U.S. patent number 3,689,618 [Application Number 05/061,399] was granted by the patent office on 1972-09-05 for use of an unadvanced silicone resin binder in resistor manufacture.
This patent grant is currently assigned to Air Reduction Company. Invention is credited to George F. Chadwick.
United States Patent |
3,689,618 |
|
September 5, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
USE OF AN UNADVANCED SILICONE RESIN BINDER IN RESISTOR
MANUFACTURE
Abstract
A carbon composition resistor and method for manufacture thereof
is disclosed, the resistor being characterized as having a body
comprising a conductive particulate component, a nonconductive
particulate component, and a silicone resin binder for said
components, said binder being advanced and cross-linked entirely in
situ in the body.
Inventors: |
George F. Chadwick (N.
Tonawanda, NY) |
Assignee: |
Air Reduction Company
(Incorporated, New York)
|
Family
ID: |
22035538 |
Appl.
No.: |
05/061,399 |
Filed: |
August 5, 1970 |
Current U.S.
Class: |
264/104; 252/511;
264/105; 264/123; 264/236; 264/347 |
Current CPC
Class: |
H01B
1/24 (20130101); H01C 17/06586 (20130101) |
Current International
Class: |
H01C
17/06 (20060101); H01B 1/24 (20060101); H01C
17/065 (20060101); H01c 007/00 () |
Field of
Search: |
;264/104,105,236,347
;252/511,512 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Donald J. Arnold
Assistant Examiner: John H. Miller
Attorney, Agent or Firm: Hefan J. Klawber H. Hume Matthews
Edmund H. Bopp
Parent Case Text
BACKGROUND OF THE INVENTION
This application is a continuation of my copending application Ser.
No. 690,897, now abandoned, which application is a
continuation-in-part of my prior application Ser. No. 410,091, now
U.S. Pat. No. 3,382,574.
Claims
1. The method of making an electrical resistor body which comprises
a. mixing 15-50 percent by weight unadvanced heat-condensable
silicone resin binder with 85-50 percent by weight of particulate
non-conductive filler selected from the group consisting of silica,
mica, wollastonite, asbestos, glass and mixtures thereof, and 0.10
to 10 percent by weight of the total of binder and filler of
electrically conductive material selected from carbon black and
graphite, said mixing being carried out at a temperature at which
the silicone resin in the mix remains unadvanced, b. pulverizing
the mixture while maintaining the temperature below that at which
advancement of the resin takes place, c. forming a shaped body by
pressing the pulverized mixture in a die while maintaining the
temperature below that at which advancement of the resin takes
place, d. removing the shaped body from the die, and e. subjecting
the shaped body to a temperature of 200.degree.- 400.degree.C for
from 20 minutes to 2 hours to cure the silicone resin.
Description
This invention relates generally to composition electrical
resistors of the type including a particulate conductive material
such as, for example, carbon black, dispersed in a suitable binder
matrix. The invention relates more specifically to a resistor of
the aforementioned type in which the binder for the resistor body
constitutes a polymerized silicone resin.
In U.S. Pat. No. 2,526,059 to H. H. Zabel, et al. there is
described a method for formation of a resistor body of the general
type with which the present invention is concerned. According to
the teaching of this patent, the resistor body is formed by
combining an advanced organo-silicone polymer binder with a
conductive particulate component (and, as desired, inert fillers),
and thereafter subjecting the combined composition to hot molding
at relatively high temperatures. The same patent also teaches that
cold molding may be utilized to form the resistor body in those
instances where the binder has already been subjected to
substantial advancement prior to the cold molding process.
In my prior U.S. Pat. No. 3,382,574 previously alluded to, I have
disclosed my discovery that silicone resin-bound resistors of
improved heat and load stability may be produced by a special
curing cycle according to which the silicone resin binder of the
molded product is subjected to a short duration high temperature
cure of from about 400.degree. to 525.degree.C for a period of from
3 to 15 minutes. Now in accordance with the present invention, I
have found that a much broader range of temperatures may be
employed in curing a silicon resin-bound resistor in those
instances where initial cold molding of the unadvanced resin-bound
resistor body is effected; and I have moreover found that excellent
products thereby result at surprisingly low cure temperatures.
In accordance with the foregoing, it may be regarded as an object
of the present invention to provide a method for producing a
resistor having improved electrical properties, primarily greater
heat stability, better moisture resistance, and longer useful life.
It is also an object of the invention to produce by the aforesaid
method a resistor body which displays the qualities set forth.
SUMMARY OF INVENTION
Now in accordance with the present invention, I have found that
resistors displaying unusually excellent properties of heat
stability, moisture resistance, and life expectancy, may be
prepared by cold-molding a composition including a dispersed
conductive phase, an unadvanced silicone binder, and as
appropriate, inert fillers, and only thereafter subjecting the
cold-molded resistor body to the heat curing which effects
polymerization of the binder. Because much linear polymerization
and essentially all cross-linking occurring in the binder takes
place in situ, which is to say in the fully formed resistor body,
unusually fine uniformity results through the cured body of the
resistor, in consequence of which, the highly desired electrical
properties sought in such products are enabled. Although any
reactive silicone can be utilized, the preferred embodiment of the
invention uses a condensable type rather than an unsaturated type.
Resistors made according to this invention may be of any convenient
shape, such as rods, cubes, etc. and any desired termination may be
employed such as pressed metallic ends or molded-in wire leads.
BRIEF DESCRIPTION OF THE DRAWING
A fuller understanding of the present invention and of the manner
in which it achieves the objects previously set forth, may now best
be gained by a reading of the ensuing detailed specification.
The single FIGURE appended hereto may be examined simultaneously
with such reading, and will be found to graphically compare the
resistance change of prior art resistors with that of resistors
made in accordance with the present invention when both classes of
devices are subjected to electrical loads for extended periods of
time.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The mixture used for preparing resistors in accordance with this
invention basically includes a silicone resin binder and a filler.
To this "basic mix" are added quantities of electrically conductive
material in amounts which depend upon the desired resistance of the
end product.
Neglecting such solvents as may be used to facilitate the mixing,
the basic mix includes the following ranges of proportions (all
percentages stated herein being by weight): 15-50% Silicone resin
50-85% Filler, such as pulverized silica, mica, wollastonite,
asbestos fibers, chopped fiber glass, or a mixture of these and
other materials. To this basic mix is preferably added from
one-tenth to 10 percent of calcined carbon black or graphite as the
electrically-conductive material. Carbon or graphite in amounts
greater than 10 percent may be added to the mix to decrease the
resistance of the resulting resistor if desired. The carbon or
graphite can be included in the original blending of ingredients of
the basic mix to produce what may be considered a homogeneous mix;
or the carbon or graphite can be added later to the already-mixed
basic mix to produce what may be considered a heterogeneous
mixture. Better results are obtained by using carbon black calcined
at 1,000.degree.C or even higher temperatures.
In constructing the typical leadless or lead-type resistors such as
are shown in FIGS. 2 to 4 of my prior U.S. Pat. No. 3,382,574, it
will of course be usual practice to provide an insulating shell for
the conductive mix referred to. The "basic mix" alluded to may be
utilized for this shell, that is to say that a composition
resembling the resistor core--but minus the conductive
component--may form the insulating sleeve for the core. A typical
formulation for such a shell might thus include 20.0 percent
silicone resin, 78.4 percent 5-micron silica sand, 0.8 percent
black iron oxide, and 0.8 percent red iron oxide, the latter two
ingredients being added merely to provide desired pigmentation.
It is often desirable to include 10 percent of asbestos fines in
the filler, this percentage being taken as a portion of the basic
mix; similarly, 10 percent of glass fibers or of mixtures of
asbestos fines and glass fibers yield especially good results. The
glass fibers and asbestos result in a materially stronger resistor
without harm to the thermal stability and moisture resistance. It
was thus found that by including 10 percent asbestos fines in place
of some of the silica powder, an almost two-fold increase in the
"fiber strength" of the mix resulted.
The silicone resin utilized in the invention is preferably a
heat-condensable resin, and excellent results have been obtained by
incorporating both alkyl aryl and alkyl silicones simultaneously
into the resistor, or by utilizing either resin alone. Among those
resins giving especially good results are the silicones sold by the
General Electric Company under trade designations 81888, SR-80,
SR-211, and SR-350. Other suitable resins include the General
Electric products SR-220 and the Dow Corning products 5061, 5581,
and 2105A. The preferred compositional range for the resins
utilized in the invention is between 18 and 22 percent by weight of
the basic mix, when silica flour is the principal filler.
The essence of the present inventive process resides in utilizing
such techniques that essentially no advancement of the silicone
resin binders occurs prior to such time as the completely molded
resistor is subjected to the heat curing which effects gross
polymerization and cross-linking of the binder. In the analagous
parlance of phenolic resin technology, this mode of operation is
thus equivalent to maintaining the resins prior to completion of
molding below the so-called B stage of polymerization, that is to
say below the stage of polymerization at which the resinous
products are no longer soluble in such organic solvents as acetone.
During the initial process steps of mixing and roll-milling, the
absence of such silicone advancement is assured by merely
eliminating the use of temperatures which could effect advancement,
a proscription which is generally contrary to teachings of the
prior art. The following examples are illustrative of the mixing
and milling techniques:
EXAMPLE I
In this example, which is illustrative of "dry processing" via a
roll mill alone, a core mix comprising by weight 22.0 percent
silicone resin, 6.0 percent carbon black, calcined, and 72.0
percent silica sand, was prepared. The silicone resin utilized was
the SR-350 resin of General Electric, a type which is essentially
"solid" at room temperature, and which in fact comprises about 98
percent solids and 2 percent acetone. The rolls on the roll mill
were heated to approximately 46.degree.C to soften the silicone
resin. The mill was then turned on and all the resin was added. The
resin immediately formed a continuous sheet around the more rapidly
moving roll. Carbon black and silica flour were then added, in that
order. After approximately 1 to 2 minutes the mix appeared
homogeneous. Milling was continued for approximately 7 minutes, at
which time the molding compound was removed as a warm sheet. Upon
cooling, the sheet became hard and brittle.
Typical times and temperatures observed in runs with approximate
parameters as in the preceding paragraph were: Initial Temperature
Faster Roll 46.degree.C Slower Roll 46.degree.C Final Temperature
Faster Roll 88.degree.C Slower Roll 71.degree.C Sheet Temperature
88.degree.C Time 5-10 minutes
EXAMPLE II
In this example, which is illustrative of "wet processing"--via a
sigma blade mixer plus a roll mill, a core mix similar to that
described in connection with Example I was utilized. Initially, the
jacket of the sigma blade mixer (Day) was heated to 82.degree.C.
Acetone and the silicone resin were then added, and blended 15
minutes to dissolve the resin. The other components were then added
and mixed 30 minutes, with the lid on, after which the lid was
removed, acetone exhausted, and the mix run to dryness. About 30 to
45 minutes was required to desolvate the mix. The resulting dry,
powdery composition was then roll-milled in the manner that has
been described in connection with Example I.
Following the mixing and milling steps set forth in the preceding
examples, the resulting compositions are prepared for cold molding
by hammer-milling and screening the mixtures:
EXAMPLE III
A cooled sheet prepared in accordance with Examples I or II (50
mils thick) was broken into smaller pieces and hammer-milled to
give a free flowing powder, which was then screened to a -40 to
+325 mesh particle size for molding.
It should be carefully observed that thus far in the practice of
the present invention only temperatures have been utilized which
are below those at which advancement of the silicone binder occurs.
That the binder does not in fact advance to B staging has been
conclusively demonstrated, by experiments of the following
type:
EXAMPLE IV
A core mix was formulated containing approximately 25 percent
silicone resin, 6 percent calcined carbon black, and 69 percent
silica filler. A suitable solvent was added, the mix was "wet
processed" in a sigma blade mixer, and desolvated to dryness at
82.degree.C. The mix was divided into two parts and further
processed on a warm roll mill. Part A was roll milled 5 minutes to
a final sheet temperature of 82.degree.C. Part B was roll milled 10
minutes to a final sheet temperature of 88.degree.C. Both parts
were hammer-milled and screened to a -40/+325 mesh particle size.
Aliquots of each were then extracted with acetone at room
temperature by tumbling four hours in sealed containers. Filtration
to retain the fillers and desolvation of the filtrate to
recrystallize the dissolved resin gave the following results: Part
A Part B Wt. % of filler recovered on filter 96 100 Wt. % of resin
recovered in filtrate 98 96 M.P. range of recovered resin
63-67.degree.C 63-67.degree.C Initial M.P. range of resin before
61-65.degree.C 61-65.degree.C processing
The composition resulting from the screening and hammermilling
operation is thereafter, in accordance with the invention,
subjected to a cold molding process in apparatus well-known and
conventional in the art. Typically, the resistor shell is thus
pre-formed at 1.0 to 1.5 T.S.I. (tons per square inch) for 30
seconds. Thereafter, the core mix is added, leads are inserted, and
the entire resistor is molded at 8-10 T.S.I. for 30 seconds.
Throughout such molding process the maximum die temperature
utilized is about 35.degree.C, so as previously indicated, no
advancement of the binder occurs. Preferably, the leads referred to
will be provided at their end portions with a lead dope coating
consisting of approximately 37.5 percent silicone resin and 62.5
percent graphite mixed with enough toluene to give proper flow.
Subsequent to cold molding, the formed resistors are ejected, and
are ready for curing.
Heat curing of the cold molded resistors can be accomplished by
baking in an oven, by infrared radiation, by microwave irradiation,
or via other means for supplying the energy required. Reference may
be had in this connection to my copending application Ser. No.
410,091 application wherein a form of apparatus suitable for this
purpose is depicted. Regardless of the particular mechanism used to
provide curing energy, however, the important point to note is that
essentially all advancement and cross-linking of the silicone
binder takes place during this cure cycle, which is to say with the
binder in situ in the completely formed resistor body. The result
of such action is to yield a resistor which displays outstanding
properties of electrical stability.
Table I is illustrative of the results achieved where a large group
of 2-watt resistors were prepared in accordance with the cold
molding method used in this invention and then subjected to
appropriate heat curing cycles. The resins used in the various test
are listed in the first column, all the SR notations representing
product designations of the supplier, General Electric Company. In
all instances, as is seen from the second column, cold mold
temperatures are utilized prior to curing.
As may be observed from the next column of Table I, (that depicting
the cure treatment) the present invention, in general, utilizes a
considerably lower range of temperatures than has previously been
considered desirable in this technology, for curing of silicone
binders. Temperatures are thus seen from this ##SPC1##table to
range, generally, from about 180.degree. to 375.degree.C with cure
times of the order of 20 minutes to 2 hours. The best overall
results have been achieved where curing temperatures in the range
of from about 250.degree. to 325.degree.C are utilized. It may be
noted that in a number of instances cited in the table the heat
cure is followed by an annealing step--most commonly 3 days at
about 180.degree.-200.degree.C-which often acts to further
stabilize the resistor; however, it is clear from the data
presented that annealing need not be utilized.
The data presented in the remaining columns of Table I provides
specific test results achieved with the resistors. The R column
here thus indicates the measured resistance value of the test item
in question; the NI column has reference to the noise index in
decibels of the item, and is an indication of the ratio mv/V, where
V is an applied standard signal and mv is the resulting spurious
signal produced in the test body. The R.T.C. column refers to the
resistance temperature coefficient of the resistor, the tabulation
being given in the table for -55.degree.C and for +105.degree.C.
The "accelerated moisture test" of the next column tabulates the
percentage resistance change upon subjecting the test body to 3
days at 70.degree.C in a relative humidity environment of 95-100
percent.
The final column in Table I represents the result of subjecting
resistors prepared in accordance with the invention to a standard
load test. In this test an appropriate electrical load (2 watts and
not over 500 volts for these 2-watt resistors, for example) is
applied at 70.degree.C for 1,000 hours. The load is applied in
cycles--90 minutes load and 30 minutes no load. The stability of
the resistor is judged by comparing the resistance before and after
the test. Data of the type collected in this column is also
graphically plotted for a typical resistor prepared in accordance
with the invention, in the figure appended to this specification.
As may be readily seen from the graph, the improvement in
stability, as compared to a conventional silicone-bound
resistor--that is to say a resistor prepared with hot molding
and/or substantial advancement of the binder prior to molding--is
most impressive.
while the present invention has been particularly described in
terms of specific embodiments thereof, it will be evident that in
view of the present disclosure numerous modifications and
variations of the invention may now be readily devised by those
skilled in the art without yet departing from the teaching herein.
Accordingly, the invention is to be broadly construed, and limited
only by the scope and spirit of the claims appended hereto.
* * * * *