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Патент USA US3085922

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Apl'll 16, 1963
Filed Feb. 24, 1960
Patented Apr. 16, 1963
3,tl85 912
this manner, a steep temperature gradient is established
radially in the Teflon insulation during the heating step.
Charles L. Friese, Towson Township, Harford County,
Md, assignor to Martin-Marietta Corporation, a cor-'
poration of Maryland
Filed Feb. 24, 1960, Ser. No. 10,580
5 Claims. (Ci. ll7—2l2)
Before an excessive amount of heat is able to build up
in the interior of the Te?on wire, the wire is cooled.
Depending on the radiant energy heat ?ux, the time of
exposure and the physical dimensions of the Te?on wire,
cooling may be effected by either allowing the processed
wire to stand in air or by cooling the wire with a forced
draft of air or by other suitable accelerated cooling
Te?on or polytetrafluoroethylene has a wax-like surface 10 means.
For the purposes of the present invention, the term
texture which cannot be permanently marked with con
“Te?on” encompasses not only the homopolymer of tet
ventional marking inks in a satisfactory manner. Hot
ra?uoroethylene but also substances wherein an organic
material is admixed with or copolymerized with tetra?uo
cases where the Te?on is used as an electrical insulation 15 roethylene in such proportion and in such manner that
stamping produces a permanent mark but causes the
Te?on to break down, which is highly undesirable in
since the stamping process reduces the insulating capacity
of the Te?on. Heretofore, Te?on-coated electrical con
ductors have been marked in a non-permanent manner,
such that the markings may be rubbed off easily or be
the resulting admixture or polymeric product partakes
of the properties of tetra?uoroethylene. The organic
additive may constitute up to about 25% of the admix
ture or copolymeric product and may, for example, be
come illegible during use. , It has been considered neces 20 a material like polyisobutylene; butyl rubber including
the elastomeric copolymers of isobutylene and diole?ns
sary in many instances to admix an identifying color with
such as butadiene; polyacrylates and polyalkylacrylates
the Te?on prior to polymerization so that the different
including polymethylacrylate, polymethyl methacrylate,
types of wire might be identi?ed by the distinctive color
polyethylacrylate, polyethyl methacrylate and the like;
ing in the Te?on. This method of identi?cation has
proven unsatisfactory, however, because it requires a 25 butadiene~acrylic copolymers including butadiene-acryl~
ate, butadiene-acrylonitrile, and butadiene-acrylamide;
large inventory of wires of different colors to be main
butadiene-styrene copolymer; plasticized polystyrene;
tained in stock. Another method of marking Te?on Wire
polyvinyl halides and polyvinylidene halides including
comprises placing ink striping on the surface of the
polyvinyl chloride, polyvinyl ?uoride, polyvinylidene
Te?on insulation and then passing the inked Te?on wire
through a gas heated oven to dry the ink.
The dried
striping, however, is not permanently affixed to the
Te?on and may be readily rubbed off.
It is a purpose of this invention to provide a method
chloride, and polyvinylidene ?uoride; and alkyl-acrylate
copolymers including copolymers of 90% methyl meth
acrylate-10% methylacrylate, 90% methyl methacrylate~
10% ethylacrylate and the like. The term “Te?on wire,”
therefore, is to be understood as a metal conductor having
with ink in such a manner that the electrical qualities of 35 a sheath of the homopolymer of tetra?uoroethylene or a
sheath of any one or more of the admixtures or co
the Te?on are not materially impaired. It has been dis
of identifying Te?on wire by permanently marking same
covered, in fact, that the present marking method actu
ally improves certain electrical qualities of the Te?on
polymeric products hereinbefore enumerated. “Te?on
ink,” in an analogous fashion refers to liquid suspensions
and then rapidly heating the surface of the impressed
mixtures or copolymeric products. Speci?cally, the com
position of such ink includes ‘(1) a polytetra?uoroethyl
or thermoplastic materials comprising a suitable pigment
coating on commercial Te?on wires.
In outline, as shown on the drawing, the present meth 40 or colored ?ller admixed with particles of tetra?uoroeth
ylene or particles of any one or more of the aforesaid ad
od comprises impressing Te?on ink on the Te?on wire
Te?on wire with radiant energy to ?x the ink marking
ene dispersion; (2) a ceramic oxide pigment; (3) a bind
permanently. The markings so produced are extremely
durable and cannot be removed except by destroying the 45 er 1(or thickener); (4) a distilled water carrier; and (5)
a ?uorocarbon wetting agent. Ink in accordance with
underlying Te?on.
this speci?cation is commercially available from the Hi
This method differs essentially from all prior marking
Temp Wire Company as Black Marking Fluid, Code
methods in that the Te?on insulation is heated by means
913A. This invention, however, is not directed to the
of radiant energy, whereas, heretofore, the Te?on has
been heated by means of convection or conduction. The 50 particular materials used; but, rather, to the method by
which Te?on wires of the type described may be perma
conduction method is exempli?ed by hot stamping, which,
nently marked with Te?on ink.
as noted above, materially decreases the electrical insulat
ing capacity of Te?on. Convection heating, utilized in
applying striping to Te?on, cannot be performed at a
In accordance with the present invention, the Te?on
Wire or other Te?on article is marked with the desired
temperature which would cause the ink to bond perma 55 identifying symbol by pressing Te?on ink on/ or into the
Te?on surface. For this purpose, any conventional print
manently to the Te?on insulation because the temperature
ing machine may be used. A particular machine which
of the wire conductor would be raised to excessive val
has been employed successfully for marking Te?on wire
ues, such that the individual strands of conductor are
is the Dual Printer made by Duncan M. Gillies Co., Inc.,
caused to stick together, thereby seriously reducing the
?exibility of the Te?on wire. For example, when strip 60 West Bozleston, Massachusetts, which impresses the
Te?on wire by opposed printing discs through which the
ing is dried in a gas heated oven at about 850° F., the
wire is fed. Each disc is provided on its periphery with
silver plated individual conductor strands become joined.
a plurality of raised symbols and is made to pass through
In the present process, heat is transferred to the outer
surface of the Te?on insulation at a high rate for a
a bath of Te?on ink whereby the raised symbols become .
short period of time, the rate at which heat is absorbed 65 coated therewith.
The Te?on wire is subjected on its marked surface to
at the outer surface of the Te?on insulation being much
a predetermined ?ux of radiant energy, the principal
greater in magnitude than the rate at which heat is con
Wavelengths of which are in infrared region, which is
ducted from the outer surface to the wire conductor. In
After processing all samples were subjected to the in
sulation resistance test, the dielectric strength test, the
absorbed by and heats the outer surface of the Te?on
wire. Heating is continued for a length of time suffi
cient to permanently bond the ink to the Te?on, where
upon heating is discontinued to prevent an undue build
National Aircraft Standard 703. An unprinted sample
up of heat in the interior of the wire as would adversely
affect the Te?on insulation or the wire conductor.
specimen for comparison.
cold bend test and the heat resistance test as detailed in
which had not been heated was included as a control
The dielectric strength test calls for the application of
The source of infrared energy may be a resistance ele
3000 volts, to Class “A” insulation for a period of ?ve
minutes without breakdown. In order to obtain a ?gure
vice. In the preferred embodiment of the present inven
tion radiant energy is supplied by a metal resistance ele 10 of relative merit for these specimens, the standard dielec
tric strength test was followed immediately by a dielectric
ment of cylindrical con?guration through which the wire
breakdown test.
to be heated is passed. The resistance element is suitably
ment, a quartz infrared lamp or other conventional de
insulated by means of a refractory material so as to form
an open ended furnace.
Results of these tests on 16 ga. Class “A” Te?on wire
are listed in Table I.
Table I.—Results of Infrared Irradiation of “Class A”
Wire at Indicated Temperature of 1800" F.
Feed Rate Durability Resistance
Sample No.
Cold Bend
Heat Resistance
ofPrinting (Megs/50
Strength bkdn.. Strength bl:dn., Strength bkdn,
Fair _____ ..
Good ____ ..
320,000 Passed.
12.3 Passed“
14.3 Passed"
2,000,000 ...-d0....
12.3 ._..d0....
2,000,000 ....d0....
11.3 ...-do....
Fall‘ _____ ..
__________ _.
200,000 __-_<1o.._.
The optimum wire feed rate through the 36 inch fur
In order to provide a better understanding of the pres
ent invention, reference is made to the following speci?c 30 nace at 1800g F. was 0.4 ft. per second.
Generally, the processed specimens exhibited marked
examples, wherein the source of infrared energy was a
heated Nichrome screen, 30 x 30 mesh, made of 0.014
inch wire.
The screen was formed into a tube 3 inches
in diameter by 3 feet long, and insulated by a wrapping
of Thermo?ex, an asbestos sheet manufactured by Johns
Mansville Co., Chicago, Illinois.
The screen temperature was monitored with a 22 ga.
Chromel-Alumel thermocouple placed between the Ni
chrome screen and the insulation midway of the tube.
The particular Te?on ink used in the following examples 40
was Black Marking Fluid, Code 9l3-A produced by Hi
Temp, vInc., Chicago, Illinois.
improvements in breakdown voltage following the cold
bend test and in insulation resistance.
However, the
processed samples showed slightly lower resistance to di
electric breakdown after having been subjected to the di
electric strength test and the heat resistance test.
In all instances it was impossible to remove the mark
ings after irradiation except by destroying the underlying
One hundred foot samples of #22 ga. Te?on insulated
wire satisfying military standard MIL W 16878 were
printed with Hi-Temp Black Marking Fluid, Code 913A.
Five 100 foot samples (A thru E) of #16 ga. Te?on
insulated wire, satisfying military standard MIL W 16878,
were printed with Hi-Temp black marking ?uid (Code
913A), a Te?on ink, and sintered at speeds between 0.3
of ‘0.40, 0.35, and 0.30 ft. per second, respectively, which
and 0.7 ft. per second.
Three samples were processed at 1800° F. at speeds
are within the range of speeds at which optimum results
were obtained with the #16 ga. Te?on insulated “Class
A" wire of Example I. The marking on one of these
samples had poor durability, and the insulation on the
The screen temperature was manually controlled at a 50 other two samples separated and burned. These failures
temperature of 1-800° F. i20°.
The following procedure was followed in bringing the
furnace to operating temperature. Four hundred am
peres at 10 volts were supplied to the Nichrome screen
until the temperature indicated at the thermocouple was
155 0° F., at which point current was reduced to 300‘ am
apparently were caused by overheating.
Three additional samples were then processed at the
same temperature, 1800"’ F., but at higher feed rates,
viz., 0.5, 0.6 and 0.7 ft. per second, respectively. The
markings after processing proved to be of fair to good
durability. The temperature of the Nichrome screen was
then raised to an indicated 1950° F. Results are listed
peres. When the indicated temperature reached 1800°
in Table ‘II.
F., the current was further reduced to 250 amperes. A
Table II.--Results of Infrared Irradiation of "Class C”
Wire at Indicated Temperature of I 950° F.
Feed Rate Durability Resistance
Sample No.
ol'I’rinting (Megs/50
forced-air cooler placed at the exit end of the furnace
Heat Resistance
Strength bkdn., Strength blrdn, Strength hkdn.,
10.9 Passed..
9.0 ..--do....
12.5 PassecL.
13.5 ..-.d0.._.
Cracked ...... .-....(l0..._
was then turned on, and the printed Te?on was fed
Cold Bend
Specimens A through E of Example II provide a com
plete spectrum of processing speeds with results ranging
through the furnace substantially coincident with the lon 75 from failure due to insu?icient heating (at 0.9 ft./sec.) to
unsatisfactory results, which were caused by excessive
gitudinal axis thereof.
heating (at 0.5 ft./‘sec.) and consequent decomposition
radiating said surface with infrared radiation so as to
of the Te?on. Any speed between 0.6 and 0.8 ft. per sec.
bond said ink permanently to said surface.
3. The method of claim 2, wherein said polytetra?uo
roethylene coated wire is cooled after the irradiating
yielded excellent durability at this furance temperature.
Decomposition of the Te?on was indicated by the col
or of the processed specimen, namely, an oyster white
Results of the tests performed on the #22 ga. Te?on in
sulated wire followed the trend observed in Example I.
Although the invention has been described with par
4. In the method of marking polytetra?uoroethylene
coated wire wherein the surface of said wire is coated
with ink so as to form an identifying symbol thereon,
said ink comprising a colored ?ller admixed with parti
ticular reference to speci?c embodiments thereof, it will 10 cles of a copolymer of tetra?uoroethylene, the improve
ment comprising irradiating said surface with infrared ra
be understood that it is susceptible of embodiment in
diation so as to cause said ink to become permanently
bonded to said surface.
many other forms, such as will appear to one skilled in
the art in view of the foregoing teachings, without de~
parting from the scope of the invention as set forth in the
following claims:
What is claimed is:
1. A method of marking articles of homopolymers and
5. The improvement of claim 4 wherein said polytet
coated wire is cooled after the irradiat
ing step.
copolymers of tet-rafluoroethylene comprising the steps
of printing the surface of such an article with ink in the
desired pattern, said ink comprising a pigment admixed 20
with particles of polytetra?uoroethylene, and irradiating
said surface with infrared radiation so as to cause said
ink to become permanently bonded to said surface.
2. A method of marking polytetra?uoroethylene coat
ed wire comprising the steps of impressing ink onto the
surface of said Wire, said ink comprising a pigment ad
mixed with particles of polytetra?uoroethylene, and ir
References Cited in the ?le of this patent
Kreidl ______________ __ Mar. 31, 1953
Roberts ______________ __ Feb. 11, 11958
Osdal ______________ __ Aug. 29, 1961
Germany ____________ __ May 24, 1956
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