U.S. patent application number 15/555999 was filed with the patent office on 2018-02-08 for pultruded articles and methods for making same.
The applicant listed for this patent is Zephyros, Inc.. Invention is credited to Craig Chmielewski, Milko Dimovski, Nick Holstine, Liwen Li, Alex Mangiapane, Henry E. Richardson, Jeffrey T. Shantz, Joseph Thomas.
Application Number | 20180036970 15/555999 |
Document ID | / |
Family ID | 55640881 |
Filed Date | 2018-02-08 |
United States Patent
Application |
20180036970 |
Kind Code |
A1 |
Chmielewski; Craig ; et
al. |
February 8, 2018 |
PULTRUDED ARTICLES AND METHODS FOR MAKING SAME
Abstract
A structural reinforcement for an article including a carrier
(10) that includes: (i) a mass of polymeric material (12) having an
outer surface; and (ii) at least one fibrous composite insert (14)
or overlay (980) having an outer surface and including at least one
elongated fiber arrangement (e.g., having a plurality of ordered
fibers). The fibrous insert (14) or overlay (960) is envisioned to
adjoin the mass of the polymeric material in a predetermined
location for carrying a predetermined load that is subjected upon
the predetermined location (thereby effectively providing localized
reinforcement to that predetermined location). The fibrous insert
(14) or overlay (960) and the mass of polymeric material (12) are
of compatible materials, structures or both, for allowing the
fibrous insert or overlay to be at least partially joined to the
mass of the polymeric material. Disposed upon at least a portion of
the carrier (10) may be a mass of activatable material (128). The
fibrous insert (14) or overlay (960) may include a polymeric matrix
that includes a thermoplastic epoxy.
Inventors: |
Chmielewski; Craig; (Shelby
Township, MI) ; Richardson; Henry E.; (Washington,
MI) ; Shantz; Jeffrey T.; (Metamora, MI) ;
Holstine; Nick; (Royal Oak, MI) ; Dimovski;
Milko; (Clinton Township, MI) ; Mangiapane; Alex;
(Macomb Township, MI) ; Li; Liwen; (Troy, MI)
; Thomas; Joseph; (Lapeer, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Zephyros, Inc. |
Romeo |
MI |
US |
|
|
Family ID: |
55640881 |
Appl. No.: |
15/555999 |
Filed: |
March 10, 2016 |
PCT Filed: |
March 10, 2016 |
PCT NO: |
PCT/US2016/021725 |
371 Date: |
September 6, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62130908 |
Mar 10, 2015 |
|
|
|
62200380 |
Aug 3, 2015 |
|
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62296378 |
Feb 17, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29K 2063/00 20130101;
B29C 70/521 20130101; B29C 70/52 20130101; B29K 2101/12 20130101;
B29C 70/86 20130101 |
International
Class: |
B29C 70/52 20060101
B29C070/52 |
Claims
1. A pultruded structure comprising: an elongated tubular structure
having a first end and a second end; at least one attachment device
adapted for attaching the tubular structure to a vehicle; one or
more strips of an activatable polymeric material on an outer
surface, the activatable material adapted for damping of vibration,
for resisting flutter, or for bonding to an adjoining structure;
wherein the elongated tubular structure has a longitudinal axis and
also has at least one reinforcement portion that includes a
continuous glass fiber reinforcement embedded in a polyurethane
matrix and has a plurality of glass fibers aligned generally
parallel with the longitudinal axis.
2-5. (canceled)
6. The structure of claim 1, wherein the continuous glass fibers
are preloaded in the at least one reinforcement portion.
7. The structure of claim 1, wherein the elongated tubular
structure has a constant profile along the longitudinal axis.
8. The structure of claim 1, wherein from about 40 to about 80% by
weight of the beam is fibers.
9-11. (canceled)
12. A method of making the structure of claim 1, wherein the
elongated tubular structure is pultruded.
13. A method of making a composite article, comprising the steps
of: i. pultruding a first polymeric composite structure having a
plurality of glass fibers embedded in a polyurethane matrix; ii.
fabricating a second polymeric composite structure having a
plurality of fibers embedded in a polymeric matrix; and iii.
securing the second polymeric composite structure with the first
polymeric composite structure to define a composite article that
includes each of the first polymeric composite structure and the
second polymeric composite structure.
14. The method of claim 13, wherein the first polymeric composite
structure includes a plurality of continuous glass fibers embedded
in a polymeric matrix in a concentration of about 40% to about 80%
by weight of the polyurethane composite structure.
15-16. (canceled)
17. The method of claim 13, wherein the second polymeric composite
structure includes a plurality of glass fibers embedded in a
polymeric matrix in a concentration of about 20% to about 80% by
weight of the second polymeric composite structure.
18. The method of claim 13, wherein the second polymeric composite
structure includes a plurality of fibers embedded in a polymeric
matrix and wherein the polymeric matrix includes an epoxy, Nylon, a
polyester, a polyether, or combinations thereof.
19. (canceled)
20. The method of claim 13, wherein the step of fabricating the
second polymeric composite structure includes a step of extruding
the second polymeric composite, injection molding the second
polymeric composite, pultruding the second polymeric composite,
thermoforming the second polymeric composite, compression molding
the second polymeric composite, or any combination thereof.
21. The method of claim 13, wherein the step of securing the first
polymeric composite and the second polymeric composite includes a
step of adhering the first polymeric composite with the second
polymeric composite, mechanically connecting the first polymeric
composite with the second polymeric composite, a step of welding
the first polymeric composite with the second polymeric composite
or a combination thereof.
22. The method of claim 20, wherein the step of securing the first
polymeric composite and the second polymeric composite includes a
step of inserting a coupling device between the first polymeric
composite and the second polymeric composite, and a step of
adhering the first polymeric composite with the second polymeric
composite via the coupling, mechanically connecting the first
polymeric composite with the second polymeric composite via the
coupling, welding the first polymeric composite with the second
polymeric composite via the coupling, or any combination
thereof.
23. The method of claim 13, wherein the shape of the first
polymeric composite and the shape of the second polymeric composite
are complementary so that they are in generally mating relationship
with each other.
24. The method of claim 21, wherein the first polymeric composite
and the second polymeric composite are similarly sized and/or
shaped.
25. The method of claim 21, wherein the first polymeric composite
and the second polymeric composite are differently sized and/or
shaped.
26. The method of claim 13, wherein one or more of the first
polymeric composite and the second polymeric composite comprise
fibers formed in a mat.
27. A method of making a pultruded article, comprising the steps
of: a) pulling a plurality of continuous fibers through a die for
defining a continuous profile that has at least two portions that
are not coplanar and have differing thickness relative to each
other; b) contacting the plurality of continuous fibers with one or
more polymeric materials; c) applying a sufficient amount of energy
to form a pultruded article having a polyurethane-based polymeric
matrix in contact with the continuous fibers and embedding the
continuous fibers therein.
28. The method of claim 27, wherein the die is about 0.2 to about 1
meters in length.
29. The method of claim 28, wherein the rate of the pultruding is
at least about 0.5 meters per minute.
30. The method of claim 28, wherein the die includes an opening
therein into which the polymeric materials are introduced so that
the step of contacting occurs within the die.
31-74. (canceled)
Description
TECHNICAL FIELD
[0001] The present invention relates generally to composite
materials, particularly to composites having a thermoplastic epoxy
polymer phase, which can be employed in a number of applications,
such as in structural reinforcements and/or baffles for use in
transportation vehicles.
BACKGROUND
[0002] There is an ongoing effort in many industries to lighten the
weight of articles. In many instances, this is achieved by the
selection of materials that have a lower density, thinner section
thicknesses or both, as compared with prior materials or
structures. As a result, there is a potential for the weakening of
structures, and the consequent need for stiffening or other
structural reinforcement.
[0003] In the field of automotive vehicle manufacturing it is
common to employ structural reinforcements within cavities of the
vehicle body structure. For instance, it has become common to
employ within a cavity of the vehicle body structure a relatively
rigid molded polymeric carrier that carries an activatable material
on one or more of its outer surfaces. For certain activatable
materials, upon being activated (e.g., by the heat from a coating
bake oven), the activatable material can expand and bond to a
surface defining the cavity.
[0004] In order to selectively control the properties of the
article reinforcement structure, it has been taught to use hybrid
reinforcement structures that include a combination of multiple
materials for the carrier. See, e.g., United States U.S. Pat. No.
8,430,448, hereby expressly incorporated by reference for all
purposes. See also, Patent Cooperation Treaty (PCT) Application No.
WO 2010/054194, hereby expressly incorporated by reference for all
purposes.
[0005] In the automotive vehicle industry, the use of computer
modeling (e.g., finite element analysis) has been employed for
simulating a vehicle crash, and for modeling how a particular
section of a vehicle will respond to the crash. Such modeling can
be utilized to determine appropriate locations for the placement of
reinforcing structures.
[0006] Notwithstanding the above efforts there remains a need for
alternative carrier structures. For example, there remains a need
for alternative carrier structures that employ a combination of
different materials that, even though they are dissimilar, are
still generally compatible (e.g., chemically and/or physically
compatible) with each other so that they can be joined together
without the need for an adhesive, a mechanical fastener, or other
means for physically joining two or more different materials. There
also remains an ongoing need for alternative carrier structures
that employ a combination of different materials that each contains
a substantial polymeric portion (e.g., a non-metallic portion) so
that weight savings can be attained. There is also a need for
polymeric materials that can be combined to increase the overall
modulus and flexural strength of a reinforcement, such that it
exceeds that of any of the materials on their own. There also
remains an ongoing need for alternative carrier structures that
employ a combination of different materials that join together at
an interface region that is generally continuous with the portions
of the carrier defined by the different respective materials. There
also remains an ongoing need for an alternative carrier that can
employ one or more localized reinforcement regions by use of a
particular material within the carrier, and which may be achieved
in the absence of a need for a structural feature (e.g., a rib) for
imparting additional strength to the localized reinforcement.
[0007] Examples of composite structures are illustrated in PCT
Publication No. WO2007/008569, U.S. Published Patent Application
Nos. 2011/0039470 and 2012/0251663, and U.S. Pat. No. 7,581,932 all
incorporated by reference for all purposes. See also, U.S. Pat.
Nos. 6,855,652, 7,125,461 and 7,318,873, and U.S. Published Patent
Application Nos. 2003/0039792, 2010/0289242, 2011/0278802, and
2009/0202294, incorporated by reference for all purposes.
[0008] The present application also is related to and incorporates
by reference for all purposes Great Britain Patent Application No.
1318595.4, filed Oct. 21, 2013.
[0009] Further to the above, thermoplastic polymers having at least
one epoxide group have been described in U.S. Pat. Nos. 5,115,075;
4,438,254; 6,011,111; and PCT Publication No. WO98/14498 (see e.g.,
pages 3-8) along with illustrative synthesis conditions, all
incorporated by reference herein (see also U.S. Pat. Nos. 3,317,471
and 4,647,648, also incorporated by reference herein). Examples of
such materials also can be found, without limitation at paragraphs
16-25 of Published U.S. Patent Application No. 2007/0270515
(Chmielewski et al), incorporated by reference for all
purposes.
[0010] The use of such thermoplastic polymers in a composite
material has been disclosed in PCT Publication No. WO/2006/010823
(addressing in situ reaction of an epoxy and an amine after
impregnation), incorporated by reference herein. Notwithstanding
the above, there remains a need for alternative composite
materials. For example, there remains a need for composite
materials that are suitable for use in a carrier for a baffle
and/or structural reinforcement for a transportation vehicle of a
type exemplified in the above discussed patent publications. For
example, in instances where it may be desirable to locally alter or
improve a property of a carrier material there remains a need for
alternative materials suitable for such purpose. There also remains
a need for materials that allow for recycling, reclamation and/or
re-use beyond the useful life of the material in its intended
application. See also, U.S. Patent Application No. 2009/0298974
(incorporated by reference).
SUMMARY OF THE INVENTION
[0011] One or more of the above needs are met by the present
teachings which contemplate improved structures and methods that
can be employed advantageously for sealing, baffling and/or
structurally reinforcing various articles, and particularly for
structurally reinforcing transportation vehicles, such as
automotive vehicles. The materials of the present teachings also
find application in a number of other applications as will be
gleaned from the following discussion. That is, the present
teachings relate generally to composite materials, and more
particularly to fibrous composite materials that employ a
distributed phase (e.g., a fibrous phase) and a thermoplastic
polymeric material (e.g., a reformable resin, a thermoplastic
reaction product) having at least one epoxide group. The material
offers the benefit of mechanical properties typically achieved
through the use of thermoset polymeric materials (e.g., thermoset
epoxy material) as some or all of a matrix phase of a composite.
However, the material has a number of physical attributes that make
it suitable for handling, processing and/or post-useful life
reclamation, recycling, and/or re-use.
[0012] The teachings herein relate to a composite article. The
composite article may be in a form suitable for use as part of a
baffle and/or structural reinforcement for a transportation
vehicle. The composite article may include at least two phases. For
example, it may include a distributed phase and a matrix phase
within which the distributed phase is distributed. The distributed
phase in the composite article may include a plurality of segmented
forms selected from fibers, platelets, flakes, whiskers, or any
combination thereof. The polymeric matrix in the composite article
in which the distributed phase is distributed may include at least
about 25% by weight of the polymeric matrix of a substantially
thermoplastic polymer having at least one epoxide functional
group.
[0013] The teachings herein also relate to a method for making a
composite article. In general, a method in accordance with the
present teachings may employ a step of contacting a plurality of
segmented forms provided for defining a distributed phase with a
thermoplastic epoxy resin, such as an hydroxy-phenoxyether polymer
(e.g., a generally thermoplastic reaction product of an epoxy and
an amine) that is in a softened state (e.g., in a liquefied molten
state). For instance, a method in accordance with the present
teachings may employ forming a composite material by extrusion,
injection molding, or a combination of both. Thus, it is envisioned
for the teachings herein that there is method of making the
composite article that includes contacting an epoxy/amine reaction
product material (e.g., a material that is a reaction product of a
diepoxide and a primary amine, such as monoethanolamine, or the
reaction product of a diepoxide resin (e.g., BPA), a mono primary
amine, a di-secondary amine, a dimer captan and/or a di-carboxylic
acid); during a step of extrusion, injection molding, pultrusion or
any combination thereof. The contacting may be only after the
reaction has completed between the epoxy and the amine (e.g., only
after the reaction of epoxy and amine). Thus it is possible that
the method herein will involve no chemical reaction between any
epoxy and amine reactants that occurs with an injection molding
machine and/or an extruder. That is, the method may include
advancing a thermoplastic polymer having at least one epoxide
functional group reaction product along a rotating feed screw
within a barrel of a polymeric material shaping apparatus.
[0014] The teachings herein provide for a pultruded part
comprising: an elongated carrier structure having a first end and a
second end; an adhesive disposed along a portion of the carrier
structure; at least one connector device adapted for attaching the
carrier structure to a vehicle; at least one securing device molded
onto the carrier structure; and at least one fastening device
molded onto the securing device. The teachings herein also provide
for a method of making such a device on an in-line pultrusion
system comprising: pulling a plurality of continuous fibers through
a die for defining a continuous profile; contacting the plurality
of continuous fibers with one or more reactants for forming a
continuously forming a polymer for a generally continuous polymeric
matrix of the a resulting pultruded article; molding one or more
securing devices and fastening devices onto the continuous profile;
and extruding a secondary material onto the continuous profile.
[0015] Composites that are made in accordance with the present
teachings can be employed as some or all of a consolidated fibrous
composite material insert and/or overlay. The fibrous material
composites herein may include a distributed phase and a matrix
phase, wherein the distributed phase includes at least one
elongated fiber arrangement in order to define a consolidated
fibrous insert for a carrier. The carrier, the consolidated fibrous
insert and/or overlay, or each may have an outer surface. The
composite, the insert and/or overlay, or each may include at least
one elongated fiber arrangement having a plurality of ordered
fibers (e.g., organic and/or inorganic fibers) that may be
distributed in a predetermined manner in a polymeric material
matrix. The polymeric material matrix may include a thermoplastic
epoxy resin material as described generally, or as described in any
of the particular illustrative materials herein. The composites of
the present teachings may be employed alone for defining a carrier
for the baffles and/or structural reinforcements of the present
teachings. The composites of the present teachings may be employed
as a fibrous insert adjoining (e.g., in a manner to achieve as a
continuous outer surface) a mass of the polymeric material (e.g.,
one that includes a polyamide such as Nylon, Nylon 6, Nylon 66,
poly-butylene terephthalate, or any combination thereof, optionally
being glass filled) for defining such a carrier. The location,
size, shape or any combination thereof, of the fibrous insert may
be selected to help improve one or more properties of the carrier
in the region where the insert is located. The carrier may carry an
activatable material over at least a portion of the outer surface
of the carrier. For example, the activatable material may be
activated by heat (e.g., heat from a paint bake oven, such as an
automotive paint bake oven) to foam, expand, adhere and/or
cure.
[0016] The teachings herein further envision A method comprising
pulling a mass of elongated fibers through a die, contacting the
mass of elongated fibers with at least two ingredients, with a
reaction product of at least two ingredients, or a combination
thereof, that infiltrate the mass of elongated fibers and react in
situ to form a pultrusion having a thermoplastic polymeric material
matrix having a glass transition temperature of less than about
200.degree. C., and assembling the pultrusion with a separate
component in the absence of a need for any added adhesive, weld or
mechanical fastener.
[0017] The surface tension of the mass of elongated fibers may be
from about 100 mN/m to about 500 mN/m. The at least two ingredients
may include a stoichiometric excess of at least one of the
ingredients for making that ingredient available for a subsequent
chemical reaction. Another of the at least two ingredients may be
provided on a separate component in an amount for reacting with the
excess of the first ingredient for forming a chemical bond having a
chemistry approximating that of the thermoplastic polymer of the
matrix. The thermoplastic polymeric material may include a filler
material for increasing the viscosity of the thermoplastic
polymeric material. The method may take place under at least a
first and second temperature condition, so that the first
temperature condition allows a reaction to occur between the at
least two ingredients and the second temperature condition allows
for infiltration of the at least two ingredients into the mass of
elongated fibers. The elongated fibers may be randomly oriented
fibers. The elongated fibers may be substantially free of any
continuous parallel fibers. The separate component may be
electrically conductive.
[0018] The teachings herein also provide for a method comprising:
providing a composite material having a thermoplastic matrix having
a glass transition temperature of less than about 200.degree. C.
and at least one reinforcing material dispersed in the
thermoplastic matrix; optionally contacting the composite material
with at least one electrically conducive material so that the
electrically conductive material is dispersed randomly or
selectively on or within the composite material; contacting a
component to be joined with the composite material; heating the
component, the composite material or both to a temperature at which
a polymer of the thermoplastic matrix material softens and forms a
bond with the component to form an assembly; and cooling the
assembly. Upon cooling, the bond remains intact over a temperature
range of from about 40.degree. F. to about 180.degree. F.
[0019] Also envisioned is a method comprising providing a first
component and a second component, introducing a thermoplastic epoxy
polymer onto either or both of the first or second component and
joining the first component with the second component by way of the
thermoplastic epoxy polymer. The first and second component may
still be separable.
[0020] One or both of first and second component may be a metal.
The first and second components may comprise dissimilar materials.
One or both of the first or second components may be composites.
One or both of the first or second components may comprise a carbon
fiber composite. The first and second components may be joined in
the absence of heat. The thermoplastic epoxy polymer may be the
result of a reaction product of a first ingredient carried on the
first component and a second ingredient carried on the second
component. One or both of the first and second component may have
an electrically conductive filler. The first and second component
may be joined by induction heating or welding.
[0021] The teachings herein also provide for a method comprising
mixing at least two reactants with a plurality of reinforcement
elements, reacting the reactants to form a thermoplastic epoxy
reaction product having the reinforcing elements dispersed therein,
and forming pellets that include the thermoplastic reaction product
having the reinforcing elements dispersed therein.
[0022] The reinforcing elements may be glass fibers dispersed in an
amount of from about 25% by weight to about 80% by weight, from
about 30% to about 60% by weight, or even from about 40%-50% by
weight. The reactants may be reacted in an extrusion or pultrusion
die. The reinforcing elements may have a weight average length of
about from about 0.25 to about 3 mils. The method may include
extruding or pultruding the pellets. The method may include cooling
the material during the extruding or pultruding at the end of a
die. The temperature in the die may not exceed 415.degree. F. The
method may include contacting the reinforcement elements with an
agent for enhancing wetting characteristics and/or rheology of the
reaction product. The reinforcing elements may be arranged randomly
within the pellets. The method may include injection molding or
thermoforming the pellets.
[0023] The teachings herein also contemplate a method comprising
forming a structure having a continuous profile along its length
and having a first shape from a reinforced thermoplastic material
formed as a reaction product of an epoxy and an amine, and applying
heat and pressure to deform the profile to a second shape. The
profile is reinforced by a plurality of fibers arranged in a random
orientation which facilitates forming of second shape.
[0024] The method may include heating the profile to join to a
secondary component. The method may include pultruding the profile.
The profile may include a conductive component. The plurality of
fibers may mitigate the difference in thermal expansion between the
profile and any secondary component attached thereto. The profile
may be installed in a vehicle after the vehicle has completed a
paint bake oven treatment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is a side sectional view of a portion of one
illustrative part in accordance with the present teachings. FIG. 2
is a side sectional view of a portion of another illustrative part
in accordance with the present teachings.
[0026] FIG. 3 is a side sectional view of a portion of yet another
illustrative part in accordance with the present teachings.
[0027] FIG. 4a is a top perspective view of one illustrative
carrier in accordance with the present teachings.
[0028] FIG. 4b is a bottom perspective view of the carrier of FIG.
4a.
[0029] FIG. 5 is an exploded perspective view of one illustrative
lay-up of a fibrous insert of the present teachings,
[0030] FIG. 6a is a perspective view of an illustrative fibrous
insert in accordance with the present teachings.
[0031] FIG. 6b is a perspective view of an illustrative part
incorporating the fibrous insert of FIG. 6a.
[0032] FIG. 7a is a perspective view of another illustrative
fibrous insert in accordance with the present teachings.
[0033] FIG. 7b is a perspective view of an illustrative part
incorporating the fibrous insert of FIG. 6a.
[0034] FIG. 8 is a schematic illustrating the formation of an
illustrative part in accordance with the present teachings.
[0035] FIG. 9 is an illustrative example of a profile of an
elongated article (e.g., a carrier) having an illustrative overlay
in accordance with the present teachings.
[0036] FIG. 10 is a schematic of a system for making an article in
accordance with the present teachings.
[0037] FIG. 11a is a perspective view of an illustrative part in
accordance with the present teachings.
[0038] FIG. 11b is an exploded perspective view of the part of FIG.
11a.
[0039] FIG. 12a is a perspective view of an illustrative part in
accordance with the present teachings.
[0040] FIG. 12b is an exploded perspective view of the part of FIG.
12a.
[0041] FIG. 13a is a perspective view of an illustrative part in
accordance with the present teachings.
[0042] FIG. 13b is an exploded perspective view of the part of FIG.
13a.
DETAILED DESCRIPTION
[0043] The present teachings meet one or more of the above needs by
the improved devices and methods described herein. The explanations
and illustrations presented herein are intended to acquaint others
skilled in the art with the teachings, its principles, and its
practical application. Those skilled in the art may adapt and apply
the teachings in its numerous forms, as may be best suited to the
requirements of a particular use. Accordingly, the specific
embodiments of the present teachings as set forth are not intended
as being exhaustive or limiting of the teachings. The scope of the
teachings should, therefore, be determined not with reference to
the above description, but should instead be determined with
reference to the appended claims along with the full scope of
equivalents to which such claims are entitled. The disclosures of
all articles and references, including patent applications and
publications, are incorporated by reference for all purposes. Other
combinations are also possible as will be gleaned from the
following claims, which are also hereby incorporated by reference
into this written description.
[0044] The present application is related to the teachings of PCT
Application No. PCT/U.S.14/070853, filed Dec. 17, 2014; U.S.
Provisional Application Ser. No. 61/916,884, filed on Dec. 17,
2013; and PCT Application No. PCT/U.S.14/61531, filed Oct. 21,
2014, the contents of these applications being hereby incorporated
by reference for all purposes.
[0045] This application claims the benefit of the filing dates of
U.S. Provisional Application Ser. No. 62/130,908, filed Mar. 10,
2015; U.S. Provisional Application Ser. No. 62/200,380, filed Aug.
3, 2015; and U.S. Provisional Application Ser. No. 62/296,378,
filed Feb. 17, 2016, all of which are incorporated by reference for
all purposes.
[0046] As noted, the present teachings relate generally to
composite materials. In this regard, there are various composites
to which the teachings pertain. The composites share the common
characteristic that they each employ a fibrous composite material
that has a distributed phase (e.g., a fibrous phase) and a
thermoplastic polymeric material having at least one epoxide group.
The thermoplastic polymeric material haying at least one epoxide
group may define a matrix material in which the distributed phase
resides. The thermoplastic polymeric material having at least one
epoxide group may be hydroxy-phenoxyether polymer, such as a
polyetheramine thermoplastic material as described herein. For
example, such thermoplastic polymeric material having at least one
epoxide group may be a product (e.g., a thermoplastic condensation
reaction product) of a reaction of a mono-functional or
di-functional species (i.e., respectively, a species having one or
two reactive groups, such as an amide containing species), with an
epoxide-containing moiety, such as a diepoxide a compound having
two epoxide functionalities), reacted under conditions for causing
the hydroxyl moieties to react with the epoxy moieties to form a
generally linear backbone polymer chain with ether linkages.
Examples of the composite structures disclosed herein can be found
in U.S. Provisional Application Nos. 62/130,832, filed Mar. 10,
2015; U.S. Provisional Application No. 62/183,380, filed Jun. 23,
2015; U.S. Provisional Application No. 62/294,160, filed Feb. 11,
2016; U.S. Provisional Application No. 62/296,374, Feb. 17, 2016,
all incorporated by reference herein for ail purposes. The
reformable thermoplastic polymeric material may be formed as a
sheet or film and may be substantially free of any distributed
(e.g., fibrous) phase, in one non-limiting example, the
thermoplastic polymeric material may be formed as a film which may
be in contact with a fibrous layer. The reformable thermoplastic
polymeric material may be formed as a yarn.
[0047] The teachings contemplate the possibility that a structure
may be fabricated using a thermoplastic material in accordance with
the teachings generally herein. In particular, the structure may be
made from a thermoplastic material in accordance with the present
teachings that is reinforced with a reinforcement phase. The
reinforcement phase may be distributed in a matrix of the
thermoplastic material (e.g., a polyamide as described and/or a
reformable resin material as described). For example, the
reinforcement phase may be at least a majority (by volume) of the
total material. It may be greater than about 60% by volume or
greater than about 70% by volume. It may be below about 90% by
volume, below about 80% by volume, or below about 70% by volume.
Any reinforcement phase may be distributed randomly, generally
uniformly, and/or in one or more predetermined locations of an
article.
[0048] The fibrous composite materials may be employed as a portion
of another composite material. For example it may be employed as an
insert (e.g., a fibrous insert) and/or an overlay of a composite
that includes one or more other materials.
[0049] The teachings herein relate to a composite article. The
composite article may be in a form suitable for use as part of a
baffle and/or structural reinforcement for a transportation
vehicle. The composite article may be in a form suitable for use as
a panel structure. The composite article may be in a form suitable
for use as a building construction material, as a furniture
material, as a sporting good material (e.g., for skis, snowboards,
bicycles, bats, tennis rackets or the like) or as protective gear
material (e.g., for police shields, armored vehicle panels, or the
like). The fibrous composite materials of any composite article
herein may include a single phase or may include at least two
phases. The fibrous composite materials of any composite article
herein may include at least two phases. For example, it may include
a distributed phase and a matrix phase within which the distributed
phase is distributed. The distributed phase in the composite
article may include a plurality of elongated (e.g., in a ratio of
at least 2:1 as between a major and minor dimension of the form)
segmented forms selected from fibers, platelets, flakes, whiskers,
or any combination thereof. For fibers employed herein, the fibers
may be employed in the distributed phase is in the form of a random
distribution, a weave, a non-woven mat, a plurality of generally
axially aligned fibers (e.g., a tow), a plurality of axially
intertwined fibers (e.g., a yarn) or any combination thereof. A
plurality of individual fibers may thus be in a generally ordered
relationship (e.g., according to a predetermined pattern) relative
to each other.
[0050] The composition of material of the distributed phase may be
the same as or different from the composition of the polymeric
matrix. For example, it is possible that material of the
distributed phase may be a thermoplastic polymer having at least
one epoxide functional group as described generally or specifically
within the teachings herein. The polymeric matrix material may also
be or include a thermoplastic polymer having at least one epoxide
functional group as described generally or specifically within the
teachings herein.
[0051] The ratio by weight of polymeric matrix to the distributed
phase may be range from about 1:10 to about 100:1 (e.g., it may
range from about 1:5 to about 10:1, about 1:3 to about 5:1, about
1:2 to about 2:1).
[0052] The polymeric matrix in the fibrous composite material in
which the distributed phase is distributed may include at least
about 25%, 33%, 50%, 67%, 85% by weight of the polymeric matrix of
a substantially thermoplastic polymer having at least one epoxide
functional group. The polymeric matrix of the substantially
thermoplastic polymer having at least one epoxide functional group
may have less than about 8%, 3%, or even 1% by weight of a
polymeric ingredient other than the thermoplastic polymer having at
least one epoxide functional group (e.g., the polymeric matrix
consists essentially of the thermoplastic polymer having at least
one epoxide functional group).
[0053] The balance of the material of the fibrous composite
material may be the distributed phase. The balance of the material
of the composite material may include the distributed phase in
addition to another phase and/or material.
[0054] The distributed phase may include one, two or more different
materials. For instance it may include a single form (e.g., a
single elongated segment form), or a plurality of different forms
(e.g., a plurality of elongated segment forms). At least about 25%,
33%, 60%, 67%, 85% by weight of the distributed phase may be
fibers. The distributed phase may have less than about 5%, 3%, or
even 1% by weight of a form other than a fiber. The matrix material
may form the end product alone and be substantially free of any
distributed phase.
[0055] The material of the distributed phase may include an organic
material, an inorganic material or a combination of each. The
material may be a naturally occurring material (e.g., a rubber, a
cellulose, sisal, jute, hemp, or some other naturally occurring
material). It may be a synthetic material (e.g., a polymer (which
may be a homopolymer, a copolymer, a terpolymer, a blend, or any
combination thereof)). It may be a carbon derived material (e.g.,
carbon fiber, graphite, graphene, or otherwise). The distributed
phase may thus include fibers selected from (organic or inorganic)
mineral fibers (e.g., glass fibers, such as E-glass fibers,
S-class, B-glass or otherwise), polymeric fibers (e.g., an aramid
fiber, a cellulose fiber, or otherwise), carbon fibers, metal
fibers, natural fibers (e.g., derived from an agricultural source),
or any combination thereof. The plurality of elongated fibers may
be oriented generally parallel to each other. They may be braided.
They may be twisted. Collections of fibers may be woven and/or
nonwoven.
[0056] The material of the distributed phase may include a
plurality of fibers having a length of at least about 1 cm, 3 cm or
even 5 cm or longer. Fibers of the distributed phase may have an
average diameter of about 1 to about 50 microns (e.g., about 5 to
about 25 microns). The fibers may have a suitable sizing coating
thereon. The fibers may be present in each layer, or in the fibrous
insert generally, in an amount of at least about 20%, 30%, 40% or
even 50% by weight. The fibers may be present in each layer, or in
the fibrous insert generally, in an amount below about 90%, 80%, or
even about 70%, by weight. By way of example, the fibers may be
present in each layer, or in the fibrous insert, in an amount of
about 50% to about 70 by weight. Fiber contents by weight may be
determined in accordance with ASTM D2584-11.
[0057] Tapes and/or sheets (e.g., films) for use in one or more of
the portions of a fibrous composite material herein may be made by
extrusion, pultrusion or otherwise. In this manner, it may be
possible to achieve ordering of the fibers in the tapes and/or
sheets. The tape and/or sheet may be formed from the thermoplastic
polymer material. The tape and/or sheet may include a fibrous phase
or may alternatively be substantially free of any fibrous phase.
The thermoplastic polymeric material may be formed into fibers
which may then form the tape and/or sheet. A method herein may
include a step of impregnating a fibrous mass with the material of
the polymeric matrix and passing the resulting impregnated material
through a die (e.g., a heated die) or other structure having an
opening so that the fibrous mass is coated with a generally
continuous mass of the material of the polymeric matrix. In this
manner, it is also possible to achieve desired ordering of fibers
relative to each other. The composite materials may be formed by
keyed extrusion, whereby a heat staking process is used to attach a
mechanical fastener, which may located into a channel formed during
the extrusion process. Alternatively, the fastener may be attached
at a location with no channel formation.
[0058] The fibrous composite materials of the present teachings may
include one or more layers (e.g., they may have 2, 3, 4, 6, or 15
or more layers) that are consolidated in the sense that they
include a plurality of individual fibers or other segmented forms
of a distributed phase, which are distributed in a cohesive mass of
the polymeric matrix material (e.g., a matrix that includes a
hydroxy-phenoxyether polymer, such as a polyetheramine
thermoplastic material as described herein). For example, the
polymer may be a product (e.g., a thermoplastic condensation
reaction product) of a reaction of a mono-functional or
di-functional species (i.e., respectively, a species having one or
two reactive groups, such as an amide containing species), with an
epoxide-containing moiety, such as a diepoxide (i.e., a compound
having two epoxide functionalities (a diepoxide resin (e.g., BPA),
a mono primary amine, a di-secondary amine, a dimer captan and/or a
di-carboxylic acid); reacted under conditions for causing the
hydroxyl moieties to react with the epoxy moieties to form a
generally linear backbone polymer chain with ether linkages.
Multiple layers may be consolidated together so that a cohesive
mass, including the multiple layers, is formed. The multiple layers
may be consolidated so as to form a predetermined shape in the form
of a three-dimensional shaped insert. For instance, the fibrous
insert may employ a plurality of layers that include a plurality of
elongated fibers (e.g., having a length of at least 1 cm, 3 cm or
even 5 cm or longer) that are oriented generally parallel or
generally unidirectionally to each other and are distributed in a
generally continuous polymeric matrix (e.g., in a continuous matrix
of the second polymeric material). A shaping operation (e.g.,
thermoforming, molding, passing through a die, rolling, or
otherwise) may be performed.
[0059] The fibers of the distributed phase may be present in an
amount, a distribution, or both for reinforcing the composite
article by the realization of an increase of one or more mechanical
properties selected from ultimate tensile strength, elongation,
flexural modulus, compression modulus, or otherwise, as compared
with the corresponding property of the polymer matrix material
alone.
[0060] The fibrous composite materials of the present teachings may
be such so that the distributed phase is distributed in the
polymeric matrix material in an ordered arrangement, in a
substantiality homogenous arrangement or both. It is possible that
the distributed phase is distributed in the polymeric matrix
material in a random arrangement. The individual fibers may be
distributed in a predetermined ordered arrangement within the
matrix of polymeric material so that at least a portion of the
fibers are ordered in their arrangement (e.g., in a generally
ordered relationship relative to each other, such as generally
parallel or unidirectional or otherwise generally axially aligned),
and thus are not randomly distributed in the polymeric matrix
material.
[0061] Turning in further detail to the materials that may be
employed in the present teachings, a variety of materials having
thermoplastic thermal characteristics may be suitable. In general,
the teachings herein extend also to certain thermoplastic polymers
(e.g., polyamides, such as Nylon 6, or Ultratape from BASF). The
materials may be employed alone, as a matrix material of a
multi-phasic material (e.g., along with a reinforcement phase, such
as carbon fibers, glass fibers, polymeric fibers, natural fibers,
or some other segmented form, as described elsewhere herein). It
may be employed as a layer of a laminate, as core or a sheath of a
core/sheath elongated material, as a core or a shell of a
core/shell material, or otherwise.
[0062] The materials may be thermoplastic in nature so that it is
capable of flowing when subjected to a temperature above its glass
transition temperature (T.sub.g), and/or a temperature at which it
melts. One particular preferred material for use herein is a
reformable resin material, and particularly a materiel that broadly
contemplates particular ingredients, reactions and reaction
products associated with polymers having an epoxide functionality
for imparting at least one mechanical characteristic consistent
with epoxy thermoset materials, and at least one processing (e.g.,
elevated temperature processing) characteristic typically
associated with thermoplastic materials (e.g., a glass transition
temperature); and still more particularly, the present teachings
relate to additive manufacturing with a thermoplastic polyether
material, such as a thermoplastic epoxy polymer material.
[0063] The materials useful in the present teachings (e.g., as a
reformable resin material) may have a relatively low glass
transition temperature (T.sub.g). It may he possible to have a
T.sub.g below about 100.degree. C., below about 90.degree. C.,
below about 80.degree. C., below about 70.degree. C., below about
65.degree. C., as measured by differential scanning calorimetry
according to ASTM E1356-08(2014). The material of the present
teachings may have a glass transition temperature as measured by
differential scanning calorimetry according to ASTM E1356-08(2014)
of at least about 45.degree. C., at least about 55.degree. C., or
at least about 60.degree. C. The use of such materials has the
ability to enhance productivity substantially. Energy consumption
can be reduced. Build times can be shortened. Still, the resulting
materials could result in materials having very attractive
mechanical and/or self-adhering characteristics that make it
attractive for additive manufacturing builds.
[0064] As the following also illustrates, the reformable resin
material may have a relatively high T.sub.g. It may be possible to
have a T.sub.g in excess of about 115.degree. C., or in excess of
about 125.degree. C., or in excess of about 135.degree. C. as
measured by differential scanning calorimetry according to ASTM
E1356-08(2014). The polymer and/or reaction product of the present
teachings may have a glass transition temperature as measured by
differential scanning calorimetry according to ASTM E1356-08(2014)
of below about 200.degree. C., below about 185.degree. C., or below
about 170.degree. C. By way of illustration, the polymer and/or
reaction product of the present teachings may have a glass
transition temperature as measured by differential scanning
calorimetry according to ASTM E1356-08(2014) of at least about
120.degree. C., and below about 170.degree. C.
[0065] The polymeric material may exhibit one or any combination of
the following characteristics: a tensile strength at yield
(according to ASTM D638-14) of at least about 15 MPa (e.g., at
least about 30 MPa or 45 MPa), a tensile elongation strength at
break (according tee ASTM D638-14) of at least about 40 MPa (e.g.,
at least about 45 or 55 MPa); an elongation at break (according to
ASTM D638-14) of at least about 15% (e.g., at least about 20%, 25
or 30%); and/or a tensile modulus of elasticity (according to ASTM
D638-14) of at least about 0.5 GPa, (e.g., at least about 1 GPa,
1.8 GPa, or 2.7 GPa).
[0066] By way of illustration of various illustrative materials,
the following identifies various possible reactions that may be
employed for making a reformable resin material.
[0067] In general, at present, any reaction suitable for achieving
the desired resulting characteristics in a reformable resin
material may be employed. At least two reaction approaches are
contemplated as within the scope of the present teachings. Either
or both in combination may be employed. In a first approach, a
reaction is employed to result in a poly(hydroxyaminoether),
(PHAE). In a second approach, a reaction is employed to result in a
thermoplastic epoxy polymer that is essentially devoid of nitrogen
and/or an amine moiety along its backbone.
[0068] Exemplary materials may be made with a difunctional epoxy
resin and a primary amine or a secondary diamine, e.g., a reaction
between diglycidyl ether of bisphenol A and monoethanolamine. For
some applications that may require a higher glass transition
temperature (Tg), it is contemplated that some or all of the
diglycidyl ether of bisphenol A may be replaced by an epoxy monomer
with less mobility. Such epoxy monomers may include diglycidylether
of fluorene diphenol or 1,6 napthalene diepoxy. Also, it is
contemplated that where fire resistance is desired, some or all of
the diglycidyl ether of bisphenol A may be replaced by a brominated
bisphenol A epoxy resin. In accordance with this approach materials
be prepared by reacting a diglycidyl ether of dihydric aromatic
compounds such as the diglycidyl ether of bisphenol A, or a
diepoxy-functionalized oly(alkylene oxide) or mixture thereof with
a primary amine or a secondary diamine or a monoamine
functionalized poly(alkylene oxide) or mixture thereof.
[0069] Such materials generally have a relatively high flexural
strength and modulus, often much higher than typical polyolefins
(i.e., polyethylene and polypropylene). Such materials may be melt
processable at temperatures such as a temperature above about
70.degree. C. about 85.degree. C. or about 90.degree. C., and/or
below about 300.degree. C., about 250.degree. C., about 230.degree.
C., or about 210.degree. C. In addition, use of the reformable
resin materials described herein for carrier structures provide for
improved rigidity and/or improved adhesion when bonded adhesively
to another article, e.g., as compared with another traditional
polymeric material such as a polyolefin, a polyamide, a polyester,
a polyurethane, a polysulfone, or the like.
[0070] As the teachings herein illustrate, other epoxide-containing
moieties may be employed. Epoxide-containing moieties may include
at least one mono-functional epoxide and/or a di-functional epoxide
("diepoxide"). Among the various diepoxides that can be employed in
the teachings, there may be a diglycidyl ether of a dihydric phenol
(e.g., resorcinol, biphenol or bisphenol A). Any epoxide-containing
moiety herein may be an aliphatic and/or an aromatic epoxide.
[0071] An illustration of one possible example of such a material
may be a reaction product of a diglycidyl ether of a dihydroxy
organic compound and an amino, namely one having two amino
hydrogens per molecule (e.g., a reaction product of a diglycidyl
ether of bisphenol A and a monoethanolamine), as described for
example at col. 1, line 4 through col. 2, line 52 in U.S. Pat. No.
3,317,471 (incorporated by reference).
[0072] Additional details of suitable reactants and conditions for
this first approach can be found in Published U.S. Application No.
20070270515 (see, e.g., paragraphs [00141]-[0025]), U.S. Pat. No.
5,164,472 (see, e.g., cols. 2-4); and U.S. Pat. No. 3,317,471 (see,
e.g., col. 1, line 4 through col. 2, line 52), all incorporated by
reference.
[0073] Referring in more detail to the second approach, without
limitation, this approach may be employed in instances when it is
desired to employ a material having a relatively high glass
transition temperature. One approach envisions a reaction that may
include a step of reacting a dihydric phenol or combination of
different dihydric phenols with a diepoxide or combination of
different diepoxides. The reaction may occur in the presence of a
catalyst, (e.g., a catalyst selected from the group consisting of
bis(trihydrocarbylphosphoranylidene)ammonium salt,
bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt, and
tetrakispris(dihydrocarbylamino)phosphoranylideneaminoiphosphonium
salt). The reaction between the dihydric phenol and the diepoxide
may be conducted in an ether or hydroxy ether solvent at a
temperature sufficiently high to produce a poly(hydroxy ether). A
particular illustration of such possible approach to forming a
reformable resin material having a relatively high glass transition
temperature may be gleaned from U.S. Pat. No. 5,401,814;
incorporated by reference. One approach envisions a reaction that
may include a step of reacting a dihydric phenol or combination of
different dihydric phenols with a diepoxide or combination of
different diepoxides. The reaction may occur in the presence of a
catalyst, (e.g., a catalyst selected from the group consisting of
bis(trihydrocarbylphosphoranylidene)ammonium salt,
bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt, and
tetrakis[tris(dihydrocarbylamino)phosphoranlideneamino]phosphonium
salt). The reaction between the dihydric phenol and the diepoxide
may be conducted in an ether or hydroxy ether solvent at a
temperature sufficiently high to produce a poly(hydroxy ether). A
particular illustration of such possible approach to forming a
reformable resin material having a relatively high glass transition
temperature may be gleaned from U.S. Pat. No, 5,401,814;
incorporated by reference.
[0074] Approaches other than the above to reactions for making
materials useful for the present teachings (e.g., a thermoplastic
polyether) may include one or more reactions selected from the
above first and second approaches, or (a) a reaction product of
diglycidyl ether of a biphenol with a dihydroxybiphenyl, in which
the repeating unit of the polyhydroxyether contains a hydrocarbon
connecting group and a hydrocarbon or halogen substituted phenylene
radical, as described in U.S. Pat. No. 4,647,648 (incorporated by
reference); (b) a reaction product of a diglydicyl ether of certain
amido-dihydric phenols and N-substituted dihydric phenols, as
described in U.S. Pat. No. 5,115,075 (incorporated by reference);
(c) a reaction product of a dihydric phenol (e.g., a diglycidyl
ether of one or more of bisphenol ketone, bisphenol sulfone,
resorcinol or hydroquinone) and at least one other dihydric phenol
such as 4,4'-ispropylidene bisphenol (bisphenol A),
4,4'-dihydroxydiphestylethylmethane,
3,3'-dihydroxydiphenyldiethylmethane,
3,4'-dihydroxydiphenylmethylpropylmethane, bisphenol,
4,4'-dihydroxydiphenyloxide 4,4'-dihydroxydiphenylcyanomethane,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenyl sulfide, 4,4-dihydroxydiphenyl sulfone,
2,6-dihydroxynaphthalene, 1,4'-dihydroxynaphthalene catechol, or
the like, as described in U.S. Pat. No. 5,164,472 (incorporated by
reference); (d) a reaction product (e.g., a reactive extrusion
product) of a diglycidyl ether of a dihydric phenol with an amine
having only two hydrogens under conditions sufficient to form the
polyetheramine, as described in U.S. Pat. No. 5,275,853
(incorporated by reference); (e) a reaction product of dihydric
phenol and a diepoxide in the presence of a catalyst selected from
bis(trihydrocarbylphosphoranylidene)ammonium salt,
bis[tris(dihydrocarbylamino)phosphoranylidene]ammonium salt, or
tetrakis[tris(dihydrocarbylamino)phosphoranyliderneamino]phosphonium
salt, as described in U.S. Pat. No. 5,401,814 (incorporated by
reference); (f) a reaction product prepared by reacting (1) a
primary amine or bis(secondary) diamine with (2) a diglycidyl ether
and (3) an amine- or epoxy-functionalized poly(alkylene oxide), as
described in U.S. Pat. No. 5,464,924 (incorporated by reference);
(g) a reaction product of a compound having an average of more than
one vicinal epoxide group per molecule and a polyhydric phenol or
thiophenol, in the presence of a catalytic amount of a
tetranydrocarbyl phosphonium salt in an essentially anhydrous
medium, as described in U.S. Pat. No, 4,438,254 (incorporated by
reference); (h) a reaction product of a diepoxide (e.g., diglycidyl
ethers of dihydric phenols) and a difunctional species selected
from dihydric phenols, dicarboxylic acids, bis-secondary amines,
primary amines, dithiols, disulfonamides, and compounds that
contain two different functionalities capable of reacting with
epoxide groups, as described in U.S. Pat. No. 6,011,111
(incorporated by reference); or (i) a hydroxy-phenoxyether reaction
product polymer prepared by reacting a difunctional species (that
is, a species having two reactive groups), such as a dihydric
phenol, with a diepoxide (that is, a compound having two epoxide
functionalities) under conditions sufficient to cause the hydroxyl
moieties to react with the epoxy moieties to form ether linkages,
as described in WO98/14498 (incorporated by reference).
[0075] Reformable resin materials according to the present
teachings may have a generally linear backbone and may also have at
least one ether linkage in repeating units of the generally linear
backbone. Materials according to the present teachings may be free
of crosslinking, or of any thermoset portion chemically bonded to a
generally linear backbone.
[0076] It is possible that two or more of the reformable resin
compositions described above may be utilized together. For example,
two or more reformable resins, each with different glass transition
temperatures may be used together for selectively varying
properties. This can be achieved by blending the two, or by
intermingling preforms of each (e.g., a yarn or weave that has
fibers of both higher and lower glass transition).
[0077] The teachings herein make advantageous use of reformable
resin materials for use in various applications, such as in the
construction, appliance, and/or transportation industries. By way
of example, reformable resin materials of the teachings find
application in transportation vehicle components, such as
structural reinforcements, baffle devices, sealing devices, panels
(e.g., wall panels, automotive body panels, roof panels, etc.),
brackets, beams (e.g., cross-vehicle beams, such as beams useful
for supporting instruments of an instrument panel), module frames
(e.g., a frame upon which a plurality of components can be mounted,
either before, during and/or after assembly of the frame into a
vehicle structure).
[0078] The resulting articles not only can be made by taking
advantage of the beneficial processing characteristics consistent
with thermoplastics of the reformable resin materials. But, upon
fabrication of the articles, the articles may be further modifiable
by forming or otherwise shaping, by heating the article to a
temperature above which at least a portion of the reformable resin
material that is incorporated into the article is elevated above
its T.sub.g. Thereafter, the article can be cooled so the material
is below the T.sub.g, thereby causing the material to retain its
desired shape. At one or more times when the reformable resin
material is above its T.sub.g the reformable resin material is such
that it becomes tacky and can form an adhesive bond with an item
placed on it. Thus, teachings herein contemplate heating an article
having a wall to which a component is to be attached to an elevated
temperature above which at least a portion (e.g., below about 60%,
about 50%, about 40% about 30%, about 20% or about 10% of the
average wall thickness) of the reformable resin material that is
incorporated into the wall of the article is elevated above its
T.sub.g. At such time when the portion of the reformable resin
material is above its T.sub.g, a component is placed in contact
with it (optionally in the presence of pressure). Thereafter, the
article can be cooled so the material is below the T.sub.g, thereby
causing the material to retain its desired shape and secure the
component to it by adhesive bonding. It is possible to make use of
the T.sub.g and adhesive characteristics of the reformable resins
in order to simplify assembly structures by removing the need for
certain attachment hardware. This allows for attaching a component
directly to the article adhesively, without mechanical fastener
hardware or overmolding a structure onto a pultruded beam (the beam
may be partially or fully encapsulated by the molded material).
[0079] With reference to the material of the polymeric matrix, for
any of the embodiments general or specific herein, it may include a
thermoplastic polymer (e.g., a thermoplastic epoxy polymer, a
reformable resin, a thermoplastic reaction product). The polymer
may be a hydroxy-phenoxyether polymer, such as a polyetheramine
thermoplastic material. For example, the polymer may be a product
(e.g., a thermoplastic condensation reaction product) of a reaction
of a mono-functional or di-functional species (i.e., respectively,
a species having one or two reactive groups, such as an amide
containing species), with an epoxide-containing moiety, such as a
diepoxide (i.e., a compound having two epoxide functionalities),
reacted under conditions for causing the hydroxyl moieties to react
with the epoxy moieties to form a generally linear backbone polymer
chain with ether linkages. The polymer may be a reaction product of
a diepoxide resin (e.g., BPA), and one or more of a mono primary
amine, a di-secondary amine, a dimer captan and/or a di-carboxylic
acid.
[0080] Though other functional species may be employed, as is
taught in U.S. Pat. No. 6,011,111 (incorporated by reference; see,
e.g., cols. 6-8) and WO 98/14498 (incorporated by reference; see,
e.g., pages 8-11) examples of such mono-functional or di-functional
species may include a dihydric phenol, a secondary amine (e.g., a
bis-secondary amine), a primary amine, or any combination thereof.
Any amine of the functional species can be an aromatic amine, an
aliphatic amine or a combination thereof. The mono-functional or
di-functional species may have one or two functionalities capable
of reacting with epoxide groups to form a generally
non-cross-linked polymer. Some particular examples, without
limitation, of functional species for reaction with an epoxy moiety
in accordance with the present teachings includes an ethanolamine
(e.g., monoethanolamine), piperazine or a combination thereof. Any
of the illustrative functional species may be substituted or
unsubstituted.
[0081] Other examples of illustrative materials, functional species
and diepoxides are described in U.S. Pat. Nos. 5,115075; 4,438,254;
6,011,111; and WO 98/14498 (see e.g., pages 3-8) along with
illustrative synthesis conditions, all incorporated by reference
herein (see also U.S. Pat. No. 3,317,471 and 4,647,648, also
incorporated by reference herein). Examples of such materials also
can be found, without limitation at paragraphs 15-25 of Published
U.S. Patent Application No. 20070270515 (Chmielewski et al.),
incorporated by reference for all purposes.
[0082] The teachings herein also relate to a method for making a
composite article. In general, a method in accordance with the
present teachings may employ a step of contacting a plurality of
segmented forms provided for defining a distributed phase with a
generally thermoplastic epoxy reaction product of reactants (e.g.,
a mono-functional or di-functional species (i.e., respectively, a
species having one or two reactive groups, such as an amide
containing species), with an epoxide-containing moiety, such as a
diepoxide (i.e., a compound having two epoxide functionalities)).
That is in a softened state (e.g., in a liquefied molten state).
For instance, a method in accordance with the present teachings may
employ forming a composite material by passing a mass of fibers and
resin through a die (e.g., by extrusion and/or pultrusion), by
molding (e.g., injection molding, compression molding, or
otherwise), or a combination of each. One or more other methods may
be employed to make articles in accordance with the present
teachings. For example, it may be possible to make a product by
thermoforming.
[0083] The contacting may be only after the reaction has completed
between the epoxy and the amine (e.g., only after the reaction of
epoxy and amine reactants). Thus it is possible that the method
herein will involve no chemical reaction between any reactants
(e.g., any epoxy and amine reactants) that occurs within a molding,
or shaping machine in which the reaction product and the intended
distributed phase materials are brought into contact. That is, the
method may include advancing a thermoplastic polymer having at
least one epoxide functional group reaction product along a
rotating feed screw within a barrel of a polymeric material shaping
apparatus, and then contacting the thermoplastic polymer with the
intended distributed phase material.
[0084] It is also possible that a portion of the intended
distributed phase material is contacted with reactants prior to any
reaction to form the thermoplastic polymer reaction product of the
present teachings. For example, it may be possible that the
intended distributed phase material is contacted with either or
both of an epoxy or amine reactant (e.g., in a liquid state) prior
to reaction to form the thermoplastic polymer reaction product. For
example, a mass of fibers may be infiltrated with a liquid epoxy
reactant, a liquid amine reactant or both. Thereafter, any
remaining reactant may be introduced (alone with exposure to any
necessary heat and/or pressure) for bringing about a reaction to
form the thermoplastic polymer reaction product in situ within the
mass of fibers. Use of the reformable resins described herein as
pultrusion polymers, when in a fluidic state, are able to provide a
surprisingly good infiltration of a mass of fibers for providing an
cohesive matrix within which the fibers are distributed.
[0085] A method for making an article in accordance with the
present teachings may be performed in a continuous manner. For
example, fibrous material from a continuous supply (e.g., a reel of
the desired fibrous material (e.g., in its desired form, such as a
strand, a yarn, a weave, nonwoven mat, or otherwise as described
herein) for use as the distributed phase) may be fed continuously
to and through a die. The fibrous material may be contacted (e.g.,
by way of a suitable coating operation, such as roll coating, or
otherwise) with the thermoplastic polymer reaction product prior to
or at the time when the fibrous material is passed through the die.
The fibrous material may be contacted (e.g., by way of a suitable
coating operation, such as role coating, or otherwise) with the
reactants for the thermoplastic polymer reaction product prior to
or at the time when the fibrous material is passed through the die.
Upon exiting the die, a composite mass remits. The fibrous material
may thus form a distributed phase within the composite mass. The
mass may be cut, shaped or otherwise subjected to another (e.g.,
secondary) operation to render a composite article suitable for use
for an intended application.
[0086] It may be possible also that a step of co-extrusion may be
employed. The step of co-extrusion may include a step of passing a
composite mass, such as described above, through a die, while also
feeding a supply of base material through the die. The base
material may be a polymeric material, a metal material or
otherwise. Conditions may be maintained while the materials are
passed through the die so that the composite mass becomes bonded to
(e.g., mechanically, adhesively, covalently, or any combination
thereof), to the resulting shaped base material. For example, it
may be possible that the heat from the base material while it is
processed through the die, or essentially immediately thereafter,
may be sufficiently hot to cause the thermoplastic polymer reaction
product to fuse with or otherwise bond to the base material.
[0087] As can be appreciated, a variety of suitable composite
profiles are possible as a result of the teachings. The profiles
may include a longitudinal axis. The composite profiles may be
symmetric or asymmetric relative to the longitudinal axis. The
composite profiles may include one or more longitudinally oriented
ribs. The composite profiles may include one or more transversely
extending flanges. The composite profiles may have one or more
outer surfaces. The composite profile may have one or more inner
surfaces. The composite profiles may include a composite overlay
that includes or consists of a composite mass of the present
teachings. The composite profiles of the teachings may include a
composite overlay that includes or consists of a composite mass of
the present teachings. The composite overlay may cover all or part
of an outer or inner surface. The composite overlay may include or
consist of a composite mass of the present teachings may define all
or part of a rib, a flange (e.g., a transversely oriented flange)
or both. The composite profiles may include a composite mass that
is at least partially or even completely embedded within the base
material over some or all of the length of the composite profile.
The composite profile may include an extruded profile structure
defining a mechanical attachment for securing the profile to
another structure (e.g., such as is disclosed in U.S. Pat. No.
7,784,186 (incorporated by reference; see, e.g., FIGS. 4 and
associated written description). The composite profile may also
have one or more push pin type fasteners such as disclosed in U.S.
Pat. No. 7,784,186 (incorporated by reference; see, e.g., FIGS. 1-3
and associated written description). Any of the above can be
employed for use as an extruded carrier for a structural
reinforcement and/or baffle (e.g., for a transportation
vehicle).
[0088] For use as an extruded carrier for a structural
reinforcement and/or baffle (e.g., for a transportation vehicle),
there may also be employed an activatable material or at least a
portion of an outer surface of the carrier.
[0089] The teachings also envision a possible manufacturing system
that may be employed for an extrusion operation in accordance with
the present teachings. Raw material for forming a base polymeric
material body are fed into a hopper associated with an extruder.
The extruder may have a die through which the raw material is
passed to form a shaped body profile (e.g., an extruded profile).
The shaped body profile may be cooled (e.g., by a vacuum cooler) to
a desired temperature (e.g., below the softening point of the
material, so that it retains its shaped state). A feed system may
feed a fibrous material (e.g., by way of rollers) to a suitable
device for applying a matrix material for defining a composite
fibrous material (e.g., a roll costar). At such device, the
material for forming a polymeric matrix is contacted with the
fibrous material. A suitable device for defining a shape of the
fibrous composite material may be employed, such as a forming
roller (or another suitable extrusion and/or pultrusion type
shaping device). The forming roller or other suitable device may
also serve to help join the fibrous composite material with the
shaped base body profile.
[0090] Upon joinder the resulting overall composite may be cooled
(e.g., by a cooling tank). Optionally, if to be employed for use as
a carrier for a baffling and/or structural reinforcement
application, the resulting overall composite may be advanced by a
conveyor device (e.g., a pulling or pushing device). An activatable
material (e.g., a polymeric heat activatable sealant, acoustic
foamable material, and/or structural reinforcement material) may be
applied to the composite by an extruder (e.g., a cross head
extruder). Thereafter, the resulting composite (with or without the
activatable material on it) may be cut by a suitable cutting device
(e.g., a traveling cut-off saw). By way of illustration, without
limitation, the raw material may be a glass filled Nylon.RTM.
heated to about 260.degree. C. Upon exiting the cooler, the
temperature may be about 150 to about 175.degree. C. The fibers may
be glass fibers that are roll coated with a reaction product of a
monoethanolamine and diglycidyl ether of bisphenol A, while the
reaction product in a softened state. Upon exiting the cooling tank
the composite may be at a temperature of about 120.degree. C. At
the time of passing the extruder, the temperature may be about
90-95.degree. C. The cross-head extruder may extrude one or more
masses of a heat activatable epoxy-based structural foam, such as
the L-55xx series of materials, available from L&L Products,
Inc. See, e.g., U.S. Pat. No. 7,892,396, incorporated by reference
for all purposes (an illustrative composition is shown therein at
Table I). The heat activatable material may be activatable to
expand by foaming, and adhere to an adjoining surface (e.g., a wall
defining a part of a vehicle, such as a wall defining a vehicle
cavity). The activation may occur upon exposure to the heat of a
paint bake oven, following an electrocoating deposition step. The
resulting activated material may be expanded to at least about 50%,
100%, 200%, 400%, 600%, or even 1000% of its original volume. The
resulting activated material may be expanded from its original
volume, but in an amount that is below about 2500%, 2000% or even
below about 1500% of its original volume.
[0091] The composite material of the present teachings offers the
benefit of mechanical properties typically achieved through the use
of thermoset polymeric materials (e.g., a thermoset epoxy material)
as some or all of a matrix phase of a composite. However, the
material has a number of physical attributes that make it suitable
for handling and processing, as can be appreciated form the above
discussion of processing. The material of the present teachings can
also provide post-useful life reclamation, recycling, and/or re-use
benefits. The present teachings thus also contemplate methods that
include one or more steps of post-useful life reclaiming,
recycling, and/or re-using the materials of the present teachings,
For example, a step may be employed of separating the polymeric
phase (e.g., the polymeric matrix phase) from the distributed
phase. A step may be employed of re-using one or more phases of the
composite of the present teachings. A step may be employed of
recycling one or more phases of the present teachings (e.g.,
processing at least one of the phases to a different form, size and
or shape, from its original form, size and/or shape in the
composite material of the present teachings. The material of the
present teachings may exhibit a high elongation factor so that it
is not brittle yet still very strong. The material may be able to
bond to a desired part, substrate, or location. This provides a
benefit that assembly operations may be free of welding. The
assembly operation may be free of an assembly tolerance stackup. As
components may be bonded together (e.g., without mechanical
fasteners), the parts may be free of holes, thereby improving
precision and eliminating inconsistent punching operations (e.g.,
with sheet metal). The material may ease geometric dimensioning and
tolerances.
[0092] The fibrous composite material of the present teachings may
be employed in any of a variety of possible forms. It may be
employed as an overlay on top of a body (e.g., a shaped polymeric
body). It may be employed as an insert (e.g., for forming a
continuous adjoining surface with a shaped polymeric body). It may
be an encapsulated insert within a shaped polymeric body. It may be
employed as a substitute for sheet metal. It may be employed as a
substitute for a tube or other generally cylindrical element (e.g.,
a roll tube or a hydroformed tube). The fibrous composite material
may be a patch, a strip, a wrap, or the like that may be used to
provide localized reinforcement to another component of an assembly
(e.g., a beam that receives some load). The fibrous composite
material may be rolled into a tubular shape (e.g., for use as or
with cross-car beams, side intrusion or impact beams, or other
automotive parts). The fibrous composite material may be
thermoformed into a desired shape (e.g., for a roof bow, bumper, or
other automotive part). The fibrous composite material may be
shaped to provide a structure and support for subcomponents of an
assembly. For example, the fibrous composite material may be shaped
to form a door inner module, which may provide an internal
structure within a vehicle door, which may also provide an area for
mounting and/or supporting subcomponents within the door (e.g., a
motor for actuating movement of the windows, the locking mechanism,
a wire harness, speaker system, ventilation components, mirror
controls, demister, and the like).
[0093] In one aspect of the present teachings there is contemplated
a baffle and/or a structural reinforcement for an article. The
baffle and/or structural reinforcement includes a carrier that
includes a mass of polymeric material having an outer surface and
including a first polymeric material (e.g., a first thermoplastic
material). The carrier may be made of a single polymeric material,
or a plurality of polymeric materials. The carrier may include a
fibrous composite material of the present teachings. That is, the
carrier may include a distributed segmented form phase and a
polymeric matrix phase. The polymeric matrix of the fibrous
composite material may include a generally thermoplastic epoxy
reaction product of reactants (e.g., a mono-functional or
di-functional species (i.e., respectively, a species having one or
two reactive groups, such as an amide containing species), with an
epoxide-containing moiety, such as a diepoxide (i.e., a compound
having two epoxide functionalities)).
[0094] The polymeric material for the matrix of the fibrous
composite material of the teachings may be the same as or different
from a polymeric body of the carrier, in instances in which the
fibrous composite material of the teachings is employed on or
within a polymeric body of the carrier.
[0095] By way of illustration, the carrier may employ at least one
consolidated fibrous insert (which may have a predetermined
ordering of fibers within the insert and/or may have a three
dimensional shaped configuration) having an outer surface. The at
least one consolidated fibrous insert includes at least one
elongated fiber arrangement (e.g., having a mass of continuous
fibers, which may be in an ordered arrangement, such as by being
generally axially aligned relative to each other) distributed in a
cohesive mass of a second polymeric material (e.g., a second
thermoplastic material). The fibrous insert and associated second
polymeric material may adjoin the mass of the first polymeric
material in a predetermined location for carrying a predetermined
load that is subjected upon the predetermined location. The fibrous
insert, the second polymeric material and the mass of first
polymeric material include compatible materials, structures or
both, for allowing the fibrous insert to be at least partially
joined to (e.g., form a single phase with or be miscible in) the
mass of the first polymeric material. The structural reinforcement
may also include a mass of activatable material selectively applied
over at least a portion of one or both of the outer surface of the
mass of the polymeric material or the fibrous insert (e.g., on
exterior peripheral surface of the carrier, within a cavity of the
carrier, or both). The mass of activatable material is capable of
activation for expansion by an external stimulus (e.g., heat,
moisture, radiation or otherwise) and is capable of curing to form
an adhesive bond to at least one surface of the article. Desirably
the outer surface of the fibrous insert may be at least partially
co-extensive and continuous with the outer surface of the mass of
polymeric material.
[0096] Materials for a carrier body herein may be a polyamide, a
polyolefin (e.g., polyethylene, polypropylene, or otherwise), a
polycarbonate, a polyester (e.g., polyethylene terephthalate), an
epoxy based material, a thermoplastic polyurethane, a carbon fiber
reinforce polymer or any combination thereof. It may be preferred
to employ a polyamide (e.g., polyamide 6, polyamide 6,6, polyamide
9, polyamide 10, polyamide 12 or the like). The materials of a
carrier body and any overlay and/or insert may be generally
compatible with each other in that they are capable of forming a
mechanical or other physical interconnection (e.g., a microscopic
interconnection) between them, they are capable of forming a
chemical bond between them, or both. For example, the first and
second materials may be such that they fuse together (e.g., in the
absence of any adhesive) when heated above their melting point
and/or their softening point. The carriers may also be overmolded
with a secondary material, such secondary material may be a
polymeric material such as a polyolefin, a polyamide, a polyester,
a polyurethane, a polysulfone, or the like, or an expandable
polymer (e.g., a structural foam or an acoustic foam).
[0097] The polymeric body of any carrier may include a polymeric
material that may be filled with chopped fibers (e.g., chopped
glass fibers), which may be present in amount of about 25 to about
40 (e.g., about 30 to about 35) weight percent chopped fibers. The
average length of such fibers may be below about 20 mm, below about
10 mm or even below about 5 mm. They may be randomly oriented. The
first and second materials may be free of any metallic
materials.
[0098] A fibrous insert and/or a fibrous composite material may
include one or more layers (e.g., they may have 2, 3, 4, 6, 15 or
more layers) that are consolidated in the sense that they include a
plurality of individual fibers that are distributed in a cohesive
mass of the second polymeric material. The individual fibers may be
distributed in a predetermined ordered arrangement within a matrix
of the second polymeric material. Preferably at least a portion of
the fibers are ordered in their arrangement (e.g., in a generally
ordered relationship relative to each other, such as generally
parallel or unidirectional or otherwise generally axially aligned),
and thus are not randomly distributed in the second polymeric
material. Multiple layers may be consolidated together so that a
cohesive mass, including the multiple layers, is formed. The
multiple layers may be consolidated so as to form a predetermined
shape in the form of a three-dimensional shaped insert. It is also
possible that a film or intermediate layer may be located in
between one or more of the multiple layers. For instance, the
fibrous insert may employ a plurality of layers that include a
plurality of elongated fibers (e.g., having a length of at least 1
cm, 3 cm or even 5 cm or longer) that are oriented generally
parallel or generally unidirectionally to each other and are
distributed in a generally continuous polymeric matrix (e.g., in a
continuous matrix of the second polymeric material). The fibers may
be mineral fibers (e.g., glass fibers, such as E-glass fibers,
S-glass, B-glass or otherwise), polymeric fibers (e.g., an aramid
fiber, a cellulose fiber, or otherwise), carbon fibers, metal
fibers, natural fibers (e.g., derived from an agricultural source),
or otherwise. Desirably the fibers are glass fibers. The plurality
of elongated fibers may be oriented generally parallel to each
other. They may be braided. They may be twisted. Collections of
fibers may be woven and/or nonwoven. The fibers may have an average
diameter of about 1 to about 50 microns (e.g., about 5 to about 25
microns). The fibers may have a suitable sizing coating thereon.
The fibers may be present in each layer, or in the fibrous insert
generally, in an amount of at least about 20%, 30%, 40% or even 50%
by weight. The fibers may be present in each layer, or in the
fibrous insert generally, in an amount below about 90%, 80%, or
even about 70%, by weight. By way of example, the fibers may be
present in each layer, or in the fibrous insert, in an amount of
about 50% to about 70% by weight. Fiber contents by weight may be
determined in accordance with ASTM D2584-11. Tapes and/or sheets
for the layers of the fibrous insert may be made by extrusion,
pultrusion or otherwise. In this manner, it may be possible to
achieve ordering of the fibers in the tapes and/or sheets. The
method herein may include a step of impregnating a fibrous mass
with the material of the polymeric matrix and passing the resulting
impregnated material through a die (e.g., a heated die) so that the
fibrous mass is coated with a generally continuous mass of the
material of the polymeric matrix. In this manner, it is also
possible to achieve desired ordering of fibers relative to each
other.
[0099] Each layer of the fibrous insert may be in the form of a
sheet, a tape or otherwise. Fibers in the sheet and/or tape
preferably may have an ordered relationship relative to each other.
For example, the fibers may be generally parallel with each other
and/or oriented unidirectionally. When consolidating multiple
layers of sheet, tape or other form of layer to form a multi-ply
fibrous insert, it is preferred that at least one layer of the
fibrous insert exhibits an ordered relationship, as opposed to a
random relationship, such as is found in fiber mats, which
typically employ chopped fibers that are randomly laid across each
other.
[0100] It is possible that the layers of the fibrous insert are
provided as being wound on a reel. Each layer may have a thickness
of at least about 0.1 mm or at least about 0.2 mm. Each layer may
have a thickness below about 0.5 mm or below about 0.4 mm. For
instance, each layer may be about 0.2 to about 0.3 mm in thickness.
Some or all of the individual layers may be anisotropic in its
mechanical properties, For example, it may exhibit a relatively
high flexural modulus and/or strength in a longitudinal direction,
but a lower flexure/ modulus and/or strength in a transverse
direction, or vice versa.
[0101] The fibrous insert may include a plurality of woven strips.
For example, it may include a plurality of strips that are cross
woven, each strip having a width of at least about 1 mm, at least
about 2 mm, or even at least about 3 mm, it may include a plurality
of strips that are cross woven, each having a width below about 10
mm, below about 8 mm, or even below about 6 mm. The woven strips
may be held together by a polymeric matrix material, e.g., a
continuous matrix of the polymeric material of the insert. Thus,
the strips are fixed in a predetermined position relative to each
other by virtue of the polymeric material. It is preferred that at
least some of the strips may each include a plurality of elongated
fibers arranged in an ordered relationship relative to each other,
desirably within a continuous matrix of polymeric material.
However, it is possible that one or more strips may include fibers
having a random orientation relationship relative to each other,
such as is derived from typical fiber mats. Strips for forming
weaves may be made by slitting a tape, sheet or other form to an
appropriate width to form strips. Alternatively, it may be possible
that the strips are pultruded, extruded or otherwise formed (as
described herein) in the desired width.
[0102] The material defining the fibrous insert may exhibit a
flexural strength per ASTM D790-10 of at least about 450 MPa (e.g.,
it may range from about 500 to about 1100 MPa). The material of the
fibrous insert may exhibit a flexural modulus per ASTM D790-10 of
at least about 5 GPa, 10 GPa, 20 GPa, or even at least about 25 GPa
(e.g., it may range from about 30 to about 35 GPa).
[0103] The fibrous insert may employ a fully densified polymer for
the polymeric matrix. The fibrous insert may have a void content
that is below about 10% by volume of the insert, and more
preferably below about 5% or even below about 2% or 1% as measured
by ASTM D2734-09. The fibrous insert may have a density that is
below about 40% the density of steel, below about 33% the density
of steel, or even below about 25% the density of plain carbon
steel.
[0104] The fibrous insert may be made to include a plurality of
adjoining layers. The adjoining layers may have fiber orientations
that are the same or different relative to each other. The fibrous
insert may include a woven layer adjoining a non-woven layer. The
fibrous insert may include a woven layer adjoining another woven
layer. The weave pattern of woven layers within the fibrous insert
may be the same or may vary between such woven layers. The width of
strips may vary between adjoining layers. The thickness of
adjoining layers may be the same or different.
[0105] Examples of weave patterns include plain weaves, twill
weaves, or otherwise. Overlapping strips may be woven generally
orthogonal to one another or at some other angle. The weave may
include a plurality of warp and waft strips. The ratio of warp to
weft strips may range from about 30:70 to about 70:30. For example
it may be about 50:50. It is possible that strips of the warp and
weft members may have generally the same width. The warp strip and
weft strip widths may vary relative to each other by 10%, 20%, 30%
or more. The warp strip and weft strip widths may vary relative to
each other by less than about 70%, 60%, 50% or less.
[0106] Each adjoining layer of tape and/or sheet in the fibrous
inserts herein may be oriented so that it has fibers (i.e., the
fibers that are embedded in the polymeric matrix of the tape and/or
sheet) aligned in a different predetermined direction relative to
fibers of an adjoining layer. Fibers in one layer may be generally
at an angle relative to fibers in an adjoining layer (e.g., the
axis of fiber orientation as between layers may differ from about
10 to about 90.degree., such as in the form of an X-ply). For
example, one multiple layer structure may include one layer that
may have fibers oriented in a first direction of a first plane, and
an adjoining layer oriented with its fibers generally in a second
plane parallel to the first plane, but at an approximately 90
degree angle.
[0107] Desirably each of the adjoining layers are joined together
as a cohesive mass. For instance, each of the layers may be bonded
together by the polymeric material of the respective layers to form
a series of continuous layers. The layers may be bonded together in
the absence of any adhesive.
[0108] The fibrous composite material, such as in the form of a
sheet or a tape (which may serve as a patch or a wrap), may be
applied to control failure modes of certain components of an
assembly which may be subject to a load, to provide localized
reinforcement, or both. For example, a hollow beam (e.g., having a
rectangular cross section) receiving a load from the top may have a
tendency to shear. Strength may be improved and/or the failure mode
may be altered by adding a fibrous composite material as disclosed
herein. The fibrous composite material may be attached to the
hollow beam to alter its deformation characteristics (e.g., with
the composite material being generally planar (or in planar contact
with a portion of the beam), acting as a shell around the beam,
surrounding the beam as a wrap in a generally helical direction, as
a generally cylindrical or tubular structure outside or inside of
the hollow beam, or another configuration). For example, a weaved
tape may be applied along the side wails of the beam to help resist
having a shear plane that arises substantially along the
longitudinal axis of the beam (traveling through the middle of the
part). The tape (or other form fibrous composite material) may be
single ply or multi-ply, with a combination of fiber orientations
(e.g., one layer having fibers generally oriented in the
longitudinal direction, another layer having fibers in an
orientation that is at an angle relative to the longitudinal
direction (e.g., at 90 degrees, 45 degrees or otherwise)). The
fiber directions may assist in resisting shear or may provide
control and/or predictability in failure of the component (e.g., a
beam) upon being subjected to a particular load. A secondary
component may be applied to further increase strength or alter the
failure mode, such as another fibrous layer having a different
orientation, or may be a metal, a foam component (inside or outside
of the hollow beam, for example), a fibrous mat, or a ductile
material (e.g., a rubber-like material). The fibrous insert may
have one or more structure/features incorporated therein or
attached thereto. For example, one or more fasteners may be
employed (e.g., one or more threaded fasteners). One or more lugs
may be formed or integrated into the fibrous insert (e.g., for
providing a gap for the passage of a coating fluid), One or more
rivets (e.g. a self-piercing rivet, a blind rivet or both) may be
integrated into the insert. One or more metal blanks may be
integrated into the insert, which may be adapted to provide a
location on a resulting part for spot welding. One or more studs
may be integrated into the insert (e.g., having a base that may
have apertures defined therein, which is located within or on a
surface of the fibrous insert and which has a post (e.g., a
threaded post) that extends outward from the base). One or more
metallic panels, sheets, or pieces may be integrated into the
insert or secured thereto, such as for providing localized
reinforcement.
[0109] The one or more structural features may be incorporated into
the fibrous insert (or other fibrous composite material) via
selective heating. In accordance with the present teachings there
is envisioned that one or more assemblies may be made by
selectively heating a portion of a structure having a wall (e.g.,
an outer wall of the fibrous insert) with a thickness to elevate at
least a portion of the thickness of the wall to a temperature above
the glass transition temperature of a polymer (e.g., a polyamide
and/or a reformable resin material as taught herein, which may be
reinforced as described herein, such as with a fiber or other
phase) that forms the wall. While the at least a portion of the
thickness of the wall is above the glass transition temperature of
the polymer that forms the wall, an article is contacted with the
structure at least partially within the heated region, optionally
under pressure. Thereafter, upon heat leaving the heated region,
the polymer that forms the wail cools so that resulting polymer in
contact with the article is cooled below the Mass transition
temperature. An adhesive bond thereby results, with the article
remaining attached to the structure by way of the bond. The above
method may be employed to form an adhesive bond either with or
without an additional applied adhesive. That is, it may be possible
that the material of the structure, when heated above its T.sub.g,
and then cooled below it, will be capable of forming an adhesive
bond directly with the contacted article. Moreover, the tenacity of
the bond may be sufficient so as to obviate the need for any
fastener for securing the article to the structure. One option for
achieving a bonded assembly accordance with the above may be to
employ an adhesive layer, wherein the adhesive layer (e.g., having
a thickness below about 5 mm, 4 mm, or 3 mm, and above about 0.05,
0.1 or about 0.5 mm) is made of a reformable resin material as
described herein.
[0110] The structure may be any of a number of suitable forms. For
example, it may be an elongated beam. It may have a length and may
be solid along all or part of the length. It may have a length and
be hollow along all or part of the length. The structure may have a
wall thickness, measured from a first exposed surface to a
generally opposing exposed surface. The wall thickness may be at
least about 0.5 mm, about 1 mm, about 2 mm, about 5 mm, about 10
mm, or about 20 min. The wall thickness may be below about 100 mm,
below about 80 mm, below about 60 mm, or below about 40 mm.
[0111] The structure may have a predetermined shape. The shape may
include one or more elongated portions. The shape may include one
or more hollow portions. The shape may include one or more walls
that define at least one cavity. The structure may include a
plurality of portions each having a different shape. The structure
may be configured to define a fascia, which optionally may be
supported by an underlying structure. The structure may be
configured to define a support that underlies a fascia. The
structure may have a panel configuration, e.g., a configuration
that resembles a transportation vehicle (e.g., an automotive
vehicle) exterior body or interior trim panel.
[0112] The structure may be configured to receive and support one
or a plurality of articles (e.g., transportation vehicle
components), such as for forming a module, By way of illustration
the one or more articles may be selected from a bracket, a hinge, a
latch, a plate, a hook, a fastener (e.g., a nut, a bolt or
otherwise), a motor, a component housing, a wire harness, a
drainage tube, a speaker, or otherwise.
[0113] Heat may be applied in any suitable way. One approach may be
to employ localized heating. For example, it is possible to employ
induction heating for selectively heating at least a portion of the
above-described structure. To illustrate, it is possible that the
structure will be made with a polymer (e.g., a polyamide and/or a
reformable resin material as taught herein, which may be reinforced
as described herein, such as with a fiber or other phase), and will
have a wall thickness. A metallic item (which may be a component
desired to be attached to the structure) may be brought into
proximity (which may or may not be in contacting relation) with the
structure at the desired location of attachment. An induction
heating device may be brought into proximity with the metallic item
for heating the metallic item, which in turn will heat the
structure in the affected location when power is supplied to the
induction heating device. Other heating devices may be employed as
well for achieving localized heating.
[0114] It is possible that time that elapses from the time the
structure is initially heated until when an article becomes
attached to it by the above steps may be relative short. For
example, the operation may take less than about 1 minute, less than
about 30 seconds, or less than about 15 seconds. It may take as low
as about 1 second, about 3 seconds, or about 5 seconds.
[0115] Another approach to forming an assembly in accordance with
the present teachings envisions forming a shaped part by heating a
of mass material in accordance with the teachings (e.g., a
polyamide and/or a reformable resin material as taught herein,
which may he reinforced as described herein, such as with a fiber
or other phase) to a temperature above the T of the material. When
at least a portion of the material is above the T.sub.g, pressure
may be applied to the mass of material to define a configured part.
For example, it may be thermoformed, molded, or otherwise shaped.
The configured part may then be joined with another part to form an
assembly. The joinder of parts may be by an adhesive bond, by a
mechanical connection (e.g., using a fastener, using a fitted joint
configuration, or both), or both. For example, without limitation,
at least two generally complementary parts may be secured to each
other. If one of the parts is made with a reformable resin material
as taught herein, they may be joined together by attaching the
parts while at least a portion of that part is above the of the
reformable resin material, and then cooling to a temperature below
the T.sub.g. Optionally, this approach may be modified to include
the employment of a layer of adhesive between the parts, wherein
the adhesive layer (e.g., having a thickness below about 5 mm, 4
mm, or 3 mm, and above about 0.05, 0.1 or about 0.5 mm) is made of
a reformable resin material as described herein.
[0116] The parts may be dissimilar materials. For example, one part
may include a reformable resin material of the present teachings.
The other part may it a polyurethane, a polyolefin (e.g., a
polypropylene), a polyamide, are acrylate, a methacrylate, a
polycarbonate, a polyester, or any combination thereof; the other
part may include a thermoset material; the other part may be made
form a sheet raiding compound or by reaction injection molding.
[0117] As indicated the fibrous inserts may have a predetermined
shape. The shape may be the result of one or more calculations
performed during a step of computer simulation of a crash, a
certain stress state or otherwise, and may be selected so as to
provide additional localized reinforcement in a predetermined
region of the part that will be subjected to a predicted stress
condition that is determined from such calculations. The fibrous
inserts herein may include one or any combination of a generally
sinusoidal geometry over some or all of its length, a pair of
spaced apart walls that are joined together by a cross wall, one or
more ledges and/or steps, a concave surface portion, a convex
surface region, or one or more apertures. As indicated, the fibrous
inserts herein may have a three dimensional configuration, in
contrast with a generally planar configuration.
[0118] The characteristics of the fibrous insert can vary from
application to application. One benefit of the present teachings is
that the layers of the fibrous insert can be selected to meet the
needs of a particular application (e.g., in response to modeling by
computer simulation (such as computer crash or stress state
simulation)). The insert can be individually built up to include a
plurality of layers based upon the performance demanded by the
application. Moreover, another benefit of the teachings herein is
that localized reinforcement can be achieved by locating the
inserts in particular locations that are indicated as requiring
additional local reinforcement (e.g., in response to modeling by
computer simulation (such as computer crash or stress state
simulation)). The teachings herein thus afford the skilled person
with a surprisingly expanded ability to selectively tune
performance of structural reinforcements. The teachings also
contemplate the use of modeling by computer simulation to determine
the location at which a carrier is expected to carry a
predetermined load in a crash or under a certain stress state.
Based upon the results of such modeling, the location at which a
fibrous insert should be located can be determined. Also, based
upon the results of such modeling, the orientation of fibers and/or
the selection of respective adjoining layers of tape or sheet in a
fibrous insert can be ascertained. Parts can thereafter be made
that are based upon the designs resulting from such modeling.
Methods employing such steps are thus within the present teachings
as well.
[0119] The carriers of the structural reinforcements may be such
that the outer surface of the fibrous insert is generally
co-extensive with the outer surface of the mass of polymeric
material. This may be over some or all of the perimeter of the
fibrous insert. It is also envisioned that the fibrous insert may
have opposing surfaces that are each exposed and thus visible in
the resulting part. For instance, the fibrous insert may have an
exposed outer surface and an exposed inner surface. Thus, the
fibrous insert may adjoin the mass of polymeric material only along
one or more side edges of the fibrous insert. The resulting visible
surfaces of the carrier may be substantially free of knit lines or
other imperfections that could provide a source of localized
weakening of the carrier.
[0120] The second polymeric may be applied directly onto the
fibrous insert. The second polymeric material may be a liquid
poured onto the fibrous insert until the insert is saturated with
the second polymeric material. The liquid absorbed by the fibrous
insert may account for at least about 30% and less than about 70%
of the total weight of the insert after saturation. The saturated
insert may polymerize at room temperature or with the addition of
heat, such that a rigid solid composite is formed. The resulting
composite may then receive the first polymeric material by locating
the composite into a tool and molding the first polymeric material
(which may be a Nylon material) about the composite.
[0121] As appreciated from the above, the carrier may have (i) a
polymeric portion defined by the mass of first polymeric material,
(ii) a localized reinforcement portion defined by the at least one
fibrous insert, and (iii) an interface portion between the
polymeric portion and the localized reinforcement portion wherein
the polymeric portion, the interface portion and the localized
reinforcement portion are a generally continuous structure. The
interface portion may include (i) an interpenetrating network
defined by the first and second polymeric materials, (ii) chemical
bonds between the first and second polymeric materials, or both (i)
and (ii).
[0122] One or more sides of the activatable material may be tacky.
Though it is also possible that one or more sides will be generally
tack free to the touch at room temperature. One or more mechanical
fasteners may be employed by attaching to or being formed integral
with the activatable material, the carrier, or both.
[0123] Suitable materials that may be employed for the activatable
material include expandable materials and materials that do not
expand. However, it is contemplated that the activatable material
can be activated to form a foam. For instance, the material may be
activated to form a structural foam (e.g., the material may include
an epoxy ingredient). The material may be activated to form an
acoustic foam. The material may be activated to flow for purposes
of sealing a region within a cavity. The material may include a
combination of a material that is activatable to expand and a
material that is not activatable to expand.
[0124] The structural reinforcement of the present teachings may be
employed for structurally reinforcing an article, such as by
locating the structural reinforcement within a cavity of the
article and activating the activatable material so that it expands
and bonds to a surface of the article. The structural reinforcement
may also be employed to seal and/or baffle the cavity. In a
preferred application, the structural reinforcement is employed to
reinforce a transportation vehicle such as an automotive
vehicle.
[0125] By way of example, the structural reinforcement may be
positioned within a cavity of a transportation vehicle (e.g., an
automotive vehicle) prior to coating the vehicle. The activatable
material may be activated when subjected to heat during paint shop
baking operations. In applications where the activatable material
is a heat activated, thermally expanding material, an important
consideration involved with the selection and formulation of the
material comprising the activatable material is the temperature at
which a material reaction or expansion, and possibly curing, will
take place. For instance, in most applications, it is undesirable
for the material to be reactive at room temperature or otherwise at
the ambient temperature in a production line environment. More
typically, the activatable material becomes reactive at higher
processing temperatures, such as those encountered in an automobile
assembly plant, when the material is processed along with the
automobile components at elevated temperatures or at higher applied
energy levels, e.g., during paint or e-coat curing or baking steps.
While temperatures encountered in an automobile assembly operation
may be in the range of about 140.degree. C. to about 220.degree.
C., (e.g., about 148.89.degree. C., to about 204.44.degree. C.
(about 300.degree. F. to 400.degree. F.)), body and paint shop
applications are commonly about 93.33'' C. (about 200.degree. F.)
or slightly higher. Following activation of the activatable
material, the material will typically cure. Thus, it may be
possible that the activatable material may be heated, it may then
expand, and may thereafter cure to form a resulting foamed
material.
[0126] As indicated, the teachings herein also relate to a method
for making a carrier for an activatable material (e.g., for
structural reinforcement for an article). The method may include a
step of inserting at least one fibrous insert (which may be
consolidated at the time of the step of inserting) having an outer
surface and including at least one elongated fiber arrangement into
a cavity of a tool. A mass of polymeric material may be molded in
contact with the fibrous insert so that a resulting molded mass of
polymeric material integrally adjoins the fibrous insert (which is
consolidated in its final state) and the outer surface of the
fibrous insert is at least partially co-extensive and continuous
with the outer surface of the resulting molded mass of polymeric
material. A mass of activatable material may be applied (e.g.,
overmolded, mechanically attached or otherwise) selectively over at
least a portion of one or both of the outer surface of the
resulting mass of the polymeric material or the fibrous insert.
Consistent with the teachings above, the mass of activatable
material may be capable of activation for expansion by an external
stimulus (e.g., to at least partially, if not completely, fill a
gap or a cavity) and may be capable of curing to form an adhesive
bond to at least one surface of the article to which it is
attached.
[0127] The method may include a step of at least partially shaping
the fibrous insert after it is placed in the cavity of the tool.
For example, the tool may be preheated to a temperature above the
softening temperature and/or the melting temperature of a polymer
of the at least one fibrous insert prior to placing the fibrous
insert in the cavity of the tool. The method may include a step of
at least partially shaping the fibrous insert after it is placed in
the cavity of the tool and while molding the mass of polymeric
material. For instance, heat and/or pressure that results from
introducing the mass of polymeric material into the cavity (e.g.,
by injection molding), may at least partially cause the fibrous
insert to assume a shape dictated by one or more of the walls
defining the cavity. Thus it is possible that the fibrous insert is
not preformed prior to placement in the cavity, and it assumes its
final shape only while in the cavity. Of course, it is also
possible that the fibrous insert is preformed prior to placement in
the cavity.
[0128] The fibrous insert, prior to the inserting step, may be
provided in the form of one or more layers of a tape and/or sheet,
in which the fibers may be fixed in position relative to each other
(e.g., as a result of consolidation, by which a cohesive mass of
the fibers distributed in a continuous polymeric matrix is formed).
The method may thus include a step of fabricating the fibrous
insert to include a plurality of layers of tape and/or sheet. For
example, the method includes a step of consolidating a plurality of
layers of tape and/or sheet while the plurality of layers is
subjected to heat and optionally an elevated pressure. For
instance, a temperature may be employed that is above the melting
and/or softening point of the polymer of the tape and/or sheet to
cause two or more adjoining layers to fuse and remain joined
together upon cooling. A pressure of about 0.1 to about 1 MPa may
be applied (e.g., about 0.2 to about 0.6 MPa). The temperature and
pressure may be employed for a desired amount of time to achieve
essentially complete densification. It will be appreciated that the
teachings afford for the formation of various consolidated insert
structures.
[0129] The fibrous insert may be thermoformed to form a
predetermined shape. The fibrous insert may be thermoformed during
a step of consolidating. A resulting thermoformed fibrous insert
may thereafter be placed in a tool cavity and molten thermoplastic
polymeric material may be introduced in contact with it.
[0130] The step of molding may include a step of introducing molten
polymeric material into the tool cavity by way of a gate that is
positioned in generally opposing relationship with the at least one
fibrous insert. In this manner, upon introduction into the cavity,
the molten polymer contacts the fibrous insert before it contacts a
wall defining the cavity.
[0131] Carriers made in accordance with the present teachings may
have a wall having a first surface and a generally opposing second
surface. The wall may have a thickness ranging from about 0.2 to
about 6 mm (e.g., about 1.5 to about 4 mm). At select regions
within a carrier, it is possible that at least about 20%, 40%, 60%,
80% or even 100% of the wall thickness is defined by the fibrous
insert or overlay. The fibrous insert or overlay may have a
contoured outer surface portion that is visibly exposed on the
carrier. The fibrous insert or overlay may have a generally flat
outer surface portion that is visibly exposed on the carrier. The
first surface and the second surface may be generally parallel to
each other.
[0132] The fibrous insert or overlay may occupy at least about 10%,
20%, 30% or even 40% by weight of the overall carrier. The fibrous
insert or overlay may be less than about 90%, 80%, or even 70% by
weight of the overall carrier.
[0133] Thus it is possible that at least a portion of the first
surface and the second surface are each visibly exposed and will be
composed of the fibrous insert or overlay. The carriers may have
one or more additional structural reinforcements or other
structural features, such as one or more ribs, bosses or otherwise.
These features may be free of or they may include a fibrous insert
in accordance with the present teachings.
[0134] It is contemplated that the materials as disclosed herein
may be paintable. Paintability may be desirable, for example, if
any surface is visibly exposed. The material may be ink jet
printed. The material may be painted with conventional e-coat
systems. The material may be paintable, as it may have an affinity
for taking paint. This may be due, at least in part, to the
polarity of the material and/or the hydroxyl functionality of the
backbone (e.g., generally linear backbone polymer chain).
[0135] Parts herein may be employed for any of a number of
purposes. For example, they may be employed to structurally
reinforce a transportation vehicle such as an automotive vehicle.
In this regard, a part may be placed in a cavity of a vehicle body
structure, such as a vehicle frame. After applying an e-coat layer
to the vehicle body (e.g., within the cavity), the part may be
subjected to heat from a bake oven, which causes the activatable
material to activate (e.g., expand and fill the cavity), and become
bonded to the vehicle body.
[0136] FIGS. 1-5 illustrate examples in accordance with the present
teachings. With reference to FIG. 1, there is seen a carrier 10
that has one or more masses 12 of a first polymeric material. A
fibrous insert 14 is shown joined to the one or more masses along
an edge of the insert. An interface portion 16 is depicted (in
exaggerated form for purposes of illustration; for simplicity such
interface is omitted from the remaining drawings, though it should
be appreciated that it may still exist in such embodiments). The
carrier has an upper surface 18 and a lower surface 20. The fibrous
insert 14 spans from the upper surface to the lower surface so that
the fibrous insert is exposed visibly top and bottom. FIG. 1 omits
any activatable material. However, activatable material can be
located over either or both of the mass 12 or the fibrous insert
14.
[0137] FIG. 2 depicts a carrier 110 having a mass of polymeric
material 112 and a fibrous insert 114, in which only the upper
surface of the fibrous insert is exposed. A lower surface and side
edges adjoin the mass of polymeric material. The interface region
is omitted in this depiction, though it may be present. In this
drawing, an expandable material 126 is located over both the mass
of the polymeric material and the fibrous insert. However, it can
be located over one or the other as well.
[0138] FIG. 3 illustrates an example of a carrier 210 having a
fibrous reinforcement portion 214 with an upper surface 218, from
which a rib 222 projects, which is made of a mass of polymeric
material (e.g., the same type of material as is otherwise present
in the carrier to which the insert adjoins). The rib includes an
outwardly projecting portion having a width w.sub.1, and an
enlarged neck region that has a width (at its largest dimension)
w.sub.2 that is larger than the width w.sub.1, such as by an amount
of at least about 10%, 20% or 30%. The with w.sub.2 may be larger
than the width such as by an amount of no greater than about 100%,
80% or 60%. A similar rib structure can be employed in the
embodiment of FIG. 2.
[0139] FIGS. 4a and 4b illustrate two views of an illustrative
carrier 310 that includes a mass of polymeric material 312 and a
pair of fibrous inserts 314. In this instance the fibrous inserts
have upper and lower surfaces that are exposed. Though it is
possible to employ a structure like in FIG. 2, in which only an
upper surface is exposed. A plurality of ribs 322 are employed
(ribs are shown in transverse disposition relative to a
longitudinal axis (however for all of the embodiments herein, ribs
may run longitudinally, transverse, diagonally, or any combination
thereof; ribs may also be arcuate)). An activatable material 326 is
shown. Though shown in a groove, it may rest on an outer surface or
otherwise be carried on the carrier for all of the embodiments
herein.
[0140] FIG. 5 illustrates an example of how fibrous inserts 14,
114, 214 or 314 can have multiple layers with two or more adjoining
layers having different fiber orientations. Though shown as
unidirectionally oriented in this example, strips of impregnated
fibers may also be provided as a woven layer. Other orientations
than those disclosed in FIG. 5 are possible. For example three
layers of uniaxially oriented fibers may be oriented at 0/90/0
degrees relative to each other, or five layers may be oriented at
0/45/90/45/0 degrees relative to each other. Other orientations are
also possible.
[0141] FIGS. 6a and 6b illustrate an example of one part in
accordance with the present teachings. The part includes a carrier
610 that is shown as a molded part. It includes a fibrous insert
614. The carrier includes a plurality of ribs 622. Activatable
materiel 626 is applied over a portion of the carrier, and is shown
as partially covering the insert 614. The insert 614, which is
overmolded for defining the carrier 610, includes an arcuate
surface, and specifically a concave surface portion 640. In the
embodiment shown, it is located toward an end of the insert 614.
The insert 614 also includes a through-hole aperture 642. The
insert includes a pair of opposing walls 644 (which may be
generally parallel or otherwise oriented) and a cross wall 646. The
insert spans a central portion of the carrier.
[0142] FIGS. 7a and 7b illustrate an example of another part in
accordance with the present teachings. The part includes a carrier
710 that is shown as a molded part. It includes a fibrous insert
714. The carrier includes a plurality of ribs 722. Activatable
material 726 is applied over a portion of the carrier, and is shown
as partially covering the insert 714. The insert 714, which is
overmolded for defining the carrier 710, includes an arcuate
surface portion 740. In the embodiment shown, it is located toward
an end of the insert 714. The insert 714 also includes a
through-hole aperture 742. The insert includes a pair of opposing
walls 744 (which may be generally parallel or otherwise oriented)
and a cross wall 746. At least one step 748 is defined in the
insert.
[0143] FIG. 8 illustrates schematically how a carrier may be made
in accordance with the present teachings. A reel of fibrous
material 850 may supply the material to define an insert 814, shown
as being sinusoidal. The insert may be overmolded to define
overmolded portions 852 (e.g., including a plurality of ribs) of a
resulting carrier 810. The resulting carrier, thus includes the
insert 614 and the overmolded portions 852.
[0144] FIG. 9 illustrates an example of an extruded profile in
accordance with the teachings for use as a carrier 910. The profile
includes a shaped (e.g., by rolling or otherwise being extruded)
fibrous composite material overlay 960 over an outer surface of
carrier shaped body 962 (e.g., an extruded polyamide or glass
filled polyamide, such as Nylon.RTM.). The carrier shaped body 962
has an inner surface 964. A rib 966 extends away (e.g., generally
orthogonally) from the inner surface 964. An activatable material A
is shown. The activatable material A may have been extruded onto
the carrier.
[0145] FIG. 10 illustrate an example of a possible manufacturing
system 1070 that may be employed for an extrusion operation in
accordance with the present teachings. Raw material for forming a
base polymeric material body are fed into a hopper 1072 associated
with an extruder 1074. The extruder 1074 has a die 1076 through
which the raw material is passed to form a shaped body profile 1078
(e.g., an extruded profile). The shaped body profile may be cooled
(e.g., by a vacuum cooler 1080) to a desired temperature. A feed
system 1082 may feed a fibrous material 1034 (e.g. by way of
rollers) to a roll coater 1086 at which the material for forming a
polymeric matrix is contacted with the fibrous material. A forming
roller 1088 (or another suitable extrusion type shaping device) may
then further define the desired shape of the resulting fibrous
composite material. The forming roller may also serve to help join
the fibrous composite material with the shaped base body profile.
Upon joinder the resulting overall composite 1090 may be cooled
(e.g., by a cooling tank 1092). Optionally, if to be employed for
use as a carrier for a baffling and/or structural reinforcement
application, the resulting overall composite 1090 may be advanced
by a conveyor device (e.g., a pulling or pushing device) 1094. An
activatable material may be applied to the composite 1090 by an
extruder 1096 (e.g., a cross head extruder). Thereafter, the
resulting composite (with or without the activatable material on
it) may be cut by a suitable cutting device 1098 (e.g., a traveling
cut-off saw). By way of illustration, without limitation, the raw
material may be a glass filled Nylon.RTM. heated to about
250.degree. C. Upon exiting the cooler, the temperature may be
about 150 to about 175.degree. C. The fibers may be glass fibers
that are roll coated with a reaction product of a monoethanolamine
and diglycidyl ether of bisphenol A, while the reaction product in
a softened state. Upon exiting the cooling tank the composite may
be at a temperature of about 120.degree. C. At the time of passing
the extruder, the temperature may be about 90-95.degree. C. The
cross-head extruder may extrude one or more masses of a heat
activatable epoxy-based structural foam, such as a structural
reinforcement material in the L-55xx series, available from
L&L, Products, Inc.
[0146] FIGS. 11a, 11b, 12a, 12b, 13a and 13b show exemplary parts
1102, 1202, 1302 made in accordance with the teachings herein.
Specifically, these parts are formed using a pultrusion process and
additional downstream and possibly in-line processes as disclosed
herein. Each part includes a pultruded carrier 1104, 1204, 1304 and
an adhesive or other secondary material 1106, 1206 1306 located
thereon. Such adhesive may be located onto the carrier during the
pultrusion process, via a secondary extrusion process, via an
injection molding process or via a robotic deposition process. The
parts are shown including one or more connector portions 1108a,
1108b, 1208a, 1208b, 1308 for connecting the part to a desired
location which may within a vehicle cavity. The parts are also
shown having one or more securing devices 1110, 1210, 1310. Such
securing device act to connect and secure certain fastening devices
1114, 1116, 1118, 1120, 1122, 1214, 1216, 1218, 1220, 1222, 1314,
1320, 1322, to the part as may be necessary for use of the part. It
should be noted that the fastening devices shown at FIGS. 11a, 11b,
12a, 12b, 13a and 13b are shown for example purposes only and that
parts formed in accordance with the teachings herein may include
one or any combination of the fasteners depicted in FIGS. 11a, 11b,
12a, 12b, 13a and 13b. The fastening devices shown include a weld
tab 1114, 1214, 1314, a tension clip 1116, 1218, an arrowhead
fastener 1118, 1218, a spring arrowhead 1120, 1220, 1320, and a
double arrowhead fastener 1122, 1222, 1322. Additional fasteners
1112, 1212, 1312 may be attached to the part without a securing
device. Such securing devices and fastening devices may be located
onto the carrier during the pultrusion process, via a secondary
extrusion process, via an injection molding process or via a
robotic deposition process. An additional material which may be a
pumpable material 1124, 1224, 1324 may be located within the
carrier. Such pumpable material may be located onto the carrier
during the pultrusion process, via a secondary extrusion process,
via an injection molding process or via a robotic deposition
process.
[0147] The manufacturing system may also include one or more
pultrusion steps. By way of example, a possible manufacturing
system may be employed for a pultrusion operation instead of or in
addition to an extrusion operation in accordance with the present
teachings. Raw material for forming a base polymeric material body
may be fed into a receptacle associated with a pultruder. The
pultruder may have a die through which the raw material is passed
to form a shaped body profile (e.g., a pultruded profile). A mass
of fibers may be pulled through the die and infiltrated while in
the die with the raw material. The raw material (which may be a
one-component or a plural-component mixture of reactive
ingredients) may have a relatively low viscosity sufficient to the
raw material to impregnate the mass of fibers and thereafter harden
in a desired shaped profile that includes the mass of fibers. The
shaped body profile may be cooled (e.g., by a vacuum cooler) to a
desired temperature. A feed system may feed a fibrous material
(e.g., by way of rollers) to the die at which the raw material for
forming a polymeric matrix is contacted with the fibrous material
(e.g., the mass of fibers). In an instance, where the pultruded
material has thermoplastic characteristics (e.g., a thermoplastic
epoxy) a forming miller (or another suitable extrusion type shaping
device) may then further define the desired shape of the resulting
fibrous composite material. The forming roller may also serve to
help join the fibrous composite material with any optional shaped
base body profile. Upon any joinder the resulting overall composite
may be cooled (e.g., by a cooling tank). Optionally, if to be
employed for use as a carrier for a baffling and/or structural
reinforcement application, the resulting overall composite may be
advanced by a conveyor device (e.g. a pulling or pushing device).
An activatable material may be applied to the composite by an
extruder (e.g., a cross head extruder). Thereafter, the resulting
composite (with or without the activatable material on it) may be
cut by a suitable cutting device (e.g., a traveling cut-off saw).
By way of illustration, without limitation, the raw material may be
a glass filled Nylon.RTM. heated to about 260.degree. C. Upon
exiting the cooler, the temperature may be about 150 to about
175.degree. C. The fibers may be glass fibers that are roll coated
with a reaction product of a monoethanolamine and diglycidyl ether
of bisphenol A, while the reaction product in a softened state.
Upon exiting the cooling tank the composite may be at a temperature
of about 120.degree. C. At the time of passing the extruder, the
temperature may be about 90-95.degree. C. The cross-head extruder
may extrude one or more masses of a heat activatable epoxy based
structural foam, such as a structural reinforcement material in the
L-55xx series, available from L&L Products, Inc.
[0148] The teachings herein can make any number of different parts.
One example is a door intrusion beam that can be installed in an
automotive vehicle for helping resist deformation that would
intrude into a vehicle body in the event of a collision. The
intrusion beam may be extruded. However, desirably it is pultruded
and has a pultrudate with a profile that may be constant or varying
along its length.
[0149] The teachings herein provide for a pultruded structure
comprising an elongated tubular pultrudate structure (e.g., a
composite having a polymeric matrix) having a first end and a
second end. At least one attachment device may be adapted for
attaching the tubular structure to a door frame (e.g., a vehicle
door frame). The elongated tubular structure may have a
longitudinal axis and also has at least one reinforcement portion
that includes a continuous fiber reinforcement embedded in a
polymeric matrix and has a plurality of fibers aligned generally
parallel with the longitudinal axis. A plurality of fibers (e.g.,
at least about 50%, 60%, 70% or more by weight of the total fiber
content) may extend from the first end to the second end; by way of
example the plurality of fibers may be generally aligned with the
longitudinal axis. The plurality of fibers may be embedded in the
polymeric matrix under a state of tension or compression.
[0150] The structure may be open or closed along its length. The at
least one attachment device may include an adhesive, a mechanical
fastener, or both for attaching to the door frame. The elongated
tubular structure may include one or more strips of an activatable
polymeric material on an outer surface, the activatable material
adapted for damping of vibration, for resisting flutter, or for
bonding to an adjoining structure, such as that disclosed in U.S.
Patent Publication No. 2002/0024233, incorporated by reference
herein for all purposes.
[0151] The continuous fibers may be preloaded in the at least one
reinforcement portion. The elongated tubular structure may have a
constant profile along the longitudinal axis. From about 40% to
about 80%, about 50% to about 70%, by weight of the beam is fibers.
The fibers may be glass fibers. The polymer of the polymeric matrix
may be an epoxy. The teachings herein further provide for a method
of making a vehicle structure including an elongated tubular
structure that is pultruded.
[0152] Turning now to a discussion in more detail of forming
profiled products using a thermoplastic epoxy in accordance with
the general teachings of that material herein, there is envisioned
a method of combining reactants and contacting the combined
reactants and/or reaction product of the reactants with a mass of
fibers. The contacting may be during a step of pultruding and/or
extruding a profile. Discussed previously above was a method for
extruding an article using a thermoplastic epoxy wherein the
thermoplastic epoxy is formed into pellets and fed into an
extrusion hopper. Another approach envisions pultruding a
thermoplastic epoxy material, which may or may not include a mass
of fibers.
[0153] Accordingly, the teachings herein also envision a method of
making a thermoplastic pultruded article, comprising the steps of
pulling a plurality of continuous fibers through a die for defining
a continuous profile that has at least two portions that are not
coplanar and have differing thickness relative to each other;
contacting the plurality of continuous fibers with one or more
reactants for forming a polymer for a generally continuous
polymeric matrix of the a resulting pultruded article, and applying
a sufficient amount of energy to cause a continuous primary
reaction of the two or more reactants to continuously forma
thermoplastic, pultruded article having a thermoplastic polymeric
matrix in contact with the continuous fibers and embedding the
continuous fibers therein.
[0154] Though described in connection with a thermoplastic epoxy,
the teachings herein are more general and may apply to pultruding
other materials as well such as thermoset materials. Examples of
other materials may include polyesters, polyurethanes, epoxies, or
otherwise. The die may be about 0.2 to about 1 (e.g., 0.5) meters
in length. The rate of the pultruding is at least about 0.5 (1, 2
or 3) meters per minute. The die may include an opening therein
into which the reactants are introduced so that the step of
contacting occurs within the die. The contacting may occur in
advance of the die (e.g., in a bath or pool).
[0155] The method may also include a step converting the
thermoplastic pultruded article to a thermoset pultruded article by
employing a secondary reaction that occurs under an energy
condition that is different from the energy condition for the
primary reaction sufficient for causing crosslinking of at least a
portion of the polymeric matrix.
[0156] In general, it may also be possible to employ one or more
reactants that permit an optional delayed cross-linking, reaction
to occur. For example, one or more of the reactants may include one
or more moieties that are capable of reacting (e.g., in the
presence of a certain stimulus, such as further heating and/or some
other form of a predetermined electromagnetic radiation (e.g.,
infrared, ultraviolet, microwave or otherwise) for achieving
cross-linking of a molecule with in itself and/or with an adjoining
molecule. Desirably such radiation affords cross-linking while
maintaining a resulting article made by additive manufacturing to
remain below its T.sub.g. Thus, it may be possible that
crosslinking may be realized within and/or between adjoining
layers. Thus, the teachings contemplate an optional step of causing
at least a portion of an article made with the teachings to include
cross-linking, such as by causing a cross-linking reaction to occur
(e.g., by subjecting feed material and/or the resulting article to
electromagnetic radiation as described).
[0157] The epoxide and the second reactant may be present in
approximately equal molar stoichiometric proportions. The cross
section may be changed along the length of the resulting
article.
[0158] The method may include a step of subjecting the resulting
article to a secondary shaping operation, selected from
thermoforming, blow molding, hydroforming, insert injection
molding, compression molding, cutting, heat shaping, joining (e.g.,
by adhesion, compression fitting or the like). The secondary
operation may be performed continuously.
[0159] The method may further comprise pulling the resulting
thermoplastic pultruded article over a heated mandrel for imparting
a curvature or other variable shape over at least a portion of the
pultruded article. The resulting article may have an ultimate
tensile strength (UTS) of at least 300 MPa to less than 1000 MPa.
The resulting article may have a tensile modulus of
[0160] The resulting article may be a structure for use as a
reinforcement within a vehicle cavity. The article may be a
structure or cross beam. The impact direction of the beam may be
transverse to fiber orientation. The beam may include fibers having
an axis oriented transversely to axis of expected impact.
[0161] Shaped articles in accordance with the teachings herein
generally (e.g., whether by pultrusion, extrusion or otherwise) may
be subjected to one or more secondary operations (e.g., cutting,
thermoforming, overmolding, machining). The secondary operation may
be performed in an in-line process which may be as part of the same
in-line process as the pultrusion or extrusion process. A
manufacturing system may be included in-line with the pultrusion
system which may allow for expedited manufacturing of parts (e.g.,
those shown at FIGS. 11a, 11b, 12a, 12b, 13a, and 13b) having a
plurality of material layers and attachments through one in-line
system. The system may include a pultrusion portion including one
or more of a roving from which the pultruded part gathers material,
a continuous mat or the like to which the roving is incorporated, a
resin bath and a forming/curing die. The forming/curing die may be
connected to or in communication with one or more secondary
processing devices including a drill press, a robotic deposition
arm, an injection molding device (in combination with an overmold
die) and a cut-off saw. Such devices may be arranged in a
sequential order, for example the drill press may be followed by a
first injection molding machine and then a first robotic deposition
arm. A second injection molding device may be followed by a second
robotic deposition arm. A third or even fourth or fifth set of
injection molding devices and robotic arms may be included. The
cut-off saw may be at the end of the system to cut parts to a
desired size. Alternatively, one or a plurality of injection
molding devices may be followed by a drill press and then a cut-off
saw, whereby a robotic deposition arm may be included at the end of
the system.
[0162] Such shaped articles may include composite articles. As a
result, the methods purposed herein include a method of making a
composite article comprising the steps of pultruding a first
polymeric composite structure having a plurality of first fibers
embedded in a first polymeric matrix, fabricating a second
polymeric composite structure having a plurality of second fibers
embedded in a second polymeric matrix, and securing the second
polymeric composite structure with the first polymeric composite
structure to define a composite article that includes each of the
first polymeric composite structure and the second polymeric
composite structure.
[0163] The first polymeric composite structure may include a
plurality of continuous glass fibers embedded in a polymeric matrix
in a concentration of from about 40% to about 80% or even from
about 50% to about 70%, by weight of the first polymeric composite
structure. The first polymeric composite structure may include a
plurality of continuous fibers embedded in a polymeric matrix
wherein the polymeric matrix includes an epoxy. The first polymeric
composite structure may include a plurality of continuous fibers
embedded in a polymeric matrix wherein the polymeric matrix
includes a thermoplastic epoxy.
[0164] The second polymeric composite structure may include a
plurality of glass fibers embedded in a polymeric matrix in a
concentration of from about 20% to about 80%, or even from about
40% to about 60% by weight of the second polymeric composite
structure. The second polymeric composite structure may include a
plurality of fibers embedded in a polymeric matrix wherein the
polymeric matrix includes an epoxy, a Nylon, a polyester (e.g.,
polybutylene terephthalate (PBT), or combinations thereof. The
second polymeric composite structure may include a plurality of
fibers embedded in a polymeric matrix wherein the polymeric matrix
includes a thermoplastic epoxy. The step of fabricating the second
polymeric composite structure may include a step of extruding the
second polymeric composite, injection molding the second polymeric,
composite, pultruding the second polymeric composite, thermoforming
the second polymeric composite, compression molding the second
polymeric composite, or any combination thereof.
[0165] The step of securing the first polymeric composite and the
second polymeric composite may include a step of adhering the first
polymeric composite with the second polymeric composite,
mechanically connecting the first polymeric composite with the
second polymeric composite, a step of welding the first polymeric
composite with the second polymeric composite, or a combination
thereof. The step of securing the first polymeric composite and the
second polymeric composite may include a step of inserting a
coupling device between the first polymeric composite and the
second polymeric composite, and a step of adhering the first
polymeric composite with the second polymeric composite via the
coupling, mechanically connecting the first polymeric composite
with the second polymeric composite via the coupling, welding the
first polymeric composite with the second polymeric composite via
the coupling, or any combination thereof. The shape of the first
polymeric composite and the second polymeric composite may be
complementary so that they are in generally mating relationship
with each other. The first polymeric composite and the second
polymeric composite may be similarly sized and/or shaped. The first
polymeric composite and the second polymeric composite are of
different size and/or shape. One or more of the first polymeric
composite and the second polymeric composite may comprise fibers
arranged in a mat.
[0166] It will be appreciated that, even though the embodiments of
FIGS. 1 through 9 are shown separately, features of one may be
combined with features of another and remain within the present
teachings. The depictions therein thus should be regarded as
generalized and applicable to the teachings as a whole herein.
[0167] The teachings herein are illustrated in connection with a
carrier for a structural reinforcement, in which the carrier is
generally elongated (e.g., it may be at least about 25 mm long, at
least about 50 mm long or even at least about 100 mm long).
However, the teachings are not intended to be so limiting. The
teachings also contemplate their usage for forming carriers for
baffling and/or sealing. The carriers may thus have lengths that
are shorter than about 25 mm (e.g.. about 15 mm or shorter). The
carriers may be longer than they are wide. The carriers may be
wider than they are long.
[0168] As can be appreciated from the teachings herein, various
benefits and/or advantages may be realized. For example, parts may
be prepared that have a carrier that is made of a material free of
a thermosetting plastic. Parts may be prepared that have at least a
portion of the activatable material located over and in contact
with a fibrous insert of the present teachings.
[0169] As used herein, unless otherwise stated, the teachings
envision that any member of a genus (list) may be excluded from the
genus; and/or any member of a Markush grouping may be excluded from
the grouping.
[0170] Unless otherwise stated, any numerical values recited herein
include all values from the lower value to the upper value in
increments of one unit provided that there is a separation of at
least 2 units between any lower value and any higher value. As an
example, if it is stated that the amount of a component, a
property, or a value of a process variable such as, for example,
temperature, pressure, time and the like is, for example, from 1 to
90, preferably from 20 to 80, more preferably from 30 to 70, it is
intended that intermediate range values such as (for example, 15 to
85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of
this specification. Likewise, individual intermediate values are
also within the present teachings. For values which are less than
one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as
appropriate. These are only examples of what is specifically
intended and all possible combinations of numerical values between
the lowest value and the highest value enumerated are to be
considered to be expressly stated in this application in a similar
manner. As can be seen, the teaching of amounts expressed as "parts
by weight" herein also contemplates the same ranges expressed in
terms of percent by weight. Thus, an expression in the of a range
in terms of "at least `x` parts by weight of the resulting
composition" also contemplates a teaching of ranges of same recited
amount of "x" percent by weight of the resulting composition."
[0171] Unless otherwise stated, all ranges include both endpoints
and all numbers between the endpoints. The use of "about" or
"approximately" in connection with a range applies to both ends of
the range. Thus, "about 20 to 30" is intended to cover "about 20 to
about 30", inclusive of at least the specified endpoints.
[0172] The disclosures of all articles and references, including
patent applications and publications, are incorporated by reference
for all purposes. The term "consisting essentially of to describe a
combination shall include the elements, ingredients, components or
steps identified, and such other elements ingredients, components
or steps that do not materially affect the basic and novel
characteristics of the combination. The use of the terms
"comprising" or "including" to describe combinations of elements,
ingredients, components or steps herein also contemplates
embodiments that consist of, or consist essentially of the
elements, ingredients, components or steps.
[0173] Plural elements, ingredients, components or steps can be
provided by a single integrated element, ingredient, component or
step. Alternatively, a single integrated element, ingredient,
component or step might be divided into separate plural elements,
ingredients, components or steps. The disclosure of "a" or "one" to
describe an element, ingredient, component or step is not intended
to foreclose additional elements, ingredients, components or
steps.
[0174] It is understood that the above description is intended to
be illustrative and not restrictive. Many embodiments as we as many
applications besides the examples provided will be apparent to
those of skill in the art upon reading the above description. The
scope of the invention should, therefore, be determined not with
reference to the above description, but should instead be
determined with reference to the appended claims, along with the
full scope of equivalents to which such claims are entitled. The
disclosures of all articles and references, including patent
applications and publications are incorporated by reference for all
purposes. The omission in the following claims of any aspect of
subject matter that is disclosed herein is not a disclaimer of such
subject matter, nor should it be regarded that the inventors did
not consider such subject matter to be part of the disclosed
inventive subject mater.
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