting at least about 5 percent by weight of the total
weight of matrix and conductive black at said midpoint.
8. The article of claim 7 wherein the percent by weight of carbon
at said midpoint is within the range from about 9 to about 15
percent.
9. The article of claim 8 wherein the percent by weight of carbon
at said surface is from about 30 to about 75 percent.
10. In a electrically conductive self-regulating article comprised
of at least two spaced-apart metallic electrodes electrically
interconnected by a composition containing conductive carbon black
dispersed in a crystalline polymeric matrix, the improvement
wherein voltage-induced resistance variance is diminished which
comprises providing at the electrode surface an effective
resistance-stabilizing amount of
poly(2,2,4-trimethyl-1,2-dihydroquinoline).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related in subject to commonly assigned U.S.
Pat. application Ser. Nos. 287,442, 287,443 and 287,444, each filed
Sept. 8, 1972.
BACKGROUND OF THE INVENTION
Semi-conductive compositions comprised of conductive carbon black
dispersed in an interconnected array of current-carrying channels
in a polymeric matrix have heretofore found wide application in
resistance heating. Such compositions as exhibit a steep-sloped
positive temperature coefficient of resistance have found
particular application in the manufacture of self-temperature
regulating heating elements, exemplary of which are those described
in the aforesaid application Ser. Nos. 287,442, 287,443 and
287,444, the disclosures of which are incorporated herein by
reference to illuminate the background of this invention. As the
temperature of such a composition increases, either through a rise
in ambient temperature or by reason of resistive heating occasioned
by the passage of current therethrough, the polymer matrix expands
at a rate greater than that of the carbon black particles which, in
an interconnected array of channels, impart the property of
conductivity. The resulting diminution in the number of
current-carrying channels decreases the amount of power generated
by I.sup.2 R heating. This self-limiting feature may be put to work
in, e.g., heat tracing pipes in chemical plants for freeze
protection, maintaining flow characteristics of viscous syrups,
etc. In such applications, articles formed from the conductive
composition ideally attain and maintain a temperature at which
energy lost through heat transfer to the surroundings equals that
gained from the current. If the ambient temperature then falls,
increased heat transfer to the surroundings is met by increased
power generation owing to the resistivity decrease associated with
the article's lowered temperature. In short order, parity of heat
transfer and power generation is again attained. Conversely, where
ambient temperature increases heat transfer from the conductive
article is reduced and the resistivity rise resulting from
increased temperature diminishes or stops I.sup.2 R heating.
Thusfar, the use of self-regulating resistance heating elements has
been largely confined to those applications in which operational
voltage does not exceed about 110 volts (herein, all voltages are
60 cps, RMS values). However, for employments like heat-tracing
pipes in refineries and in other operations in which long runs of
resistance-heating strips are desirable, it would be advantageous
to reduce line losses by operating at greater voltages. Again, in
areas of the world where 110 volt potential is not widely available
(particularly in various of the European countries), provision of
self-regulating heating elements operable at higher voltage (e.g.,
at about 220 volts) would be desirable. While the semi-conductive
compositions specifically disclosed in the aforesaid commonly
assigned applications have proved eminently suitable in
heat-tracing applications over periods of many months at 110 volts,
when subjected to voltages on the order of 220 volts and higher, we
have now found their resistance to increase substantially over
periods well within anticipated service life. The problems appears
related to the high voltage stress resulting from the confined
influence of high operational voltage and the relative contiguity
of electrodes employed in heat tracing elements. While we do not
wish to be bound by any theory, we believe the disperse nature of
conductive carbon in the polymeric matrix surrounding the
electrodes and incomplete wetting of the electrode with
black-containing polymer, under high voltage stress, creates
regions of high localized current density leading to degradation
and a concomitant increase of resistance at the interface.
BRIEF SUMMARY OF THE INVENTION
By this invention there are provided methods and means for ensuring
long-term resistance stability in self-temperature regulating
conductive article subjected to high voltage stresses, and products
enjoying that property. According to one embodiment of the
invention, the formation of localized regions of high current
density at the electrode interface is apparently discouraged by
precoating the metallic electrodes with a conductive
black-containing composition such that following disposition of the
electrodes in spaced-apart relation electrically continuous through
a black-loaded polymeric matrix or core (as by extruding the core
onto a number of electrodes), the percent by weight conductive
black contained at the electrode interface is at least about 1.5
times that of the midpoint between adjoining electrods. In another
embodiment, the objectives of the invention are achieved by
uniformly deploying in the matrix or core electrically connecting
adjoining electrodes an effective resistance-stabilizing amount of
a material selected from the group consisting of carboxylic acid
group-containing polymers of acid number greater than about 3, the
ammonium, alkali or alkaline earth metal salts of such polymers,
and polymeric amines of amine number greater than about 3.
One object of this invention is to secure self-temperature
regulating articles which exhibit enhanced resistance to voltage
stress-induced resistance variation when powered at high voltage
for extended periods.
A further object of the invention is to provide self-temperature
regulating conductive articles free from excessive resistance
increase upon subjection to high voltage stress early in their
service life.
The manner in which these and other objects and advantages of the
invention are obtained will appear in greater detail from the
description of preferred embodiments and from the accompanying
drawings in which:
FIGS. 1 and 2, respectively, graphically depict, for comparison
purposes, voltage-induced resistance variance with time in the case
of a self-temperature regulating article formed according to one
embodiment of this invention and that with a control without the
scope of the invention;
FIG. 3 graphically depicts resistance variance with temperature
data employed in normalizing resistance values employed in
constructing FIGS. 1, 2 and 4-7; and
FIGS. 4, 6 and 7 similarly permit comparison of time-related
resistance variation of other embodiments of the invention with
control results depicted in FIG. 5.
FIG. 8 is a cross-sectioned end-on view of one jacketed extrudate
formed according to the practice of this invention.
DETAILED DESCRIPTION OF THE INVENTION
Ideally, potential drops linearly toward ground across the width of
a semi-conductive material electrically connecting two electrodes
so that, in the first instance, voltage stress can be considered as
the slope of that decrease. With the configurations most commonly
heretofore employed in self-temperature regulating heat-tracing
articles (i.e., those with specific initial resistivities of about
2,000 ohm-in), where the ratio of voltage to electrode separation
in inches has been equal to or greater than about 500, significant
resistance increase over long-term powering has been encountered.
Of course, the adverse effects of voltage stress will vary
inversely with resistivity of the semi-conductive material across
which the potential is imposed. Taking q as heat generation (in
watts) per cubic inch of a given voltage per inch, q = V.sup.2 /p,
where p is resistivity in ohm-in and V is volts per inch. Where q
is greater than about 100.0 watts/inch during operation at
70.degree.F, voltage stress generates resistance degradation. In
one aspect of our invention, i.e., that in which polymeric
materials containing carboxylic acid or amine functions are
disposed in minor proportion of the electrode interface and,
preferably, throughout the semi-conductive material electrically
connecting adjoining electrodes, it may be that the resulting
resistivity stabilization is owed to improved setting of the
electrode stemming from the formation of ionic or other bonds
between the said functions on the one hand and the electrode on the
other. In any event, marked improvement has been had where
polymeric amines and acid group-containing polymers like those
referred to above have been supplied in the semiconductive
composition.
"Amine number", as used herein, refers to that quantity obtained
according to the standard ASTM D-2074-66 determination. "Acid
number" is the mg. KOH required to neutralize free acid groups
contained in 1 gm. of a particular polymer.
Particular preferred carboxylic acid group-containing polymer
addends are ethylene-acrylic acid copolymers (preferably the sodium
or zinc-neutralized salts thereof such as those sold by E. I. du
Pont de Nemours & Company, Inc. under the tradename "Surlyn")
and terpolymers of ethylene, vinyl acetate (24-29 percent) and a
minor proportion (e.g., = 5 percent) of an .alpha.-.beta.
ethylenically unsaturated carboxylic acid such as acrylic or
methacrylic acid. Exemplary of the latter category is the "Elvax"
family of acid terpolymers (acid number of about 6) available from
E. I. du Pont de Nemours and Company, Inc. As an example of an
especially suitable amine addend may be mentioned poly
(2,2,4-trimethyl- 1,2-dihydroquinoline) such as that available from
R. T. Vanderbilt and Company under the name "AgeRite Resin D."
Generally, significant improvement in resistance stability is
obtained where the semi-conductive core electrically connecting
adjoining electrodes contains from about 0.1 to about 15,
preferably 0.1 to 8 percent, by weight amine or acid additive,
based on total weight of the additive-containing semi-conductive
material. In the case of poly
(2,2,4-trimethyl-1,2-dihydroquinoline), optional results may be
obtained with as little as from 0.1 to 2 percent.
In another embodiment of this invention, the adverse effects of
voltage stress are diminished by providing the electrodes with a
coating containing sufficient carbon black to ensure that at the
electrode surface the enveloping conductive material contains at
least about 1.5 times that amount of carbon contained at the
midpoint between adjoining electrodes where the percent by weight
carbon at that midpoint is at least about 9 to 15 percent. Percent
by weight carbon at the electrode interface desirably is within the
range from about 1.5 to about 7 times that of the midpoint. Most
preferably, the electrode coating when dry contains from about 30
to 75 percent by weight carbon black. This differentiation in
relative content of carbon is most conveniently achieved by coating
onto the electrode a carbon black-rich aqueous composition,
preferably one comprised of conductive black in deionized water.
The coating composition may optionally contain fillers such as
colloidol silica for strength enhancement, etc.
Preferred materials for electrodes include copper, tinned copper,
and nickel- and silver-plated copper. The electrodes may vary
conventionally in configuration, e.g., flat, round, solid,
stranded, etc.
In order to most optimally obtain self-limiting compositions, the
polymeric matrix in which conductive black is dispersed in whatever
proportion should exhibit overall an appropriately non-linear
coefficient of thermal expansion, for which reason a degree of
crystallinity is believed useful. Polymers exhibiting at least
about 20 percent crystallinity as determined by x-ray diffraction
are suited to the practice of the invention. Among the many
polymeric matrices with which the invention may be practiced are
polyolefins such as low, medium and high density polyethylenes and
polypropylene, polybutene-1, poly (dodecamethylene
pyromellitimide), ethylenepropylene copolymers and terpolymers with
non-conjugated dienes, polyvinylidine fluoride, polyvinylidine
fluoride-tetrafluoroethylene copolymers, etc. As is known, blends
of polymeric substances may also be employed as the matrices in
which the carbon black is dispersed. Typically, the minor polymeric
blend component is chosen for superior compatibility with carbon
black relative to the blend component present in major proportion,
while the latter component is selected for the particular physical
properties desired in the overall extrudate. The principal blend
component is preferably present in at least about 3:1 weight ratio
relative to the minor component with which the black is first
mixed. Presently, the blends most preferred have a polyethylene as
the principal component, the other being an ethylene-vinyl ester
copolymer, such as ethylene-vinyl acetate or ethylene-ethylacrylate
copolymers. An especially preferred extrudate contains about 70:20
polyethylene: ethylene-ethyl acetate copolymer by weight. As will
be recognized by those skilled in the art, limiting temperatures
tailored to the application intended (e.g., freeze protection,
thermostatting, etc.) may be obtained by appropriate selection of
polymeric matrix material. For example, elements which self-limit
at temperatures on the order of 100.degree.F, 130.degree.F,
150.degree.F, 180.degree.F and 250.degree.F may be produced with,
respectively, wax-poly (ethylene-vinyl acetate) blends, low density
polyethylene, high density polyethylene, polypropylene and
polyvinylidene fluoride. Other criteria of polymer selection will,
in particular instances, include desired elongation, environmental
resistance, ease of extrusibility, etc. as is well known.
The carbon blacks employed are those conventionally used in
conductive plastics, e.g., high structure varieties such as furnace
and channel blacks. Other conventional addends such as
antioxidants, etc, may be employed provided only that their
quantities and characteristics do not subvert the objects of the
invention. An especially interesting class of beneficial addends
are materials such as waxes which, while compatible with the
predominant blend component, melt at lower temperature. The result
is to permit obtainment of a given wattage at lower temperature,
owing to a first peaking effect of the wax on the
resistivity-temperature curve. Compounding of the core material
intended for extrusion about coated or uncoated electrodes is
conventional and generally involves banburying, milling and
pelletizing prior to pressure extrusion of the self-limiting
element from the melt. Where a polymeric amine or carboxylic acid
group-containing polymeric addend is employed as a component of the
polymeric matrix material according to one embodiment of the
invention, it may be added at any point in compounding of that
material.
Preferably, as will appear from FIG. 8, the black-containing matrix
1 is extruded onto a spaced-apart pair of elongate electrodes 2 to
form an element rod-shaped or, most preferably, dumbbell-shaped in
cross-section, the extruded thermoplastic both encapsulating and
interconnecting the electrodes.
To reduce resistivity of extruded product to acceptable initial
levels it is preferably annealed at a temperature greater than
about 250.degree.F, preferably at least about 300.degree.F, and in
any case at or above the melting point or range of the polymeric
matrix in which the carbon black is dispersed. The period over
which annealing is effected will, it will be appreciated, vary with
the nature of the particular matrix and the amount of carbon black
contained therein. In any case, annealing preferably occurs over a
time sufficient to reduce resistivity of the annealed element to
satisfaction of the equation 2 L+ 5 log.sub.10 R.ltoreq.45,
preferably .ltoreq.40 (L being percent by weight black in the
matrix and R resistivity of the extrudate in ohm-cm) and the time
necessary in a particular case may be readily determined
empirically. Typically, annealing is conducted over a period in
excess of 15 hours, and commonly at least about a 24 hour anneal is
had. Where the element is held at anneal temperature continuously
throughout the requisite period, it is advisable to control cooling
upon completion of the anneal so that at least about 11/2 hours are
required to regain room temperature. However, control of cooling is
substantially less important where the requisite overall annealing
residence time is divided into at least about 3 roughly equal
stages and the element returned to room temperature between each
annealing stage.
Because the polymeric matrix of black-containing extrudate is in
the melt during annealing, that extrudate is preferably supplied
prior to annealing with an insulative extruded jacket 3 (see FIG.
8) of a thermoplastic material which is shape-retaining when
brought to the annealing temperature. Suitable jacketing materials
are discussed in length in the aforesaid application S.N.
287,442.
Upon completion of annealing and optional addition of a further
insulative jacket 4 of, e.g., polyethylene, the self-limiting
element is desirably subjected to ionizing radiation sufficient in
strength to cross-link the black-containing core. Radiation dosage
is selected with an eye to achieving cross-linking sufficient to
impart a degree of thermal stability requisite to the particularly
intended application without unduly diminishing crystallinity of
the polymer matrix, i.e., diminution of overall crystallinity of
the cross-linked black-containing matrix to less than about 20
percent is preferably avoided. Within those guidelines, radiation
dosage may in particular cases range from about 2 to 15 megarads or
more and preferably is about 12 megarads.
The invention is further illustrated by reference to preferred
embodiments thereof in the Examples which follow, in which all
parts and percentages are by weight and all temperatures are
expressed in Fahrenheit degress unless otherwise noted.
EXAMPLE 1
A. preparation of Electrode Coating Composition
To a tank were added, with stirring, 200 lbs. colloidal silica
("Ludox HS-40," E. I. duPont de Nemours & Company, Inc.), 40
lbs. of a 25 percent aqueous solution of Tamol 731 (a sodium salt
of a polymerized carboxylic acid available from Rohm & Haas),
60 lbs. dionized water and sufficient ammonium hydroxide to adjust
pH to about 9.5.
To a second tank were added, again with stirring, 140 lbs. dionized
water and 6 lbs. dicyandiamide-formaldehyde condensate ("Sun Pro
528," available from Sun Chemical Company).
The two masterbatches prepared above were then mixed together under
shear for about 15-20 minutes, and the resulting mixture let stand
for about 24 hours. Thereafter, 236 lbs. conductive acetylene black
(Shawinigan Company) was added to the mixture under shear and the
resulting black-loaded composition let stand for a further 24 hour
period. Viscosity was then adjusted for optional coating by the
addition of about 61 lbs. dionized water.
B. preparation of Core Material
76 lbs. of polyethylene (density 0.929 gm/cc, 32 lbs. of a mixture
of 34 percent Vulcan XC-72 and ethylene ethyl acrylate copolymer
(density 0.930 gm/cc, 18 percent ethyl acrylate) were loaded with 1
lb. of antioxidant into a Banbury mixer. The ram was closed and
mixing commenced. When temperature reached about
240.degree.-50.degree.F the batch was dumped, placed in a 2-roll
mill, cut off in strips and pelletized in a suitable extruder.
C. extrusion onto Electrodes
Two tinned copper electrodes (20 AWG 19/32) were passed through the
coating composition prepared as in Part A above and contained in a
recirculant tank to form a coating of about 1 mil thickness and the
coating dried by radiant heat. The pelletized material formed in
Part B above was then extruded onto two parallel coated electrodes
to form an extrudate generally dumbbell-shaped in cross-section.
The electrodes were 0.275 inch apart (center-to-center), the
interconnecting web being about 15 mils in thickness, at least 8
mils thickness of the semiconductive composition surrounding the
electrodes. Extrusion was performed in a plasticating extruder with
crosshead attachment (Davis-Standard 2 inch extruder, 24/1 L/D,
with PE screw). Thereafter, the same extruder was arranged to
extrude an 8 mil thick insulation jacket of polyurethane (Texin
591-A, available from the Mobay Corporation). For optional
geometric conformation, a conventional tube extrusion method was
employed in which a vacuum (e.g., 5-20 inch H.sub.2 O) is drawn in
the molten tube to collapse it about the semiconductive core within
about 3 inches of the extrusion head. The jacketed product was next
spooled onto aluminum disks (26 inches diameter) and exposed to
300.degree.F for 24 hours in a circulating air oven. Following this
thermal structuring procedure, the extrudate was cooled to room
temperature over about 11/21/2 hours.
For comparison, a control was prepared following the foregoing
procedure save that the core material was extruded about uncoated
electrodes. The resistance of a 1 foot section of the control
extrudate was measured at various temperatures with a wheatstone
bridge, the resulting values divided by measured resistance at
70.degree., and FIG. 3 prepared from the resulting values.
D. voltage-Induced Resistance Variance Compared
Three 1-foot lengths of each of the control and electrode-coated
extrudates were next respectively subjected to voltages of 110, 220
and 330 volts over an extended period of time. Periodically, the
samples were deactivated, cooled to ambient and resistance readings
taken with a Weston Digital voltage ohm meter (Model 1240). As an
addition control, the resistance of a fourth strip of each
extrudate held at zero voltage was periodically determined. The
data was then plotted on FIGS. 1 and 2, respectively, for
electrode-coated and control extrudates, after normalization to
account for variance in ambient resistance measurement
temperatures. The normalized resistance at any time R.sub.T (or, at
zero time, R.sub.i) was determined by dividing resistance measured
at a particular ambient temperature by the coefficient on the
ordinate of FIG. 3 obtained at that same temperature.
A comparison of FIGS. 1 and 2 makes plain that the electrode-coated
extrudate exhibits stable resistance characteristics under high
voltage stress, whereas the control does not. The extrudate
prepared according to this invention markedly differs from the
control both in terms of resistance stability after extended
powering and in freedom from excessive resistance increase in early
operational life.
EXAMPLES 2-4
In these examples, voltage stress resistance is enhanced by the
addition of acidic or amine polymers to the core material itself
without resort to the electrode-coating technique described in
Example 1. The following core additives were employed in the
proportions stated (based on total weight of core material and
addend).
______________________________________ Example Additive Percent
______________________________________ 2 Surlyn A-1760 5 3 Elvax
4355 5 4 AgeRite Resin D 1
______________________________________
In the case of Examples 2 and 3, 71 lbs. of polyethylene (density
0.929 gm/cc), 32 lbs. of a mixture of 34 percent conductive oil
furnace black (Vulcan XC-72, Cabot Corporation) and ethylene
ethylacrylate copolymer (density 0.930 gm/cc, 18 percent
ethylacrylate) and 1 lb. antioxidant were loaded with additive in
the above proportions into a Banbury mixer. In Example 4 the same
procedure was followed save that 76 lbs. of polyethylene were
employed and the optional antioxidant excluded. In each example,
the resulting mixture was mixed, milled, extruded and annealed to
form a jacketed heating element as in the "control" of Example 1
(i.e., the electrodes were uncoated). As in Example 1, resistance
of each extrudate was periodically measured as the extrudates were
subjected to various voltages over a lengthy period, and the result
data for Examples 2, 3 and 4 plotted as before, respectively, on
FIGS. 4, 6 and 7. FIG. 5 depicts data similarly obtained with a
control identical to that of Example 2 save that Surlyn resin was
replaced with an equal weight of polyethylene. Just as in the case
of Example 1, the plots obtained in Examples 2-4 demonstrate the
markedly superior long-term resistance characteristics obtainable
according to this invention.
* * * * *