Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ lC4~921
HOSE REINFORCED WITH DISCONTINUOUS
F IBERS ORIENTED IN THE RADIAL DIRECTION `~
This application is a divisional of copending applica-
tion serial number 257,645, filed July 23, 1976.
This invention relates to hose reinforced with
discontinuous fibers, particularly to hose reinforced with
discontinuous fibers oriented in the radial direction. The
invention also relates to methods for preparing discontin-
uous fiber reinforced hose by extrusion, and particularly
to methods for preparing extruded hose reinforced with
discontinuous fibers oriented in the radial direction.
BACKGROU~D OF THE INVENTION
It is known that forcing a matrix containing
discontinuous fibers through a restricted space, by milling
or extrusion, orients the fiber in the direction of flow.
The alignment of the fibers is similar to the alignment of
logs in a moving stream. Thus, extrusion of a matrix
containing discontinuous fibersthrough conventional dies
gives a hose in which the fibers are oriented in the axial
direction (the direction parallel to the axis of the die).
Applicants in their
described a hose
reinforced with discontinuous fibers oriented in the circum-
ferential direction which hose is prepared by extruding a
polymer matrix containing discontinuous fibers through a
die channel having inner and outer surfaces which diverge
from the axis of the die to such extent that the ratio of
the channel outlet to channel inlet area is two or more.
Hoses with fibers oriented in the axial direction
have great longitudinal strength because of the fiber
reinforcement in that direction, ~.7hereas, hoses with fibers
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oriented in the circumferential direction can withstand greater
internal pressure with less expansion because of the fiber
reinforcement around the circumference of the hose. However,
in both the aforesaid hoses the fibers are oriented parallel to
the surface of the hose and the hoses are essentially free of
fiber reinforcement in the radial direction.
It has been discovered that forcing a composite of
extrudable polymer and discontinuous fiber through a channel of
proper geometry formed between a mandrel and an outer die
member results in an extrudate with improved radial proper~ies.
In a preferred embodiment of the present invention, there
is provided a hose of extrudable polymer reinforced with dis-
continuous fibers in which upon exposure to an organic solvent
the percent change in wall thickness is less than the percent
change in diameter.
The present invention provides a hose of extrudable
polymer reinforced with discontinuous fibers oriented in the
radial direction. The invention also provides a process for
pxeparing an extruded hose in which the radial component of fiber
orientation exceeds the circumferential component of fiber orie~l-
tation, which comprises extruding a composite of extrudable
polymer and discontinuous fibers through a die having a channel
of curvilinear cross-section, preferably an annular cross-section
formed between surfaces of a central mandrel and an outer die
member in which the channel outlet area is about two or more
times the channel inlet area, the channel outlet width is two or
more times the channel inlet width and the ratio of the channel
outlet width to the channel inlet width is two or more times the
ratio of the channel outlet mean radius to the channel inlet mean
radius. The radial component of fiber orientation, which relates
to the fiber reinforcement of the hose in the radial direction, is
therefore controlled relative to the axial and circumferential
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components by selecting a die of proper geometry. For
example, a hose in which the fiber reinforcement in the
radial direction exceeds the fiber reinforcement in the
- circumferential direction is prepared by extruding composite
through a die in which Ao is about two or more and Wo is
Ai Wl
two or more times Ro wherein Ao is the channel outlet
Ri
area, Ai is the channel inlet area, Wo is the channel width
at the outlet, Wi is the channel width at the outlet, Ro
is the channel outlet mean radius (distance from axis to
center of channel) and Ri is the channel inlet mean radius.
The channel inlet is considered to be the point of shortest
distance between the die members. It is understood that
when Ao is about two or more and Wo is two or more times
Al
Ro then Wo is also two or more. A hose in which the fiber
Wl
reinforcement in the radial direction exceeds that in the
circumferential direction and also exceeds that in the axial
direction is prepared by extruding composite through a die
in which Wo . Ro is two or more and the channel outlet axea
Wi Ri
is about three or more times the channel inlet area. A hose
in which the fibers are highly oriented toward the radial
direction giving a high degree of reinforcement in that
direction is prepared by extruding a composite through a
die in which Wo . Ro is two or more and the channel outlet
area is about five or more times the channel inlet area.
Preferably, the value of Wo Ro is three or more and,
Wi Ri
more preferably, is four or more.
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lO~l9Zl
The angular placement of the individual fibers
throughout the extruded composite constitutes the orient-
ation distribution which determines the directional or
anisotropic physical properties of the hose. There is a
direct correspondence between the orientation distribution
of the fibers and the directional material properties,
such as mechanical strength, modulus, or elongation measured
under an applied stress or under an internal stress generated
by the swelling action of a solvent. The reinforcement
anisotropy can be characterized by specifying either the
components of the fiber orientation or a corresponding
material property for each of the three principal directions
in the hose: axial, circumferential and radial.
The term "composite" as used herein means "a mixture
of discontinuous reinforcing fibers in a matrix comprising
extrudable polymer." The term "channel width" as used herein
means the distance between the surface of the mandrel and the
surface of the outer die member which forms the channel.
The term "components of fiber orientation" means the direction
cosines of the fiber axes averaged over the entire population
of fibers present in the hose. Fiber orientation may be
described by the direction cosines of each fiber axis relative
to the x, y and z coordinates, in which x is a coordinate
parallel to the axis of the die which passes through one
end of the fiber, y is the coordinate tangent to a circle
concentric to the axis which passes through the same fiber
end, and z is the coordinate perpendicular to the plane
defined by x and y. Thus, when the y and z intercepts are
zero so that the fiber is lying along the x-axis,
the direction cosines cos ~y = cos ~z = ~ = z = 0 and
cos ~x = x = 1, where Q is the fiber length. Conversely,
when x and y are zero, then z is equal to the fiber length,
and the fiber is oriented entirely in the radial direction.
Typically, the value for each direction cosine is greater
than zero, meaning that the fiber is tilted away from any
particular plane. A mean orientation vector (of unit
length) can be derived by averaging the direction cosines
over the entire population of individual fibers. The fibers
can then be said to be oriented in general toward one of the
principal directions, or to have a predominant orientation
in that direction, if the mean direction cosine for that
direction exceeds each of those for the other two directions.
The reinforcing effect of the fibers will of course also be
highest in the direction of hignest direction cosine. The
term "highly oriented" as used herein means the situation
when the square of the mean direction cosine for any principal
direction exceeds a value of 0.5. In other words, the square
of the mean direction ~osine for any principal direction, by
geometrical considerations, exceeds the sum of the squares
of the mean direction cosines for the other two directions.
The orientation may be conveniently determined by swelling
a specimen of composite hose and measuring the amount of
swell in each of the principal directions. The amount of
swelling in each direction indicates relative fiber orientation.
The specimen swells the least in the direction having the
largest component of fiber orientation.
. .
.
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1041921
A hose of this invention has a smooth surface and
is pliable while in a plastic condition,which facilitates
bending to form a shaped hose without significant distortion
or loss of surface smoothness. A plastic condition means a
state in which the hose is soft enough to be shaped yet capable
of retaining a fixed shape after being formed. Thermoplastic
polymers, including thermoplastic elastomers, are generally
in a plastic condition at elevated temperature and harden upon
cooling. Thermosetting polymers, including vulcanizable
elastomers, are in a plastic condition while being masticated,
compounded, extruded and shaped but lose plasticity upon curing.
Thus, with vulcanizable elastomers, a hose is extruded, bent
to the desired shape and cured, whereas, with the thermoplastic
elastomers, a hose is extruded, bent to the desired shape and
then cooled.
The process of the invention is applicable to any die
having a channel of curvilinear cross-section formed between
- surfaces of a central mandrel and an outer die member which
surfaces may independently be substantially parallel to,
converge toward or diverge from the axis of the die provided
the relationships, as recited above, of the ratios of channel
area Ao~ channel width WO and channel radius Ro are met.
Ai Wi Ri
Thus, nine arrangements of channel surfaces are possible:
(1) the mandrel surface is parallel to the axis with the
interior wall of the outer die member diverging from the axis,
(2) the mandrel surface converges toward the axis with the
intarior wall of the outer die member parallel to the axis,
(3) the mandrel surface converges toward the axis and the
interior wall of the outer die member diverges from the axis,
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109~9Zl
(4) the surfaces of both the mandrel and the interior wall
of the outer die member are parallel to the axis of the die,
(5) the mandrel surface is parallel to the axis with the
interior wall of the outer die member converging toward the
axis,
(6) the mandrel surface diverges from the axis with the
interior wall of the outer die member converging toward the
axis,
(7) the mandrel surface diverges from the axis with the
interior wall of the outer die member parallel to the axis,
(8) the surfacesof both the mandrel and the interior wall
of the outer die converge toward the axis, and
(9) the surfaces of both the mandrel and the interior wall
of the die diverge from the axis.
A channel surface diverges from the axis of the die
when the surface is farther from the axis at the channel
outlet than at the channel inlet, and conversely, a channel
surface converges toward the axis of the die when the
surface is nearer the axis of the die at the channel outlet
than at the channel inlet.
To achieve radial orientation when the channel
surfaces are formed in accordance to arrangements (1) through
(3), the length of the channel must extend a sufficient
distance in the direction of extrusion to achieve the
necessary increase in channel width and channel area. To
achieve radial orientation when the channel surfaces are -
formed in accordance to arrangements (4) through (7), it
is necessary to constrict the channel inlet to obtain the
required increases in channel width and channel area in
the direction of extrusion. To achieve radial orientation
1041921
when the channel surfaces are formed in accordance to
arrangements (8) and (9), it is only necessary to constrict
the channel inlet when the surfaces are substantially
parallel or do not diverge sufficiently from each other
to provide the required increases in channel width and
channel area. ~he channel inlet may be conveniently
! constricted by having a weir protruding either from the
interior wall of the outer die member or from the surface
of the mandrel or both. The height of the weir may be
varied to provide any desired channel width at the inlet
and corresponding channel inlet area. As previously
described, the radial component of fiber orientation may be
controlled by varying the ratio of the channel outlet area
to the channel inlet area. Of course, it is understood
that a weir may also be used in dies having channel surfaces
formed in accordance to arrangements (1) through (3), if
desired. Dies in which the channel surfaces are formed in
accordance to arrangements (1) through (4) are preferred
because the requirements of Ao and WO Ro are more readily
Ai Wl Ri
obtained. Surface arrangements (5) through (9) are suitable
for achieving radial orientation but require greater
constriction at the inlet (weirs of greater height) because
channel surfaces which converge toward each other (5, 6 and
7) or converge toward the axis (8) tend to orient fibers
in the axial direction and channel surfaces which diverge from
the axis (9) tend to orient fibers in the circumferential
direction. A better understanding of the invention may be
obtained by reference to the drawings.
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DESCRIPTION OF THE DRAWINGS
Figure 1 is a graphic representation of a reinforced
hose with a section removed to show the arrangement of
discontinuous fibers oriented in the radial direction.
Figure 2 is a graphic representation of a reinforced
hose with a section removed to show the arrangement of dis-
continuous fibers oriented in the axial direction.
Figure 3 is a graphic representation of a reinforced
hose with a section removed to show the arrangement of dis-
continuous fibers oriented in the circumferential direction.
Figure 4 is a side view of a section of a die cutalong a plane through its axis which die has a weir protruding
from the outer die member.
Figure 5 is a side view of a section of a die cut
along a plane through its axis which die has a weir protruding
from the mandrel.
Figure 6 is a side view of a section of a die cut ~;
along a plane through its axis which die has a channel which
increases in a cross-sectional area in the direction of
extrusion.
- DETAILED DESCRIPTION
Referring to Figure 1, hose 1 with a section removed
illustrates a hose having fibers 2 oriented in the radial
direction. Radial orientation of the fibers is shown in the
end cross-section of hose 1 by fibers 2 being aligned so that
they point toward the axis of symmetry of the hose. In the
portion of hose 1 in which a section is removed, only the ends
of fibers 2(or cross-sections of fibers) are in view.
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~1041921
Figure 2 shows hose 3 having fibers 4 oriented
in the axial direction in which the fibers are aligned
substantially parallel to the axis of symmetry of the hose.
In the end cross-section of hose 3, only the ends of fibers 4
(or cross-sections thereof) are in view, whereas, substant-
ially the entire length of fibers 4 are visible in the portion
of hose 3 in which a section is removed.
Referring to Figure 3, hose S is shown having fibers 6
oriented in the circumferential (hoop) direction in respect
; 10 to the axis of the hose. In circumferential orientation,
fibers 6 are aligned in the direction of the circumference
of the hose, therefore, substantially the entire lengths of
fibers 6 are visible in both the end cross-section of hose 5
and in the portion of hose 5 in which a section is removed.
Of course, it is understood that Figures 1, 2 and 3
are idealistic representations. Normally, a number of fibers
are tilted from any particular plane of orientation and all
three orientations, axial, circumferential and radial, co-exist
with one type of orientation generally predominating.
Axial orientation as shown in Figure 2 may be
achieved by extruding a matrix containing discontinuous
fibers through a die having a channel of equal or diminishing
channel width which channel is essentially parallel to the
direction of extrusion; however, minor numbers of fiber may
still be oriented in the other two planes. Circumferential
orientation as shown in Figures 3 may be achieved by extruding
a matrix containing discontinuous fibers through a die having
1041921
a channel in which both channel walls diverge outwardly
from the axis. Radial orientation as shown in Figure 1
is achieved by extruding a matrix containing discontinuous
fibers through dies illustrated in Figures 4, 5 and 6.
Figure 4 shows a die comprising mandrel 10 with
surface 14 and outer die member 11 with interior wall 13.
Surface 14 and interior wall 13 form channel 12. Weir 16
of height h and width w protrudes from outer die member 11.
Height h may be varied to give any desired ratio of channel
outlet area to channel inlet area. The width w of weir 16
is not critical, it may be small, for example 0.1 millimeter
or less or may be large such as several centimeters or more.
The angles at which the walls of weir 16 join die member 11
may vary. The angle of the upstream weir wall is designated
by the symbol and the angle of the downstream weir wall
is designated by the symbol ~. When ~ is large, for example,
from about 30-90, the downstream wall of weir 16 extends
a short distance or not at all toward the outlet with interior
wall 13 remaining substantially parallel to the axis of
symmetry of the die. However, when ~ is small, for example,
; less than about 25, the downstream wall of weir 16 is
relatively long and becomes interior wall 13 which wall
diverges from the axis of the die as shown by phantom line 13.
When interior wall 13 diverges from the axis, it is preferred,
that a portion of 13 near outlet 15 remains parallel to the
die axis forming land 18. Surface 14 and the top of weir 16
form inlet li which inlet 17 has a cross-sectional area less
than the cross-sectional area of outlet 15. The direction
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of extrusion is from left to right. A composite is fed
through inlet 17 and an extrudate containing oriented fibers
discharges from outlet 15.
Referring to Figure 5, another die of the invention
is illustrated comprising mandrel 20 with surface 24 and
outer die member 21 with interior wall 23. Surface 24
i and interior wall 23 form channel 22. Weir 26 of height h
and width w protrudes from mandrel 20. The designation of
the angles at which the walls of weir 26 join mandrel 20
are the same as in Figure 4. When ~ is large, interior
wall 24 is substantially parallel to the axis of symmetry
of the die. When ~ is small, the downstream wall of weir 26
becomes surface 24 which surface converges toward the axis
of the die as shown by phantom line 24. When surface 24
converges toward the axis, it is preferred that a portion
of 24 remains parallel to the die axis forming land 28.
Optionally, land 28 may provide for a mode~t constrictionin
the width of channel 22 as shown by the phantom lines on the
end of mandrel 20. Interior wall 23 and the top of weir 26
form inlet 27 which inlet 27 has a ~maller area than outlet 25.
Figure 6 shows a die comprising mandrel 30 with surface
37 converging toward the axis and surface 34 being substant-
ially parallel to the axis and outer die member 31 with interior
wall 35 diverging from the axis and interior wall 33 being
Rubstantially parallel to the axis. Interior wall 35 and
surface 37 foxm channel 43. Interior wall 33 and surface 34
form channel 32 and comprise the land portion of the die.
Interior wall 39 of outer die member 31 and surface 40 of
mandrel 30 form inlet 38. A composite is fed through inlet 38
and an extrudate containing oriented fibers issues from
outlet 36.
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In one embodiment of the invention, hoses with
improved burst strength are prepared by extruding composite
through dies as previously described in which the channel is
constricted near the outlet to reduce the outlet area about
5% to about 25% from the maximum channel area within the die.
In accordance to this embodiment, when the channel is constric-
ted at the outlet, the outlet area is still greater than the
inlet area, and preferably the outlet area is two or more
times the inlet area.
The reduction of the channel area at the outlet is
conveniently effected by providing a constriction of the
amount necessary to give the desired reduction in area at the
channel outlet, for example, a constriction as illustrated by
the phantom lines on the end of mandrel 20 of Figure 5.
Alternately, the constriction may be situated on the interior
wall of the outer die member at the outlet or two constrictions
may be provided at the outlet with one on the mandrel and the
other on the outer die member. The area reduction effected by
the constriction at the outlet may be abrupt or gradual, i.e.,
the upstream edge of the constriction may either join the
mandrel, for example, perpendicularly providing a sharp leading
edge or at an angle to provide a tapered leading edge. The
length of the constriction at the outlet (forming a land
portion of the die) is desirably equal or greater than the
channel width at the outlet, preferably, the length is 4 to 6
times the channel width. The preparation of hoses by extruding
composite through dies having constricted outlets as explained
above results in hoses still having fibers oriented toward the
radial direction but which exhibit substantially improved burst
strength.
~041921
Factors other than die geometry may affect fiber
orientation at least to a limited extent. For example,
such factors as fiber size, fiber loading, matrix viscosity
and extrusion conditions, such as temperature and feed rate,
will affect fiber orientation. An extrudate issuing from
the die which retains its shape indicates that all these
variables are within satisfactory limits. However, over
wide ranges of fiber size, fiber loading, matrix properties
and extrusion conditions, the channel geometry (i.e. the
increase in area) is the dominant factor. Also, it is under-
stood that the fiber orientation at the entrance of the die
may influence the orientation achieved as the composite passes
through the die. Usually the orientation is axial at the
entrance. However, the process of the invention is applicable
to other orientations at the throat and to randomly disposed
fiber.
The length of the channel is variable. For example,
the channel length may be about equal to the channel width
but generally the channel length is two or more times the
channel width. Preferably, the channel length is five or
more times the channel width and often is ten or more times.
However, it will be appreciated that a lengthy channel
increases the pressure drop through the die and that the walls
of the channel tend to orient the fiber parallel to their
surface in the direction of extrusion. Although not essential,
it is preferred when using channels having non-parallel
surfaces, to provide a land portion at the channel outlet,
the surfaces of the land portion being parallel to the axis
of the die. Generally, the length of the land is two or more
times, preferably, about 5 or 6 times the width of the channel.
10419~1
Hose with an annular profile is obtained by extrud-
ing composite through a die with a circular outlet in which
the mandrel is concentric with the outer die member. Hose
with a non-symmetrical curvilinear profile is obtained by
extruding composite through a die having a non-circular out-
let such as an oval or cigar shaped outlet. Hose with non-
uniform wall thickness is obtained by extruding composite
through a die in which the mandrel or outer die member have
different profiles or by extruding composite through a die
in which the mandrel is set off-axis. Hose with non-uniform
wall thickness are especially useful in preparing pneumatic
tire preforms. The hose is cut to the appropriate length,
; bent to conform to a tire mold with the thickest area at
the crown portion of the tire thereby forming the tread. Hose
with either symmetrical or non-symmetrical profiles may be
split and laid flat to form a sheet which sheet has a proportion
of fibers (more or less depending upon the area expansion
through the die) oriented perpendicularly to the surface of the
sheet. Normally, when making sheet a hose of 30 centimetersor ~-
more in diameter is used. Of course, there is no limit on the
size of hose which may be prepared in accordance to the invention.
Typically hose size does not exceed ten centimeters in diameter
and one centimeter in wall thickness. The invention is partic-
ularly advantageous for making small size hose of four centi-
meters in diameter or less and wall thickness of one to five
millimeters.
Any discontinuous fiber may be used. Fibers which
reinforce matrices generally include fibers having an average
aspect ratio o~ 10-3000 and more commonly are fibers having
an average aspect ratio of 20-1000. A preferred aspect ratio
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is 20-350 with an aspect ratio of 50-200 being particularly
desirable. Various types of organic and inorganic discontin-
uous fibers are suitable either in monofilament or stranded
form (including bundles of fibers bonded together to make a
single element which serves as a single fiber in the sense of
orientation and reinforcement). Illustrative examples of
- satisfactory discontinuous fibers are nylon, rayon, polyester,
cotton, wood cellulose, glass, carbon, steel, potassium
titanate, boron, alumina and asbestos fibers.
The fiber loading is limited only by the workability
; of the composite. A workable fiber concentration depends upon
fiber aspect ratio, minimum clearance through the die and the
viscoelastic properties of the matrix. The amount of fiber
dispersed in the matrix is generally between 5-200 parts by
weight per 100 parts by weight matrix with amounts of 5-75
parts by weight per 100 parts by weight matrix being especially
suitable and 10-40 parts by weight per 100 parts by weight
matrix being preferred. The aforesaid fiber loading is calc-
ulated by considering all of the other ingredients of the
composition (polymer, pigments, antioxidants, bonding agents,
etc.) besides the fiber, as being the matrix and is not to be
confused with fiber loading expressed in parts by weight per
100 parts by weight polymer which is often done for convenience
in formulation. The composite may be comprised entirely of
polymer and discontinuous fiber with the polymer being the sole
matrix material but generally the polymer comprises only a ~ -
portion of the matrix because of the presence of other compound-
ing ingredients. Typically, the polymer comprises 10-80 weight
percent of the composite but more usually, the polymer comprises
about 20 to about 50 weight percent of the composite. The
-17-
104~921
proportions of the fiber will usually fall within the range
of 20-150 parts expressed as parts by weight per hundred of ~-
polymer. Some synthetic rubber formulations normally contain
much higher proportions of other ingredients than natural
rubber formulations.
The invention is applicable to any extrudable polymer
in which fibers can be dispersed. Any polymer which may be
extruded through dies by application of pressure is suitable
in the practice of this invention. Thermoplastic polymers
are particularly suitable, examples of which are polyvinyl
chloride, polyethylene, polypropylene, polyvinyl acetate,
polyester polymers, for example, poly(ethylene terephthalate),
ABS copolymers, polyamides, for example nylon. A preferred
class of extrudable polymers are elastomeric polymers. One
class of suitable elastomeric (rubbery) polymer comprises
thermoplastic elastomers which do not require vulcanization
but are shaped above their softening temperature and develop
elastomeric properties upon cooling. Examples of satisfactory
thermoplastic elastomers are polyurethane-polyester elastomers
(commercially available under the Trademark Texin), segmented
polyethers and polyesters (commercially available under the
Trademark Hytrel), nylon block polymers and dynamically
` partially cured blends of polyolefin resin and mono-olefinic
rubber, (commercially available under the Trademark TPR). U. S.
patents 3,806,558, 3,023,192, 3,651,014, 3,763,109, 3,775,373-5,
3,784,520 and 3,533,172 illustrate suitable thermoplastic
elastomers. Vulcanizable elastomers comprise another class of
extrudable polymers, especially sulfur-vulcanizable diene
elastomers. Either natural or synthetic rubbers or mixtures
thereof are satisfactory. Illustrative examples of suitable
-18-
.~ ...... .. . . . . .
~ .
10419Zl
.,: .
synthetic rubbers include cis-4-polybutadiene, butyl rubber,
neoprene, ethylene proplene terpolymers, polymers of 1,
3-butadiene, polymers of isoprene, ethylene vinyl-acetate
copolymers and copolymers of 1, 3-butadiene with others
monomers, for example, styrene, acrylonitrile, isobutylene
and methylmethacrylate.
The matrix may, in addition to polymer and fiber,
contain other ingredients commonly found therein, and
especially those ingredients necessary for achieving the
desired properties of the composite composition. Such
- materials may include, for example, plasticizers, extender
oils, antidegradants, reinforcing and non-reinforcing
pigments such as zinc oxide, barium oxide, strontium oxide,
iron oxide, silica, carbon black and organic pigments,
bonding agents, vulcanizing agents such as sulfur, peroxides
and vulcanization accelerators. Preferred elastomer compositions
- are wood cellulose fiber-elastomer composition described in
U.S. patent 3,697,364 and discontinuous mixed fiber-elastomer
compositions described in U.S. patent 3,709,845, both
disclosures of which are incorporated herein by reference.
DESCRIPTION OF PREFERRED EMBODIMENTS
. .
To illustrate the invention, a composite comprising
cellulose fiber and vulcanizable rubber composition is
extruded through dies having constant channel width but having
different area expansions to form 1.27 cm ID hose having about
4.2 mm wall thickness. The extrudate is cut to provide hoses
of any desired length. The uncured hose is vulcanized either
in an autoclave or in a mold. When making shaped hose, the
- hose is bent to the desired shape and vulcanized; preferably
vulcanization is carried out in a mold.
--19--
- . . , ... .. :
1041921
When the shape of the hose is not too complex, an open
one-half mold is all that is necessary to maintain the
shape during cure. Shaping of the hose and curing in a
mold does not significantly affect fiber orientation.
' A composite feed material is prepared by incorp-
orating 65 parts of wood cellulose fiber treated to
reduce fiber-to-fiber interaction comprising about 66%
fiber with the remainder comprising mainly rubber, lubricant
and bonding agent, into the following rubber composition.
Parts by Weight
EPDM Rubber 100
FEF carbon black 122
Extender oil 85.3
Zinc oxide 5
Stearic acid
Polymethoxymethylmelamine
Sulfur 1.5
Dimorpholinodisulfide 0.8
Tellurium diethyldithiocarbamate 0.8
Benzothiazyl disulfide 1.5
Zinc dibutyldithiocarbamate 2.5
Total 321.4
A number of hoses are prepared using dies according
to Figures 4 and 5. The dies have constant channel width
(both surfaces of the channel being parallel to the axis).
The mandrel diameter is 1.27 cm. Other features of the dies
are tabulated in Table I.
-20-
1041921
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104~921
~; The composite feed material is extruded using a
8.9 cm vented extruder through dies shown in Table I. The
rate of extrusion is about 3 meters per minute with a head
pressure in excess of 210 Kg/sq. cm. The die temperature
is 100C+ about 10C. All hoses are cured for forty minutes
at 160C. Hose strength is determined by applying steadily
increasing hydraulic pressure to a section of hose until `-
burst occurs. The pressure at which the hose ruptures is
recorded. Fiber orientation is determined by soaking
sections of hose in benzene for 24 hours and measuring the
! amount of swell. The percent swell is calculated by dividing
the original dimension into the change in dimension and
multiplying by 100. Axial orientation influences swell in
the direction of length, circumferential orientation influences
swell in the diameter and radial orientation influences swell
in wall thickness. The amount of swell in any principal
direction or dimension is inverse to the component of fiber
orientation in that direction. (Coran et al, J. Applied
Polymer Science, V15, P. 2471-2485, 1971). The burst strengths
and percent swell values for hoses prepared using the dies of
Table I are shown in Table II.
TABLE II
Pressure @
Die Ai Burst, kg/sq.cm Axial = Radial
A 1 17.0 0 19.8 22.0
B1.8 16.9 3.2 16.5 16.1
C3.4 15.5 8.7 13.8 6.8
D 5 15.2 12.2 13.1 4.8
E 4 - 14.6 11.7 7.8
F4.8 17.5 16.4 10.2 5.6
G7.6 17.9 18.4 8.8 3.4
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~041921
The data show that fiber reinforcement of the hose
in the radial direction and hence the component of fiber
orientation in that direction increases with the increase in
the ratio of channel outlet area to channel inlet area with
a corresponding decrease in the component of fiber orientation
in the axial direction. The component of fiber orientation
in the circumferential direction also increases as the ratio
of outlet area to inlet area increases but is always less than
the radial component.
Die A is a die having an unobstructed straight channel.
The swell data show that essentially all of the fibers are
oriented in the axial direction since there is zero swell in
that direction. Dies B, C and D are of the same dimensions
except they have weirs of different heights protruding from the
mandrel which difference in weir height results in different
outlet area to inlet area ratios. The swell data for a ho3e
produced with Die B having an area expansion of 1.8:1 shows
(compared to a hose produced with Die A) a reduction in the
component of fiber orientation in the axial direction since
the hose swells 3.2 percent in that direction. The swell
data further indicates since the percent swell in the radial
direction is less than the percent swell in the circumferential
direction that the component of fiber orientation in the
radial direction exceeds the component of fiber orientation
in the circumferential direction. In a hose produced with
Die C having an area expansion of 3.4:1, the swell data
indicates that the component of fiber orientation in the radial
direction exceeds the components of fiber orientation in both
the axial and circumferential directions. The swell data of
-23-
104~92~
a hose produced with Die D having an area expansion of 5:1
shows that the fibers are highly oriented toward the radial
direction. The data confirm that the majority of fibers are
oriented toward the radial direction since the reciprocal of
percent swell in the radial direction (1 . 4.8 = 0.208) is
greater than the sum of the reciprocals of the percent swell
in the axial and circumferential directions (1 - 12.2 = 0.082)
+ (1 . 13.1 = 0.076) = 0.158. The swell data for a hose
produced with Die E having an area expansion of 4:1 indicates
that changes in both the fiber loading of the composite and
the angle of the walls of the weir do not significantly
influence the degree of fiber orientation since the component
of fiber orientation in the radial direction still exceeds
either of the components of fiber orientation in the other
directions. Dies F and G have weirs of different heights
protruding from the outer die member. The data indicate that
in hoses produced with this die configuration the component
of fiber orientation in the circumferential direction is
greater than obtained in hoses produced with dies having
weirs on the mandrel at egual area expansion but that the
componer.t of fiber orientation in the radial direction still
exceeds the components of fiber orientation in either of
the other directions.
The preparation of hoses exhibiting improved burst
strength are demonstrated in Tables III and IV. Composite
is extruded and cured in a manner similar to the hoses of Tables
I and II except dies with constrictions located near the channel
outlet are used to constrict the extrudate immediately upstream
-24-
1041921
from the channel outlet. The meaning of the symbols for the
channel dimensions are as follows: Doo is the diameter of the
outer die member at the channel outlet; Dmo is the diameter
of the mandrel at the channel outlet; Dic is the diameter of the
mandrel between the channel inlet and the constriction at the
outlet; Lio is the length of the channel from the inlet to
the outlet; Lco is the length of the constriction located at
the outlet. Die H has about 20% constriction at the outlet
whereas Die I is a control having no constriction at the outlet;
in the table the dimension Dic is therefore given being the
same as Dmo because there is no constriction. The constriction
should not be confused with an upstream weir when present. The
ratio of the channel area of Die H preceding the constriction
and the channel inlet is about 3.4:1. Dies J and K each have
about a 10~ constriction at the outlet. Die K is a hybrid of
the dies of Figures 4 and 5 since it has two weirs opposite each
- other at the inlet, i.e., the outer die member of Die K corres-
ponds to an outer die member of Figure 4 and the mandrel of
Die K corresponds to a mandrel of Figure 5. ~ constriction on
the mandrel at the outlet of Die K provides the indicated
reduction in area. The ratio of the channel area of Die J
preceding the constriction and the channel inlet area is about
4.8:1 and the ratio of the channel area of Die R preceding the
constriction and the channel inlet area is about 8.4:1. The
dimensions of the dies are shown in Table III.
-25-
.
o o ~ ~`
O ~
~ ~' o o ~ ~ 1a419ZI
o o ~ o
o .,,
~o
~1~1
. I
a~
r
CD ~ ~ c~
u~
.,11 o o ~ ~D 3
~ 3~ o ~ ~ ~ o
o~ ~~ 3 ~ ~
- .~ ~ ~ ~ ~ ~,
~ 81 ~ o u~ u~ ~ .
,, ~ ~ ~ ~
Ha~ ~ ~ ~1 ~1
H~ 1 1 D ~ u~ ul H
~.C ~ ~J
~ I
E~ ~ m
l ~ o a~
~ ,, ,, o o
~n
81 ~
1 o o O O O
~1 o o u) In o I ~ ~ er ,~
~1 ~ ~ ~ ~o
Z
u~ u7 ~ ~r In
rl
C~ ~ H 1
~1 ~
1041~1
Properties of hoses prepared using the dies of Table
III are shown in Table IV. Comparison of the pressure at
burst of hoses prepared using Dies H and I demonstrate that
the hoses prepared with Die H exhibit improved burst strength.
Similarly, a comparison between a hose prepared with Die K and
a hose prepared with Die G (no constriction) of Table II
indicates that Die K with constriction at the outlet exhibits
about 10~ higher burst strength. The overall area expansion
of Die J falls between that of Dies C and D of Table II.
However, the burst strength of hose produced by Die J exceeds
that of hoses from either Die C or Die D by over 30%.
The invention includes multilayer hoses in which two
or more layers of material are joined to form a single hose
having different fiber orientation in each layer. For example,
via a cross-head extruder, two hoses are extruded in which
one hose envelops the other to form a single bi-layer hose.
By selecting a die of the proper geometry for each layer a
- hose having radial orientation in the inner layer and axial
orientation in the outer layer or vice versa may be prepared.
A bi-layer hose in which ~he inside layer is reinforced with
fibers predominately oriented in the circumferential direction
and the outer layer is reinforced with fibers predominately
oriented in either the radial or the axial directions is
especially recommended for high performance applications. By
operation of two cross-head extruders in tandem tri-layer hoses
may be prepared in which predominate fiber orientation may be
different in each layer. Alternately, layered hoses may be
prepared in a co-extrusion process using a single head
fed by multiple extruders.
-27-
..
. lO~ll9Zl
Although the invention has been illustrated by
typical examples, it is not limited thereto. Changes and
modifications of the examples of the invention herein chosen
for purpose of disclosure can be made which do not constitute
departure from the spirit and scope of the invention.
-28-
