U.S. patent application number 11/059834 was filed with the patent office on 2006-08-17 for surfacing and/or joining method.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Clayton A. George, Dmitriy Salnikov.
Application Number | 20060182949 11/059834 |
Document ID | / |
Family ID | 36648319 |
Filed Date | 2006-08-17 |
United States Patent
Application |
20060182949 |
Kind Code |
A1 |
Salnikov; Dmitriy ; et
al. |
August 17, 2006 |
Surfacing and/or joining method
Abstract
A method for surfacing a polymeric composite article and/or for
joining (for example, by bonding or by co-curing) the article and
an adherend (for example, a second polymeric composite article)
comprises (a) providing a cured or curable polymeric composite
article; (b) providing a curable composition comprising (1) at
least one thermosetting resin, and (2) at least one preformed,
substantially non-functional, particulate modifier comprising at
least one elastomer; and (c) directly or indirectly applying the
composition to at least a portion of at least one surface of the
article.
Inventors: |
Salnikov; Dmitriy;
(Woodbury, MN) ; George; Clayton A.; (Afton,
MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
36648319 |
Appl. No.: |
11/059834 |
Filed: |
February 17, 2005 |
Current U.S.
Class: |
428/327 ;
427/180; 427/384; 428/411.1; 428/413 |
Current CPC
Class: |
C08L 2666/02 20130101;
Y10T 428/31511 20150401; C08J 7/043 20200101; C09J 121/00 20130101;
C09J 133/04 20130101; Y10T 428/31721 20150401; Y10T 428/31504
20150401; Y10T 428/254 20150115; C08L 81/06 20130101; Y10T
428/31786 20150401; C08L 77/10 20130101; C09J 163/00 20130101; C08L
2666/04 20130101; C08J 7/0427 20200101; C08L 9/02 20130101; C09J
163/00 20130101; C08L 2666/02 20130101; C09J 163/00 20130101; C08L
2666/04 20130101 |
Class at
Publication: |
428/327 ;
428/413; 428/411.1; 427/180; 427/384 |
International
Class: |
B32B 27/18 20060101
B32B027/18; B32B 27/38 20060101 B32B027/38; B05D 1/12 20060101
B05D001/12 |
Claims
1. A method comprises (a) providing a cured or curable polymeric
composite article; (b) providing a curable composition comprising
(1) at least one thermosetting resin, and (2) at least one
preformed, substantially non-functional, particulate modifier
comprising at least one elastomer; and (c) directly or indirectly
applying said composition to at least a portion of at least one
surface of said article.
2. The method of claim 1, wherein said article is a cured polymeric
composite article.
3. The method of claim 1, wherein said thermosetting resin is
selected from the group consisting of epoxide resins, maleimide
resins, cyanate ester resins, and mixtures thereof.
4. The method of claim 3, wherein said thermosetting resin is an
epoxide resin.
5. The method of claim 1, wherein said modifier is a core-shell
polymer modifier.
6. The method of claim 5, wherein said core-shell polymer modifier
has a polyacrylate shell and a synthetic rubber core.
7. The method of claim 1, wherein said modifier is in the form of
microparticles.
8. The method of claim 1, wherein said modifier is included in said
curable composition in a concentration of about 2 to about 30
weight percent, based upon the total weight of said curable
composition.
9. The method of claim 1, wherein said method further comprises
bringing at least a portion of at least one surface of at least one
adherend into contact with said composition in a manner such that
said composition becomes sandwiched between said article and said
adherend.
10. The method of claim 9, wherein said adherend comprises at least
one of a polymeric composite article, a protective article, a paint
replacement system, and a lightning protection system.
11. The method of claim 10, wherein said paint replacement system
comprises a paint replacement applique and said lightning
protection system comprises a lightning protection applique.
12. The method of claim 1, wherein said method further comprises at
least partially curing the composition.
13. The method of claim 9, wherein said method further comprises at
least partially curing the composition.
14. The method of claim 1, wherein said thermosetting resin is an
epoxide resin and said modifier is a core-shell polymer
modifier.
15. A method comprising (a) applying an uncured mass of a curable
composition to at least one of a polymeric composite article and an
adherend, said curable composition comprising (1) at least one
thermosetting resin, and (2) at least one preformed, substantially
non-functional, particulate modifier comprising at least one
elastomer; (b) sandwiching said uncured mass of said curable
composition between said article and said adherend; and (c) curing
said composition to form a joint between said article and said
adherend.
16. A structure comprising (a) a cured or curable polymeric
composite article; and (b) a cured or curable composition
comprising (1) at least one thermosetting resin, and (2) at least
one preformed, substantially non-functional, particulate modifier
comprising at least one elastomer; said composition being in
contact with at least a portion of at least one surface of said
article.
17. The structure of claim 16, wherein said article is a cured
polymeric composite article.
18. The structure of claim 16, wherein said thermosetting resin is
selected from the group consisting of epoxide resins, maleimide
resins, cyanate ester resins, and mixtures thereof.
19. The structure of claim 18, wherein said thermosetting resin is
an epoxide resin.
20. The structure of claim 16, wherein said modifier is a
core-shell polymer modifier.
21. The structure of claim 20, wherein said core-shell polymer
modifier has a polyacrylate shell and a synthetic rubber core.
22. The structure of claim 16, wherein said modifier is in the form
of microparticles.
23. The structure of claim 16, wherein said modifier is included in
said cured or curable composition in a concentration of about 2 to
about 30 weight percent, based upon the total weight of said
composition.
24. The structure of claim 16, wherein said composition is at least
partially cured.
25. The structure of claim 16, wherein said structure is a joined
structure that further comprises at least one adherend that is
joined to said article by at least one joint comprising said cured
composition.
26. The structure of claim 25, wherein said adherend comprises at
least one of a polymeric composite article, a protective article, a
paint replacement system, and a lightning protection system.
27. The structure of claim 26, wherein said paint replacement
system comprises a paint replacement applique and said lightning
protection system comprises a lightning protection applique.
28. The structure of claim 16, wherein said thermosetting resin is
an epoxide resin and said modifier is a core-shell polymer
modifier.
Description
FIELD
[0001] This invention relates to methods for surfacing polymeric
composite articles and for joining (for example, by bonding or by
co-curing) such articles and various substrates. In another aspect,
this invention also relates to surfaced structures and joined
structures prepared thereby.
BACKGROUND
[0002] Adhesives have been used in many structural applications
including use in constructing vehicles, computer cases, buildings,
appliances, and the like. For example, structural adhesives have
been used in vehicle assembly (for example, automobile and aircraft
assembly) to replace or augment conventional joining techniques
such as welds, nuts and bolts, and rivets.
[0003] Epoxide resins are monomers or pre-polymers that react with
curing agents to yield high performance cured resins. The cured
resins exhibit numerous desirable chemical and physical
characteristics (for example, thermal and chemical resistance,
adhesion retention, low shrinkage, abrasion resistance, and high
dielectric strength) and are widely utilized (for example, in the
construction and electronics industries) as protective coatings for
electrical insulation, as composite matrix resins, and as
structural adhesives.
[0004] Frequently, it is desired that the cured epoxy resins have a
relatively high glass transition temperature (T.sub.g), so as to be
strong at relatively high temperatures. A common method of
increasing the glass transition temperature has been by introducing
a high degree of crosslinking.
[0005] Cured resins having a high crosslink density have had
shortcomings, however. For example, such resins have typically been
very brittle (that is, not very tough or ductile). Thus, it has
often been necessary or desirable to incorporate various
resin-insoluble modifiers to reduce brittleness and increase
toughness (thereby increasing impact resistance, as well as
resistance to failure resulting from vibration and fatigue
loading).
[0006] In addition to exhibiting brittleness problems, the cured
resins have sometimes exhibited undesirable moisture uptake
characteristics (especially when a high concentration of polar
groups has been utilized), resulting in reduced structural adhesive
performance.
SUMMARY
[0007] Thus, we recognize that there is a continuing need for
higher performance adhesives in order to meet the changing needs of
various industries such as, for example, the vehicle assembly
industry. In particular, for the joining of polymeric composite
parts in the aircraft industry, we recognize that there is a need
for joining methods that can provide high performance joints, even
in the presence of significant prebond humidity.
[0008] Briefly, in one aspect, the present invention provides a
method for surfacing a polymeric composite article (for example, to
reduce or eliminate surface imperfections and provide a more
paintable surface) and/or for joining (for example, by bonding or
by co-curing) the article and an adherend (for example, a second
polymeric composite article). The method comprises [0009] (a)
providing a cured or curable polymeric composite article; [0010]
(b) providing a curable composition comprising [0011] (1) at least
one thermosetting resin, and [0012] (2) at least one preformed,
substantially non-functional, particulate modifier comprising at
least one elastomer; and [0013] (c) directly or indirectly applying
the composition to at least a portion of at least one surface
(preferably, a composite surface) of the article. Preferably, the
article is a cured polymeric composite article, the thermosetting
resin is an epoxide resin, and/or the modifier is a core-shell
polymer modifier. The method preferably further comprises bringing
at least a portion of at least one surface of at least one adherend
into contact with the composition in a manner such that the
composition becomes sandwiched between the article and the
adherend, and/or at least partially curing the composition.
[0014] It has been discovered that thermosetting compositions
comprising certain types of particulate modifiers can be used as
surfacing materials and/or to form high performance joints between
polymeric composite parts and various adherends (including, for
example, other cured or curable polymeric composite parts).
Surprisingly, such compositions exhibit an ability to resist the
negative effects of prebond humidity (including, for example, the
negative effects of the moisture content of the article at the time
of surfacing or joining).
[0015] Such negative effects can include a reduction in cohesive
strength (for example, due to a lowering of glass transition
temperature (T.sub.g)), a reduction in cure rate, and/or a
reduction in toughness (for example, due to morphology changes).
Relative to structural adhesives commonly used in the aerospace
industry, the compositions can show significantly improved
retention of performance characteristics without the need for
prebond conditioning (for example, drying).
[0016] Thus, at least some embodiments of the method of the
invention meet the above-stated need in the art for joining methods
that can provide high performance joints, even in the presence of
significant prebond humidity. The ability to provide such joints
can enable reliable and consistent parts manufacture and can reduce
the costly need for restrictive temperature and humidity control of
preformed parts (and part assembly areas) in aircraft assembly.
[0017] In another aspect, this invention also provides a surfaced
or joined structure comprising [0018] (a) a cured or curable
polymeric composite article; and [0019] (b) a cured or curable
composition comprising [0020] (1) at least one thermosetting resin,
and [0021] (2) at least one preformed, substantially
non-functional, particulate modifier comprising at least one
elastomer; the composition being in contact with at least a portion
of at least one surface (preferably, a composite surface) of the
article. Preferably, the structure is a joined structure that
further comprises at least one adherend that is joined to the
article by at least one joint comprising the cured composition.
DETAILED DESCRIPTION
[0021] Definitions
[0022] As used in this application:
[0023] "cure" means to effect polymerization and/or to effect
crosslinking (as evidenced, for example, by a change in density,
viscosity, modulus, color, pH, refractive index, or other physical
or chemical property);
[0024] "co-cure" (in reference to the joining of a polymeric
composite article and an adherend by using a curable composition)
means to simultaneously effect at least partial cure of the curable
composition and at least partial cure of the article and/or the
adherend;
[0025] "bond" (in reference to the joining of a polymeric composite
article and an adherend by using a curable composition) means to
join by a technique other than co-curing;
[0026] "cured" means that a sufficient number of the primary
polymerizable or crosslinkable functional groups of a thermosetting
resin (for example, the epoxide groups of an epoxide resin) have
been consumed through chemical reaction to enable the resin to
function for its intended purpose;
[0027] "preformed" (in reference to a particulate modifier as a
component of a curable composition comprising thermosetting resin)
means formed prior to initiation of the curing of the thermosetting
resin as discrete particles that substantially maintain their
discreteness during and after curing; and
[0028] "substantially non-functional" (in reference to a
particulate modifier as a component of a curable composition
comprising thermosetting resin) means bearing essentially no
functional groups that are capable of both (1) contact and (2)
chemical reaction with the thermosetting resin.
Polymeric Composite Article
[0029] Polymeric composite articles (also sometimes called
composite parts) are known and include articles that comprise
reinforcing fibers (for example, carbon or glass) embedded in an
organic resin matrix (for example, comprising a thermosetting resin
that can be cured to form a glassy network polymer). Polymeric
composite articles can be as simple as one or more layers of
curable (that is, uncured or partially cured) resin-impregnated
fiber or fabric (such single- or multi-layer structures being
termed "prepreg"), or they can be as complex as sandwich
constructions comprising a metallic or non-metallic honeycomb core
and prepreg or cured prepreg. Articles typically used in structural
applications include composite stringers, composite skin, and the
like, which can be used to construct flaps, alirons, radomes,
horizontal or vertical stabilizers, wings, and other portions of
aircraft.
[0030] Suitable thermosetting resins for use in making composite
articles include, for example, epoxide resins, curable imide resins
(especially maleimide resins, but also including, for example,
commercial K-3 polyimides (available from duPont) and polyimides
having a terminal reactive group such as acetylene, diacetylene,
phenylethynyl, norbornene, nadimide, or benzocyclobutane), vinyl
ester resins and acrylic resins (for example, (meth)acrylic esters
or amides of polyols, epoxides, and amines), bisbenzocyclobutane
resins, cyanate ester resins, phenolic resins (including nitrile
phenolics), and the like, and mixtures thereof. The resins can be
utilized in the form of either monomers or prepolymers.
Thermoplastic resins (for example, polysulfones,
poly(ether-ether-ketone) (PEEK), polyphenylene sulfide, polyamides,
polyethersulfone, polyetherimides, polycarbonates, and the like,
and mixtures thereof) can also be utilized.
[0031] Preferred resins include thermosetting resins (more
preferably, epoxide resins, maleimide resins, cyanate ester resins,
and the like, and mixtures thereof). Epoxide resins are most
preferred due to their processing characteristics, high temperature
properties, and environmental resistance.
[0032] Suitable reinforcing fibers (preferably, continuous
reinforcing fibers) for use in preparing composite articles include
both organic and inorganic fibers (for example, carbon or graphite
fibers, glass fibers, ceramic fibers, boron fibers, silicon carbide
fibers, cellulose fibers, polyimide fibers, polyamide fibers,
polyethylene fibers, and the like, and combinations thereof).
Fibers of carbon, glass, or polyamide can be preferred due to
considerations of cost, physical properties, and processability.
Such fibers can be in the form of, for example, a unidirectional
array of individual continuous fibers, woven fabric, knitted
fabric, yarn, roving, braided constructions, or non-woven mat.
Generally, the compositions can contain, for example, from about 30
to about 80 (preferably, from about 45 to about 70) volume percent
fibers, depending upon structural application requirements.
[0033] Useful fiber-containing resin compositions can further
comprise additives such as curing agents, cure accelerators,
catalysts, crosslinking agents, dyes, flame retardants, pigments,
impact modifiers (for example, rubbers or thermoplastics), flow
control agents, and the like, and mixtures thereof.
[0034] Composite articles can be made by a variety of conventional
processes including, for example, resin transfer molding, filament
winding, tow placement, resin infusion processes, and traditional
prepreg processes. Prepregs can be prepared by impregnating an
array of fibers (or a fabric) with a resin (or with a blend or
solution of resin in volatile organic liquid) and then layering the
impregnated tape or fabric. The resulting prepreg can then be cured
by application of heat, along with the application of pressure or
vacuum (or both) to remove any trapped air.
[0035] Composite parts can also be made by a resin transfer molding
process, which is widely used to prepare composite parts for the
aerospace and automotive industries. In this process, fibers can
first be shaped into a preform that can then be compressed to final
part shape in a metal mold. The resin can then be pumped into the
mold and heat-cured. A low resin viscosity can facilitate this
process in that such a resin can flow through the compressed
preform in a short amount of time, without preform distortion.
[0036] A filament winding process is typically used to prepare
cylinders or other composites having a circular or oval
cross-sectional shape. In this process, a fiber tow or an array of
tows can be impregnated with resin by running it through a resin
bath (preferably, containing a low viscosity resin) and immediately
winding the impregnated tow onto a mandrel. The resulting composite
can then be heat-cured.
[0037] A pultrusion process (a continuous process used to prepare
constant cross-section parts) can also be used to make composites.
In such a process, a large array of continuous fibers can first be
wetted out in a resin bath (preferably, containing a low viscosity
resin). The resulting wet array can then be pulled through a heated
die, where trapped air can be squeezed out and the resin cured.
Curable Composition
[0038] (1) Thermosetting Resin
[0039] Resins suitable for use in preparing the curable composition
of the method of the invention include thermosetting resins. Such
resins can be cured by exposure to heat or radiation to form a
glassy network polymer. Suitable resins include, for example,
epoxide resins, curable imide resins (especially maleimide resins,
but also including, for example, commercial K-3 polyimides
(available from duPont) and polyimides having a terminal reactive
group such as acetylene, diacetylene, phenylethynyl, norbornene,
nadimide, or benzocyclobutane), vinyl ester resins and acrylic
resins (for example, (meth)acrylic esters or amides of polyols,
epoxides, and amines), bisbenzocyclobutane resins, cyanate ester
resins, and the like, and mixtures thereof. The resins can be
utilized in the form of either monomers or prepolymers. Preferred
resins include epoxide resins, maleimide resins, cyanate ester
resins, and the like, and mixtures thereof. Epoxide resins are
especially preferred due to their processing characteristics, high
temperature properties, and environmental resistance.
[0040] Epoxide resins are well-known in the art and comprise
compounds or mixtures of compounds that contain one or more epoxide
groups of the structure ##STR1## The compounds can be saturated or
unsaturated, aliphatic, alicylic, aromatic, or heterocyclic, or can
comprise combinations thereof. Compounds that contain more than one
epoxide group (that is, polyepoxides) are preferred.
[0041] Polyepoxides that can be utilized in the curable composition
of the method of the invention include, for example, both aliphatic
and aromatic polyepoxides, but aromatic polyepoxides are preferred
for high temperature applications. The aromatic polyepoxides are
compounds containing at least one aromatic ring structure (for
example, a benzene ring) and more than one epoxide group. Preferred
aromatic polyepoxides include the polyglycidyl ethers of polyhydric
phenols (for example, bisphenol A derivative resins, epoxy
cresol-novolac resins, bisphenol F derivative resins, epoxy
phenol-novolac resins), glycidyl esters of aromatic carboxylic
acids, glycidyl amines of aromatic amines, and the like, and
mixtures thereof. The most preferred aromatic polyepoxides are the
polyglycidyl ethers of polyhydric phenols.
[0042] Representative examples of aliphatic polyepoxides that can
be utilized in the curable composition include
3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, [0043]
2-(3',4'-epoxycyclohexyl)-5,1''-spiro-3'',4''-epoxycyclohexane-1,3-dioxan-
e, [0044] bis(3,4-epoxycyclohexylmethyl)adipate, the diglycidyl
ester of linoleic dimer acid, [0045]
1,4-bis(2,3-epoxypropoxy)butane, [0046]
4-(1,2-epoxyethyl)-1,2-epoxycyclohexane, [0047]
2,2-bis(3,4-epoxycyclohexyl)propane, polyglycidyl ethers of
aliphatic polyols such as glycerol or hydrogenated
4,4'-dihydroxydiphenyl-dimethylmethane, and the like, and mixtures
thereof.
[0048] Representative examples of aromatic polyepoxides that can be
utilized in the curable composition include glycidyl esters of
aromatic carboxylic acids (for example, phthalic acid diglycidyl
ester, isophthalic acid diglycidyl ester, trimellitic acid
triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the
like, and mixtures thereof); N-glycidylaminobenzenes (for example,
N,N-diglycidylbenzeneamine, [0049]
bis(N,N-diglycidyl-4-aminophenyl)methane, [0050]
1,3-bis(N,N-diglycidylamino)benzene, [0051]
N,N-diglycidyl-4-glycidyloxybenzeneamine, and the like, and
mixtures thereof); the [0052] polyglycidyl derivatives of
polyhydric phenols (for example, the polyglycidyl ethers of
polyhydric phenols such as [0053] 2,2-bis-[4-hydroxyphenyl]propane,
tetrakis(4-hydroxyphenyl)ethane, pyrocatechol, [0054] resorcinol,
hydroquinone, [0055] 4,4'-dihydroxydiphenyl methane, [0056]
4,4'-dihydroxydiphenyl dimethyl methane, [0057]
4,4'-dihydroxy-3,3'-dimethyldiphenyl methane, [0058]
4,4'-dihydroxydiphenyl methyl methane, [0059]
4,4'-dihydroxydiphenyl cyclohexane, [0060]
4,4'-dihydroxy-3,3'-dimethyldiphenyl propane, [0061]
4,4'-dihydroxydiphenyl sulfone, and [0062]
tris-(4-hydroxyphenyl)methane); polyglycidyl ethers of novolacs
(reaction products of monohydric or polyhydric phenols with
aldehydes in the presence of acid catalysts), and the derivatives
described in U.S. Pat. No. 3,018,262 (Schoeder) and U.S. Pat. No.
3,298,998 (Coover et al.), the descriptions of which are
incorporated herein by reference, as well as the derivatives
described in the Handbook of Epoxy Resins by Lee and Neville,
McGraw-Hill Book Co., New York (1967) and in Epoxy Resins,
Chemistry and Technology, Second Edition, edited by C. May, Marcel
Dekker, Inc., New York (1988); and the like; and mixtures thereof.
A preferred class of polyglycidyl ethers of polyhydric phenols for
use in the curable composition are the diglycidyl ethers of
bisphenol that have pendant carbocyclic groups (for example, those
described in U.S. Pat. No. 3,298,998 (Coover et al.), the
description of which is incorporated herein by reference). Examples
of such compounds include
2,2-bis[4-(2,3-epoxypropoxy)phenyl]norcamphane and
2,2-bis[4-(2,3-epoxypropoxy)phenyl]decahydro-1,4,5,8-dimethanonaphthalene-
. Preferred compounds include dicyclopentadiene-containing
polyepoxides (for example, TACTIX 756 and TACTIX 556, available
from Huntsman Advanced Materials Americas, Inc., Brewster,
N.Y.).
[0063] Suitable epoxide resins can be prepared by, for example, the
reaction of epichlorohydrin with a polyol, as described, for
example, in U.S. Pat. No. 4,522,958 (Das et al.), the description
of which is incorporated herein by reference, as well as by other
methods described by Lee and Neville and by May, supra. Many
epoxide resins are also commercially available.
[0064] Maleimide resins suitable for use in the curable composition
of the method of the invention include bismaleimides,
polymaleimides, and polyaminobismaleimides. Such maleimides can be
conveniently synthesized by combining maleic anhydride or
substituted maleic anhydrides with di- or polyamine(s). Preferred
are N,N'-bismaleimides, which can be prepared, for example, by the
methods described in U.S. Pat. No. 3,562,223 (Bargain et al.), U.S.
Pat. No. 3,627,780 (Bonnard et al.), U.S. Pat. No. 3,839,358
(Bargain), and U.S. Pat. No. 4,468,497 (Beckley et al.) (the
descriptions of which are incorporated herein by reference) and
many of which are commercially available.
[0065] Representative examples of suitable N,N'-bismaleimides
include the N,N'-bismaleimides of 1,2-ethanediamine,
1,6-hexanediamine, trimethyl-1,6-hexanediamine, 1,4-benzenediamine,
4,4'-methylenebisbenzenamine, 2-methyl-1,4-benzenediamine,
3,3'-methylenebisbenzenamine, 3,3'-sulfonylbisbenzenamine,
4,4'-sulfonylbisbenzenamine, 3,3'-oxybisbenzenamine,
4,4'-oxybisbenzenamine, 4,4'-methylenebiscyclohexanamine,
1,3-benzenedimethanamine, 1,4-benzenedimethanamine,
4,4'-cyclohexanebisbenzenamine, and the like, and mixtures
thereof.
[0066] Co-reactants for use with the bismaleimides can include any
of a wide variety of unsaturated organic compounds, particularly
those having multiple unsaturation, either ethylenic, acetylenic,
or both. Examples include acrylic acids and amides and the ester
derivatives thereof, for example, acrylic acid, methacrylic acid,
acrylamide, methacrylamide, and methylmethacrylate;
dicyanoethylene; tetracyanoethylene; allyl alcohol;
2,2'-diallylbisphenol A; 2,2'-dipropenylbisphenol A;
diallylphthalate; triallylisocyanurate; triallylcyanurate;
N-vinyl-2-pyrrolidinone; N-vinyl caprolactam; ethylene glycol
dimethacrylate; diethylene glycol dimethacrylate;
trimethylolpropane triacrylate; trimethylolpropane trimethacrylate;
pentaerythritol tetramethacrylate; 4-allyl-2-methoxyphenol;
triallyl trimellitate; divinyl benzene; dicyclopentadienyl
acrylate; dicyclopentadienyloxyethyl acrylate; 1,4-butanediol
divinyl ether; 1,4-dihydroxy-2-butene; styrene; .alpha.-methyl
styrene; chlorostyrene; p-phenylstyrene; p-methylstyrene;
t-butylstyrene; phenyl vinyl ether; and the like; and mixtures
thereof. Of particular interest are resin systems employing a
bismaleimide in combination with a bis(alkenylphenol). Descriptions
of a typical resin system of this type can be found in U.S. Pat.
No. 4,100,140 (Zahir et al.), the descriptions of which are
incorporated herein by reference. Particularly preferred components
are 4,4'-bismaleimidodiphenylmethane and o,o'-diallyl bisphenol
A.
[0067] Cyanate ester resins suitable for use in the curable
composition of the method of the invention can be prepared by
combining cyanogen chloride or bromide with an alcohol or phenol.
The preparation of such resins and their use in
polycyclotrimerization to produce polycyanurates are described in
U.S. Pat. No. 4,157,360 (Chung et al.), the descriptions of which
are incorporated herein by reference. Representative examples of
suitable cyanate ester resins include 1,2-dicyanatobenzene,
1,3-dicyanatobenzene, 1,4-dicyanatobenzene,
2,2'-dicyanatodiphenylmethane, 3,3'-dicyanatodiphenylmethane,
4,4'-dicyanatodiphenylmethane, and the dicyanates prepared from
biphenol A, bisphenol F, and bisphenol S, and the like, and
mixtures thereof. Tri- and higher functionality cyanate ester
resins are also suitable.
[0068] (2) Particulate Modifier
[0069] Particulate modifiers that are suitable for use in preparing
the curable composition of the method of the invention include
preformed, substantially non-functional particulate modifiers that
comprise at least one elastomer. Such modifiers preferably comprise
both a rubbery phase (for example, having a glass transition
temperature (T.sub.g) less than or equal to about 0.degree. C.
(preferably, less than or equal to about -20.degree. C.)) and a
thermoplastic or glassy phase (for example, having a glass
transition temperature above about 25.degree. C. (preferably, above
about 50.degree. C.)). The rubbery phase can optionally be
crosslinked. Although the modifiers are substantially
non-functional, a small amount of reactive functionality can be
tolerated to the extent that the moisture uptake characteristics of
the modifier (as evidenced by, for example, thermogravimetric
analysis (TGA)) are not significantly affected.
[0070] Useful particulate modifiers can have any of a wide range of
particle sizes (as measured prior to addition to the thermosetting
resin). For many applications, however, microparticles can be
effectively utilized. Preferred particles can have an average
diameter of at least about 0.1 micron, 0.2 micron, or 2 microns up
to (and including) about 10 microns, 50 microns, 100 microns, 200
microns, or 500 microns (where any lower size limit can be paired
with any upper size limit, depending upon the properties desired
for a particular application). (As used herein, the term "diameter"
refers not only to the diameter of substantially spherical
particles but also to the longest dimension of non-spherical
particles.) Since the particulate modifiers are preformed, their
particle size is predetermined, but some change in size can occur
upon addition to the thermosetting resin (for example, due to
swelling).
[0071] Suitable modifiers include core-shell polymer modifiers
having a polymerized rubbery core surrounded by a polymerized
thermoplastic or glassy shell, and the like, and mixtures thereof.
Useful modifiers of these types are described in Polymer
Toughening, edited by Charles B. Arends, Chapter 5, pages 131-174,
Marcel Dekker, Inc., New York (1996), the descriptions of which are
incorporated herein by reference. Useful modifiers can also include
elastomeric polymer modifiers that lack the above-described
thermoplastic or glassy shell, provided that the modifier is at
least somewhat swellable in the selected thermosetting resin while
substantially maintaining its discreteness.
[0072] Preferred modifiers include core-shell polymer modifiers,
and the like, and mixtures thereof. More preferred are core-shell
polymer modifiers having a polyacrylate or polymethacrylate
(hereinafter, designated jointly as poly(meth)acrylate) shell and a
synthetic rubber core (most preferably, a poly(meth)acrylate shell
and a core selected from styrene-butadiene rubber,
acrylonitrile-butadiene rubber, and combinations thereof, including
copolymers).
[0073] Useful glassy shells include those that comprise polymerized
acrylic acid ester or methacrylic acid ester (preferably,
C.sub.1-C.sub.4 alkyl-substituted methacrylate; more preferably,
polymethylmethacrylate or a copolymer of alkyl methacrylate and
butyl acrylate); polymerized monovinyl aromatic hydrocarbon; a
polymerized mixture of acrylic or methacrylic acid ester and
monovinyl aromatic hydrocarbon (for example, a copolymer of methyl
methacrylate and styrene); and the like; and combinations
thereof.
[0074] Useful rubbery cores include those that comprise
polyacrylate (for example, poly(butyl acrylate), poly(isooctyl
acrylate), or a copolymer of ethyl acrylate and butyl acrylate);
polysiloxane (for example, polydimethylsiloxane); polymerized diene
(for example, polybutadiene); a polymerized mixture of diene and
monovinyl aromatic hydrocarbon (for example, a copolymer of
butadiene and styrene); a polymerized mixture of diene and acrylic
monomer (for example, a copolymer of butadiene and acrylonitrile);
a polymerized mixture of acrylic or methacrylic acid ester and
monovinyl aromatic hydrocarbon (for example, a copolymer of butyl
acrylate and styrene); and the like; and combinations thereof (for
example, copolymers of alkyl methacrylate, butadiene, and
styrene).
[0075] Useful modifiers include core/shell polymers such as
methacrylate-butadiene-styrene (MBS) copolymer wherein the core is
crosslinked styrene/butadiene rubber and the shell is
polymethylacrylate (for example, ACRYLOID KM653 and KM680,
available from Rohm and Haas, Philadelphia, Pa.), those having a
core comprising polybutadiene and a shell comprising poly(methyl
methacrylate) (for example, KANE ACE M511, M521, B11A, B22, B31,
and M901 available from Kaneka Corporation, Houston, Tex. and
CLEARSTRENGTH C223 available from ATOFINA, Philadelphia, Pa.),
those having a polysiloxane core and a polyacrylate shell (for
example, CLEARSTRENGTH S-2001 available from ATOFINA and GENIOPERL
P22 available from Wacker-Chemie GmbH, Wacker Silicones, Munich,
Germany), those having a polyacrylate core and a poly(methyl
methacrylate) shell (for example, PARALOID EXL2330 available from
Rohm and Haas and STAPHYLOID AC3355 and AC3395 available from
Takeda Chemical Company, Osaka, Japan), those having an MBS core
and a poly(methyl methacrylate) shell (for example, PARALOID
EXL2691A, EXL2691, and EXL2655 available from Rohm and Haas); and
the like; and mixtures thereof. Preferred modifiers include the
above-listed ACRYLOID and PARALOID modifiers; and the like; and
mixtures thereof.
[0076] (3) Other Components
[0077] The curable composition can further comprise one or more
additives including, for example, soluble thermoplastic additives
(for example, to modify viscosity or rheology to ensure a
handleable film); curing agents; cure accelerators; catalysts;
crosslinking agents; dyes; flame retardants; pigments; flow control
agents; reinforcing fillers, fibers, or particles (including
silica, calcium carbonate, barium sulfate, glass beads, and the
like); electrically or thermally conductive particles; scrim or
embedded carrier (for example, woven or nonwoven glass, woven or
nonwoven polymeric fabrics such as those of polyamide or polyester,
and metal meshes or foils such as those of aluminum or copper); and
the like; and mixtures thereof. The additives can be, for example,
partially or wholly embedded in the composition or borne on a
surface thereof. The composition itself can also be borne on a
carrier (for example, a release liner).
[0078] Epoxide resins can be cured by a variety of curing agents,
some of which are described (along with a method for calculating
the amounts to be used) by Lee and Neville in Handbook of Epoxy
Resins, McGraw-Hill, pages 36-140, New York (1967). Useful epoxide
resin curing agents include polyamines such as ethylenediamine,
diethylenetriamine, aminoethylethanolamine, and the like, as well
as aromatic amines such as diaminodiphenylsulfone,
9,9-bis(4-aminophenyl)fluorene,
9,9-bis(3-chloro-4-(aminophenyl)fluorene,
9,9-bis(3-methyl-4-(aminophenyl)fluorene, and the like; hydrazides
such as isophthalic dihydrazide; amides such as dicyandiamide;
polycarboxylic acids such as adipic acid; acid anhydrides such as
phthalic anhydride and chlorendic anhydride; polyphenols such as
bisphenol A; and the like; and mixtures thereof. Generally, the
epoxide resin and curing agent are used in stoichiometric amounts,
but the curing agent can be used in amounts ranging from about 0.1
to 1.7 times the stoichiometric amount of epoxide resin.
[0079] Epoxide resin curing agents also include catalysts (for
example, Lewis acids and bases; tertiary amines; thermal cationic
catalysts including Br.phi.nsted acids; anionic catalysts including
imidazoles such as 4,5-diphenylimidazole; complexed Lewis acids;
and photocatalysts including organometallic compounds and salts).
Thermally-activated catalysts can generally be used in amounts
ranging from about 0.05 to about 5 percent by weight, based upon
the amount of epoxide resin present in the curable composition.
[0080] N,N'-bismaleimide resins can be cured using diamine curing
agents, for example, such as those described in U.S. Pat. No.
3,562,223 (Bargain et al.), the description of which is
incorporated herein by reference. Generally, from about 0.2 to
about 0.8 moles of diamine can be used per mole of
N,N'-bismaleimide. N,N'-bismaleimides can also cure by other
mechanisms, for example, co-cure with aromatic olefins (such as
bis-allylphenyl ether, 4,4'-bis(o-propenylphenoxy)benzophenone,
o,o'-diallyl bisphenol A, and the like) or thermal cure via a
self-polymerization mechanism.
[0081] Cyanate ester resins can be cyclotrimerized by application
of heat and/or by using catalysts such as zinc octoate, tin
octoate, zinc stearate, tin stearate, copper acetylacetonate, and
chelates of iron, cobalt, zinc, copper, manganese, and titanium
with bidentate ligands such as catechol. Such catalysts can
generally be used in amounts of from about 0.001 to about 10 parts
by weight per 100 parts of cyanate ester resin.
Preparation of Curable Composition
[0082] The curable composition of the method of the invention can
be prepared by combining at least one particulate modifier, at
least one resin, and any other components (optionally, with
stirring or agitation). The resins can be liquid, solid, or a
combination thereof, and thus the resulting composition can be, for
example, in the form of a paste or a film. Depending upon its
particular formulation and viscoelastic characteristics, such a
film can be handled with or without the aid of a supporting
material (for example, an embedded scrim or release liner).
[0083] Preferably, the particulate modifier can be well-dispersed
in the resin, so as to be substantially non-agglomerated. Solvent
can be used to aid in combination and dispersion, if desired,
provided that the chosen solvent is one that cannot react
appreciably with the components of the composition and that cannot
appreciably dissolve or swell the particulate modifier (especially
the elastomer component(s) of the modifier). Suitable solvents
include, for example, acetone, heptane, toluene, isopropanol, and
the like, and mixtures thereof.
[0084] Preferably, little or no solvent is utilized. Solventless
compositions can be prepared by simply combining the components
with or without the use of mild heating. In a more preferred method
of forming the curable composition, the components are combined in
a solvent-free process, wherein the resultant mixture is both
heated and stirred until a relatively uniform mixture is
formed.
[0085] The particulate modifier can generally be included in the
composition in a concentration of about 2 to about 30 weight
percent, based upon the total weight of the composition.
Preferably, the modifier is present in a concentration of about 5
to about 20 weight percent, based upon the total weight of the
composition.
[0086] Preferably, at least one thermally- or
photolytically-activatable curing agent is included in the curable
composition in order to facilitate low temperature processing. Such
curing agents are preferably incorporated into the composition at
temperatures lower than the activation temperature of the curing
agents. Preferred curing agents include imidazoles, amides (for
example, dicyandiamide), aromatic amines, modified ureas, anhydride
curing agents, hydrazide curing agents, thermal cationic catalysts,
anionic catalysts, photocatalysts, and mixtures thereof. Most
preferred are amides, hydrazides, modified ureas, aromatic amines,
and mixtures thereof. The further addition of a flow control agent
to the curable composition can facilitate the achievement of
desired film formation and other Theological characteristics.
[0087] In a preferred method, the curable composition can be formed
by combining the particulate modifier(s) and the resin(s) at
elevated temperatures (for example, temperatures sufficient to melt
the resin so as to facilitate its relatively uniform mixing with
the modifier) and then cooling the resulting combination to a
temperature below the activation or melting temperature of the
curing agent(s). The curing agent(s) can then be blended into the
combination.
Application of Curable Composition
[0088] The curable composition used in the method of the invention
can be applied to the composite article (and/or to an adherend,
which is a body that is to be adhered to the composite article at
their interface) by any of a variety of application methods. Useful
application methods include, for example, coating (using roll,
spray, brush, or extrusion techniques), lamination, reticulation,
vacuum lamination, troweling, and the like, and combinations
thereof. Cutting techniques (for example, die cutting, Gerber
cutting using a heated cutting element, and laser cutting) can also
be employed to provide particular shapes prior to application. At
least one of the surfaces to which the composition is applied is a
composite surface. Solvent-free application of the composition is
preferred and can be accomplished, for example, by transfer
lamination of the composition in film form to a desired
surface.
[0089] In surfacing a composite article, the curable composition
can be applied by, for example, transfer lamination followed by
vacuum compaction (if the composition is in film form) or by
troweling followed by smoothing (if the composition is in paste
form). The surfacing method of the invention can be used to cover
surface imperfections (for example, those caused by honeycomb
mark-off or fiber weave pattern telegraphing) and to provide a
relatively smooth, paintable surface.
[0090] In joining the composite article and an adherend, the
curable composition can be applied to the article directly, or it
can be applied to the article indirectly by, for example, direct
application to the adherend to form a composition-bearing adherend,
followed by bringing the article and the composition-bearing
adherend together in a manner such that the composition is
sandwiched between the article and the adherend. Thus, the joining
method of the invention can comprise (a) applying an uncured mass
of the curable composition (for example, in the form of a film or a
paste) to at least one of a polymeric composite article and an
adherend; (b) sandwiching the uncured mass of the curable
composition between the article and the adherend; and (c) curing
the composition to form a joint between the article and the
adherend. If desired, such joining method can be carried out by
simply inserting the composition (for example, in the form of a
film) between the article and the adherend as they are brought
together.
[0091] Adherends can be chosen from a wide variety of polymeric
composite articles, films, sheets, and other surfaces, depending
upon the particular joining application. The curable composition
can form adhesive bonds between a polymeric composite article and
metallic components (for example, iron, aluminum, titanium,
magnesium, copper, stainless steel, and the like, and alloys
thereof) and between a polymeric composite article and non-metallic
substrates (for example, reinforced and unreinforced thermoplastic
and thermoset polymers, as well as other organic materials (or
organic composite materials) and inorganic materials including
glass and ceramics).
[0092] Preferably, the adherend comprises a polymeric composite
article. More preferably, the adherend comprises a polymeric
composite article and the resulting joined structure forms at least
a portion of a vehicle (most preferably, a portion of an
aircraft).
[0093] Preferred adherends also include those that comprise
protective articles, paint replacement systems, and/or lightning
protection systems. Such adherends can comprise, for example, one
or more polymeric composite layers, one or more layers of the
curable composition (cured or uncured), one or more layers of metal
(for example, metal mesh, which can optionally be embedded in the
curable composition prior to cure), and/or one or more protective
article, paint replacement applique, and/or lightning protection
applique layers. Such lightning protection appliques can comprise,
for example, a polymer film (preferably, a fluoropolymer film), a
pressure-sensitive adhesive (preferably, an acrylic
pressure-sensitive adhesive), and a metal layer that can optionally
be embedded in the pressure-sensitive adhesive or bonded directly
to the polymer film using any of the methods described in the art.
Alternatively, the pressure-sensitive adhesive (of the lightning
protection applique, or of a paint replacement applique) can be
omitted and optionally replaced with a thermosetting adhesive
composition (for example, the curable composition used in the
method of the invention). Useful protective articles, paint
replacement appliques, and lightning protection systems include
those described in U.S. Patent Application Publication No. US
2002/0179240 (Clemens et al.), U.S. Pat. No. 6,475,616 (Dietz et
al.), International Patent Application Publication No. WO 99/64235
(Minnesota Mining and Manufacturing Company), U.S. Pat. No.
6,177,189 (Rawlings et al.), U.S. Pat. No. 6,790,526 (Vargo et
al.), U.S. Patent Application Publication No. US 2002/0081921
(Vargo et al.), U.S. Pat. No. 4,912,594 (Bannink, Jr. et al.), U.S.
Pat. No. 6,432,507 (Brick et al.), and European Patent Application
Publication No. EP 1 011 182 (Minnesota Mining and Manufacturing
Company), the descriptions of which are incorporated herein by
reference.
[0094] The method of the invention can comprise one or more
surfacing steps, one or more joining steps, the use of one or more
polymeric composite articles, and/or the use of one or more
adherends.
Curing
[0095] The curable composition used in the method of the invention
is thermosettable. A "thermosettable" or "thermosetting"
composition is one that can be cured (that is, crosslinked) by
exposure to, for example, thermal radiation (or heat), actinic
radiation, moisture, or other means (preferably, thermal radiation)
to yield a substantially infusible (that is, thermoset) material.
Combinations of various curing means can also be used (for example,
a combination of heat and actinic radiation).
EXAMPLES
[0096] Objects and advantages of this invention are further
illustrated by the following examples, but the particular materials
and amounts thereof recited in these examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
Test Methods
Weight Loss by Thermogravimetric Analysis (TGA)
[0097] Cured polymeric composite articles were evaluated for
moisture content using a Thermogravimetric Analyzer TGA-2950
(available from TA Instruments, New Castle, Del.). The cured
article was removed from the conditioning chamber (where
applicable) and small pieces were broken off using a pliers to
provide samples which were 2 to 3 plies thick and that weighed
between 4.968 and 19.209 milligrams. These samples were essentially
immediately placed in a small closed vial until tested, between 15
and 30 minutes later. The samples were heated from approximately
25.degree. C. to 200.degree. C. at a rate of 10.degree. C./minute
in a nitrogen atmosphere at a flow rate of from 40 to 60
milliliters/minute. Weight loss over this temperature range was
calculated using the software provided with the equipment. Results
are reported as % weight loss (of moisture).
Overlap Shear Strength (OLS)
[0098] Cured joined structures were evaluated for overlap shear
strength. More specifically, cured joined structures measuring 7
inches (17.8 centimeters) long were obtained which were then cut in
the lengthwise direction into 1 inch (2.54 centimeters) wide
(nominal) test strips. Next, one groove was cut in the crosswise
direction through the thickness of the cured polymeric composite
article on each side of a cured joined structure test strip in an
offset manner, so as to form a 0.5 inch (12.7 millimeters) long
overlap section at the center of the test strip. This formed a test
strip similar to that described in ASTM D 3165-95, which was then
positioned in a tensile tester (available from MTS Systems
Corporation, Eden Prairie, Minn.) such that the gripping jaws were
approximately 5 inches (12.7 centimeters) apart and each jaw
gripped approximately 1 inch (2.5 centimeters) of the test strip. A
30,000 pound-force (Ibf) (13.3 kiloNewtons) load cell was employed.
A grip separation rate of 0.05 inches/minute (1.27
millimeters/minute) was applied until failure occurred. Testing was
conducted at one of two different test temperatures (93.degree. C.
or 136.degree. C.), as determined by means of a thermocouple
attached to the test strip. Samples were equilibrated at
temperature for between 10 and 20 minutes prior to testing. For
each cured joined structure three test strips were evaluated and
used to obtain an average value. The results are reported in
pounds/square inch (psi) and in MPa.
Environmental Conditioning
[0099] Cured polymeric composite articles were conditioned prior to
testing using one of the following methods.
Method 1: Dry
[0100] A cured polymeric composite article was dried in an oven at
235.degree. F. (113.degree. C.) for 9 days, then removed and
allowed to cool for 1 hour to about 72.degree. F. (22.degree. C.)
after which it was essentially immediately either evaluated by
thermogravimetric analysis (TGA) or used to prepare a cured joined
structure.
Method 2: Ambient
[0101] A cured polymeric composite article was stored at ambient
conditions, approximately 72.degree. F. (22.degree. C.) and 50%
Relative Humidity (RH), for 21 days, after which it was essentially
immediately evaluated by TGA.
Method 3: Wet
[0102] A cured polymeric composite article was conditioned in a
temperature/humidity chamber at 160.degree. F. (71.degree. C.) and
100% RH for 9 days, then allowed to cool on a benchtop to room
temperature for approximately 30 minutes, after which it was
essentially immediately either evaluated by TGA or used to prepare
a cured joined structure.
Materials
[0103] DER 332 A liquid bisphenol A-based polyepoxide resin having
an epoxide equivalent weight of from 171 to 175 grams/equivalent,
available as DER.TM. 332 resin from Dow Chemical Company, Midland,
Mich. [0104] EPON 828 A liquid bisphenol A-based polyepoxide resin
having an epoxide equivalent weight of from 185 to 192
grams/equivalent, available as EPON.TM. 828 resin from Resolution
Performance Products, Houston, Tex. [0105] EPON SU-2.5 A liquid
bisphenol A-based novolac polyepoxide resin having an average
epoxide group functionality of about 2.5, available as EPON.TM.
SU-2.5 resin from Resolution Performance Products, Houston, Tex.
[0106] EPON SU-8 A solid bisphenol A-based novolac polyepoxide
resin having an average epoxide group functionality of about 8,
available as EPON.TM. SU-8 resin from Resolution Performance
Products, Houston, Tex. [0107] EPON 1004F A medium molecular weight
bisphenol A-based polyepoxide resin having an epoxide equivalent
weight of from 800 to 950 grams/equivalent, available as EPON.TM.
1004F resin from Resolution Performance Products, Houston, Tex.
[0108] EPON 1009F A very high molecular weight solid bisphenol
A-based polyepoxide resin having an epoxide equivalent weight of
from 2300 to 3800 grams/equivalent and a melting point of between
130 and 140.degree. C., available as EPON.TM. 1009F resin from
Resolution Performance Products, Houston, Tex. [0109] TACTIX 756 A
dicyclopentadiene-based polyepoxide resin, having an epoxide
equivalent weight of from 245 to 265 grams/equivalent, available as
TACTIX.TM. 756 resin from Huntsman Advanced Materials Americas,
Incorporated, Brewster, N.Y. [0110] CG 1400 Dicyandiamide
(1-cyanoguanidine)), available as Amicure.TM. CG-1400 from Air
Products and Chemicals, Incorporated, Allentown, Pa. [0111] OMICURE
U52 An aromatic substituted urea (4,4'-methylene-bis(phenyl
dimethyl urea), available as OMICURE.TM. U52 from CVC Specialty
Chemicals Incorporated, Moorestown, N.J. [0112] DEH 85 An
unmodified phenolic hardener having an active hydrogen equivalent
weight of from 250 to 280 grams/equivalent, available as DEH.TM. 85
Epoxy Curing Agent from Dow Chemical Company, Midland, Mich. [0113]
IPDH Isophthaloyldihydrazide, having an amine equivalent weight of
49.2 grams/equivalent. [0114] o-TBAF
9,9-bis(3-methyl-4-aminophenyl)fluorene, having a theoretical amine
hydrogen equivalent weight of 94.5 grams/equivalent. [0115]
EXL-2691A A core/shell impact modifer having a crosslinked
poly(butadiene/styrene) core with a grafted poly(methyl
methacrylate) shell, available in powder form as PARALOID
EXL.TM.-2691A from Rohm and Haas, Philadelphia, Pa. [0116] DUOMOD
5047 A carboxyl-functional elastomeric powder having a target
average particle size of 50 micrometers and a target glass
transition temperature of approximately 19.degree. C. (obtained as
DuoMod.TM. 5047 toughener from Zeon Chemicals L.P., Louisville,
Ky.). [0117] DUOMOD 5097 An epoxy-functional elastomeric powder
supplied in a fine agglomerate form with at least 99 percent of the
agglomerate particles having a size of less than 105 micrometers,
and with a target individual particle size of 0.3 micrometers
(obtained as DuoMod.TM. 5097 toughener from Zeon Chemicals L.P.,
Louisville, Ky.). [0118] BOLTORN E1 An epoxy-functional, dendritic,
viscous liquid (at room temperature) polymer having a highly
branched aliphatic polyester backbone, a molecular weight of
approximately 10,500 grams/mole, an epoxy equivalent weight of
approximately 850 to 900 grams/equivalent, and an average of 11
reactive epoxide groups per molecule, available as BOLTORN.TM. E1
polymer, an experimental material, from Perstorp Specialty
Chemicals AB, Sweden. [0119] Rubber Toughener Diprimary amine
endcapped poly(tetramethylene oxide), having a number average
molecular weight of about 7500. [0120] CTBN #1 A liquid,
carboxyl-terminated butadiene/nitrile rubber polymer, having a
molecular weight of about 3800, a glass transition temperature of
-66.degree. C., and a carboxyl content of 28 (acid number),
available as HYCAR.TM. CTBN 1300.times.31 from Noveon,
Incorporated, Cleveland, Ohio. [0121] CTBN #2 A liquid,
carboxyl-terminated butadiene/nitrile rubber polymer, having a
molecular weight of about 3150, a glass transition temperature of
-30.degree. C., and a carboxyl content of 32 (acid number),
available as HYCAR.TM. CTBN 1300.times.13 from Noveon,
Incorporated, Cleveland, Ohio. [0122] VTBN A liquid,
vinyl-terminated butadiene/nitrile rubber polymer, having a
Brookfield viscosity of 425,000 mpa-sec at 27.degree. C. and a
glass transition temperature of -45.degree. C., available as
HYCAR.TM. VTBN 1300.times.43 from Noveon, Incorporated, Cleveland,
Ohio. [0123] P1800 A powdered grade of polysulfone thermoplastic
polymer having a glass transition temperature of 185.degree. C.,
available as UDEL.TM. P1800 from Solvay Advanced Polymers, LLC,
Alpharetta, Ga. [0124] TWARON Aramid Pulp TWARON.TM. 2091 aramid
microfibers (poly-(paraphenylene terephthalamide)), having a linear
molecular skeleton structure, available in pulp form from TEIJIN
TWARON BV, The Netherlands. [0125] AF-163-2M 3M.TM. Scotch-Weld.TM.
Structural Adhesive Film having a non-woven supporting carrier,
based on a modified thermosetting epoxy structural adhesive
designed for curing at temperatures of 225.degree. F. (107.degree.
C.) to 300.degree. F. (149.degree. C.), available from 3M Company,
St. Paul, Minn. [0126] AF-3109-2K 3M.TM. Scotch-Weld.TM. Structural
Adhesive Film having a knit scrim support, based on a nonvolatile,
modified thermosetting epoxy structural adhesive designed for
curing at temperatures of 225.degree. F. (107.degree. C.) to
350.degree. F. (177.degree. C.) and having an areal weight of 0.80
to 0.90 pounds/square foot (390 to 439 grams/square meter),
available from 3M Company, St. Paul, Minn. [0127] AF-191 3M.TM.
Scotch-Weld.TM. Structural Adhesive Film; an unsupported,
thermosetting, nonvolatile, modified epoxy film adhesive designed
for curing at a temperature of 350.degree. F. (177.degree. C.) and
having an areal weight of 0.05 pounds/square foot (244 grams/square
meter)), available from 3M Company, St. Paul, Minn. [0128] AF-325
3M.TM. Scotch-Weld.TM. Low Density Composite Surfacing Film; a
non-woven polyester supported, low volatility, thermosetting epoxy
film for composite surfacing, designed for curing at temperatures
of 250.degree. F. (121.degree. C.) to 350.degree. F. (177.degree.
C.) and having an areal weight of between 147 and 195 grams/square
meter, available from 3M Company, St. Paul, Minn.
Preparation of Curable Resin Compositions
[0129] Two different preblends of polyepoxide resin and flow
modifier were provided and used to prepare curable resin
compositions:
[0130] Preblend #1: 92.4 grams of EPON 1004F was placed into a 150
milliliter reactor and heated to approximately 230.degree. F.
(110.degree. C.) using a paddle blade at approximately 200
revolutions per minute (rpm) for constant agitation until the
polyepoxide resin was essentially completely melted. Then 7.6 grams
of TWARON.TM. 2091 aramid fiber flow modifier was added to the
polyepoxide resin and mixed for 15 minutes. The dispersion that was
obtained was removed from the reactor and placed on a
silicone-treated release liner and allowed to cool to room
temperature for approximately 3 hours. The resulting solid material
was then ground using a micro-pulverizing type hammer mill having a
0.38 inch (9.5 millimeters) diameter screen. The maximum particle
size was 0.38 inch (9.5 millimeters) in diameter. The majority of
the particles had a significantly smaller diameter.
[0131] Preblend #2: 150 grams of EPON 828 was placed into a 250
milliliter reactor and heated to approximately 200.degree. F.
(93.degree. C.) using a paddle blade at approximately 200 rpm for
constant agitation. Next, 30 grams of P1800 polysulfone resin flow
modifier was slowly added to the polyepoxide resin. The temperature
was then increased to approximately 350.degree. F. (177.degree. C.)
and the agitation speed reduced to approximately 150 rpm. The
dispersion was heated and agitated under these conditions until it
became a substantially homogeneous mixture. This mixture was
allowed to cool to room temperature to provide a viscous,
yellow-colored, transparent liquid.
[0132] Polyepoxide resins and the above-described preblends were
charged into a 200 gram capacity plastic container in the
appropriate ratios to provide the amounts shown for the various
Examples in Table 1 below. The container was heated for about 15
minutes in a forced air oven set at 150.degree. C., after which it
was removed and placed in a planetary-type mixer (SPEED MIXER.TM.,
Model DA 400 FV, available from Synergy Devices Limited,
Buckinghamshire, United Kingdom) set at a speed of 2750 rpm for 1
minute. The container and its contents were then returned to the
oven and equilibrated at about 120.degree. C. for between 15 and 20
minutes. Next, a toughening modifier was added to this blend, and
it was mixed as described above, after which the container was
removed from the planetary mixer and allowed to cool below
100.degree. C. The curing agents were then added, and the blend was
again mixed as described above. After removal from the mixer, the
inside wall of the container was scraped down, followed by putting
the container back into the mixer for another cycle. The curable
resin composition obtained was used essentially immediately to
prepare a curable, liner-supported adhesive film.
Preparation of Curable, Liner-supported Adhesive Films
[0133] The heated composition (having a temperature of about
90.degree. C. (194.degree. F.)) from the "Preparation of Curable
Resin Compositions" procedure above was coated between two 0.005
inch (0.13 millimeters) thick paper liners, each having a silicone
coating on one side and a polyethylene coating on the opposite
side, such that the curable resin composition contacted the
silicone-coated side of each liner. This was done using a
knife-over-bed coating station having a gap setting of 0.008 inches
(0.20 millimeters) greater than the total combined release liner
thickness and a bed and knife temperature of 194.degree. F.
(90.degree. C.). A liner-supported, curable adhesive film was
obtained as a liner/curable adhesive film/liner sandwich, which was
stored for 24 hours at room temperature (about 72.degree. F.
(22.degree. C.)), and then stored at -20.degree. F. (-29.degree.
C.) until it was used to prepare curable, nylon fabric-supported
adhesive films.
Preparation of Curable, Nylon Fabric-Supported Adhesive Films
[0134] A sample of a liner/curable adhesive film/liner sandwich was
equilibrated at room temperature prior to use. The liner from one
side of the sandwich, measuring about 11.5 inches (29.2
centimeters) long and about 6 inches (15.2 centimeters) wide, was
removed, and a supporting, nonwoven nylon fabric (available as
Cerex.TM. 23 fabric, with a round filament geometry, from Cerex
Advanced Fabrics. L.P., Cantonment, Fla.) having an areal weight of
0.4 ounces/square yard (13.6 grams/square meter), which had been
corona treated on both sides, was placed on the exposed adhesive
surface. This fabric was slightly larger in size than the sandwich.
The liner was replaced over the nonwoven nylon fabric, and the
resulting lay-up was passed between two rubber-coated, heated nip
rollers at a temperature of approximately 140.degree. F.
(60.degree. C.). The position of the upper roller and its contact
pressure with the lower drive roller was controlled by air
pressurized pistons having an air supply pressure of about 20 psi
(137.9 kPa). A curable adhesive film having a nonwoven nylon fabric
embedded therein, and having a release liner on each side, was
obtained. Curable, nylon fabric-supported adhesive films prepared
in this manner were subsequently used in the Examples described
below.
Cured Polymeric Composite Articles
[0135] Cured, unidirectional carbon fiber reinforced polymeric
composite articles were provided in two different manners. In the
first manner (hereinafter, designated "Source 1"), carbon fiber
prepreg material was obtained and cured into unidirectional carbon
fiber reinforced polymeric composite articles as next described.
More specifically, ten plies of carbon fiber prepreg (available as
"Toray 3900-2/T800S", having an areal weight of 190
grams/meter.sup.2 and a resin content of 35%, from Toray Carbon
Fibers America, Incorporated, Decatur, Ala.) measuring 8 inches by
6 inches (20.3 centimeters by 15.2 centimeters), were laid up
unidirectionally, and a layer of "Polyester Release Peel-Ply
Fabric" protective material (Style 56009, Code 60001, having an
areal weight of 2.5 ounces/square yard (8.5 grams/square meter) and
a nominal thickness of 0.0055 inches (0.140 millimeters), available
from Precision Fabrics Group, Incorporated, Greensboro, N.C.) was
positioned on the upper outer major surface of the resulting
construction. The "Polyester Release Peel-Ply Fabric" protective
material is hereinafter referred to as "Peel-Ply". This layup was
placed in a vacuum bag, which was then positioned in an autoclave.
A partial vacuum of about 1.9 inches (48.3 mm) Hg was applied at
room temperature (approximately 72.degree. F. (22.degree. C.)) for
10 to 15 minutes, after which the external pressure was gradually
increased to 85 psi (586 kPa). The vacuum bag was then vented to
release the vacuum, and the temperature was raised at 5.degree.
F./minute (2.8.degree. C./minute) up to 350.degree. F. (177.degree.
C.) and held there for 2 hours. The cured polymeric composite
article with "Peel-Ply" on one surface was then cooled at
10.degree. F./minute (5.5.degree. C./minute) to room temperature,
at which point the pressure was released, and the cured article
having an approximate thickness (not including the "Peel-Ply"
layer) of 0.075 inches (1.9 millimeters) was removed from the
autoclave and vacuum bag.
[0136] In the second manner (hereinafter, designated "Source 2"),
cured polymeric composite articles measuring approximately 12
inches by 6 inches by 0.075 inches (30.5 centimeters by 15.2
centimeters by 1.9 millimeters) were obtained. These cured
composite articles had been prepared using both the prepreg
material and essentially the same procedure as described above. The
cured articles had a layer of "Peel-Ply" protective material on one
of their two major outer surfaces. The thickness of these articles
was measured without the "Peel-Ply" in place.
Preparation of Cured Joined Structures
[0137] Cured joined structures, prepared from the above-described
curable nylon fabric-supported adhesive film and two of the
above-described cured polymeric composite articles, were provided
for evaluation of overlap shear strength. More specifically, two
cured polymeric composite articles measuring 6 inches by 12 inches
(15.2 centimeters by 30.5 centimeters), or 6 inches by 8 inches
(15.2 centimeters by 20.3 centimeters) were conditioned in one of
the ways described above in "Environmental Conditioning". The
"Peel-Ply" protective material was then removed from the
conditioned articles. After removing the protective liner from one
side of the curable nylon fabric-supported adhesive film, the film
was applied to the entire surface of a conditioned article, from
which the "Peel-Ply" had been removed, by hand using a small rubber
roller in such a manner as to exclude entrapped air and ensure
intimate contact between the exposed adhesive and the article.
After removing the second liner from the curable adhesive film (and
the "Peel-Ply" from a second cured polymeric composite article),
the newly exposed surface of the second composite article was
placed in contact with the exposed adhesive surface to give a
sandwich assembly with a cured polymeric composite article on each
side of the curable adhesive film, the articles and film all having
the same length and width dimensions. Next, the resulting assembly
was fastened together using a pressure-sensitive adhesive tape at
each end and then placed on a vacuum table for 15 minutes at full
vacuum. The assembly was then cured in an autoclave in the
following manner. After applying a vacuum to reduce the pressure to
about 1.9 inches (48.3 mm) Hg, an external pressure of about 45 psi
(310 kPa) was applied, and the temperature of the autoclave was
heated from about room temperature (72.degree. F. (22.degree. C.))
to either 250.degree. F. (121.degree. C.) or 350.degree. F.
(177.degree. C.), depending on the particular adhesive film
employed, at a rate of 4.5.degree. F./minute (2.5.degree.
C./minute). The vacuum was released when the pressure reached about
15 psi (103.4 kPa). The final temperature and pressure were
maintained for 120 minutes before cooling to room temperature at a
rate of 5.degree. F./minute (2.8.degree. C./minute), at which point
the pressure was released and a cured joined structure was
obtained.
Cured Composite Article with a Surfacing Layer
[0138] An aluminum panel surface was polished with fine steel wool,
then cleaned with methyl ethyl ketone (MEK). Masking tape was
applied to the outer edges of the panel surface, and the panel
surface was then wiped with release agent Loctite.TM. Frekote.TM.
700-NC Mold Release Agent (a water-based release agent available
from Loctite Corporation, Rocky Hill, Conn.), which was allowed to
air dry after which the masking tape was removed. The resulting
release coating was then cured at 250.degree. F. for 30-60 min.
After cooling to room temperature, the panel surface was polished
with a lint free cloth (Kimwipes.TM. EX-L, available from
Kimberly-Clark Corporation, Rosswell, Ga.). Next, after removal of
the paper liner from one side, a curable nylon fabric-supported
adhesive film measuring approximately 8 inches by 6 inches (20.3
centimeters by 15.2 centimeters) was positioned such that its newly
exposed surface contacted the polished panel inside the edges that
had been masked off. The adhesive film was rolled down using a
rubber roller. Paper liner was removed from the second, upper side
of the adhesive film, and a cured composite article, measuring
approximately 8 inches by 6 inches (20.3 centimeters by 15.2
centimeters), was placed on the exposed, top surface of the
adhesive film. This assembly was then placed on a vacuum table for
15 minutes at full vacuum. Next, the assembly was positioned in a
vacuum bag and cured in an autoclave in the following manner. After
applying a vacuum to reduce the pressure to about 1.9 inches (48.3
mm) Hg, an external pressure about 45 psi (310 kPa) was applied,
and the temperature of the autoclave was heated from about room
temperature (72.degree. F. (22.degree. C.)) to either 250.degree.
F. (121.degree. C.) or 350.degree. F. (177.degree. C.), depending
upon the particular adhesive film employed, at a rate of
4.5.degree. F./minute (2.5.degree. C./minute). The vacuum was
released when the pressure reached about 15 psi (103.4 kPa). The
final temperature and pressure were maintained for 120 minutes
before cooling to room temperature at a rate of 5.degree. F./minute
(2.8.degree. C./minute), at which point the pressure was released
and, upon removal from the aluminum panel, a cured composite
article having a surfacing layer on one side was obtained. The
cured composite article with surfacing layer was evaluated visually
by eye for general appearance (for example, as to uniformity and
surface smoothness) and pin holes (for example, as to quantity and
size). A value of 1 (worst) to 10 (best) was assigned for each
characteristic for each article evaluated.
Cured Composite Article with Lightning Protection System
[0139] An aluminum panel surface was polished with fine steel wool,
cleaned with methyl ethyl ketone (MEK), then polished with a
lint-free cloth (Kimwipes.TM. EX-L, available from Kimberly-Clark
Corporation, Rosswell, Ga.). A gray fluoropolymer film, having both
surfaces etched, was provided by coextruding a uniform mixture of
pellets having 97 percent (by weight) clear DYNEON.TM. THV 500 (a
tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride
terpolymer, available from Dyneon (a wholly owned subsidiary of 3M
Company), Oakdale, Minn.) and 3 percent (by weight) of gray
pigmented DYNEON.TM. THV 200 as described in U.S. Pat. No.
6,475,616 (Dietz et al.), Example 1. A solvent-based acrylic
pressure sensitive adhesive was applied to one side of the
fluoropolymer film and dried to give a 0.0003 inch (about 0.008
millimeters) thick adhesive layer. Next, an aluminum mesh (Part No.
1.5AL6-075F, having areal weight of 0.0075 pounds/square foot (36.6
grams/square meter) and an overall thickness of 0.0015 inches
(0.038 millimeters), available from Dexmet Corporation, Naugatuck,
Conn.) was laminated, at room temperature, onto the acrylic
adhesive surface. A second layer of the solvent-based acrylic
pressure sensitive adhesive was applied on top of the aluminum mesh
and dried to give a fluoropolymer film having a pressure sensitive
acrylic adhesive layer with an embedded aluminum mesh on one side.
The total adhesive layer thickness, including the mesh, was about
0.003 inches (0.08 millimeters). A low density polyethylene (LDPE)
protective liner was placed over the adhesive layer.
[0140] The resulting coated fluoropolymer film was positioned on
the aluminum panel with the protective liner layer facing outward.
Next, the protective liner was removed to expose the acrylic
adhesive surface, and the first protective liner from one side of a
350.degree. F. (177.degree.) curable, nylon fabric-supported
adhesive film was removed to expose one surface of the curable
adhesive film. The two exposed surfaces were brought into contact
with each other and the combined structure was rubbed down by hand
to remove any wrinkles and ensure intimate contact between the
acrylic adhesive layer and the curable adhesive film. The second
protective liner was removed from the top side of the curable,
nylon fabric-supported adhesive film and, after removal of their
respective protective liners, two plies of fiberglass prepreg
material (Part No. PP500H, available from Critical Materials
Incoporated, Poulsbo, Wash.) were placed on the exposed curable
adhesive surface. A second sheet of curable, nylon fabric-supported
adhesive film was provided and, after removal of the protective
liner from one side of it, the exposed surface of this second sheet
was applied by hand to the second outer, exposed surface of prepreg
material and rubbed down by hand as described above. Next, after
removal of the second protective liner from the second curable,
nylon fabric-supported adhesive film, the exposed surface of the
adhesive film was brought into contact with a glass fabric
reinforced honeycomb structure impregnated with phenolic resin
(HexWeb.TM. HRP-3/16-8.0, available from Hexcel Corporation,
Stamford, Conn.). After removal of the appropriate protective
liners, another layer of curable, nylon matte-supported adhesive
film was applied to the opposite side of the honeycomb structure
and an additional two plies of fiberglass prepreg were positioned
on the outside surface of this curable adhesive film. Finally, a
layer of "Peel Ply" was placed on the outer, exposed prepreg
surface.
[0141] This entire assembly was then placed on a vacuum table for
5-10 minutes at full vacuum for compaction. The compacted assembly
was then positioned in a vacuum bag and cured in an autoclave in
the following manner. After applying a vacuum to reduce the
pressure to about 1.9 inches (48.3 mm) Hg, an external pressure of
about 45 psi (310 kPa) was applied, and the temperature of the
autoclave was heated from about room temperature (72.degree. F.
(22.degree. C.)) to 350.degree. F. (177.degree. C.) at a rate of
4.5.degree. F./minute (2.5.degree. C./minute). The vacuum was
released when the pressure reached about 15 psi (103.4 kPa). The
final temperature and pressure were maintained for 120 minutes
before cooling to room temperature at a rate of 5.degree. F./minute
(2.8.degree. C./minute), at which point the pressure was released
and a cured composite article having a lightning protection system
was obtained.
Examples 1-3 and Comparative Examples 1-9
[0142] Examples 1-3 and Comparative Examples (CE) 1-9 in Tables 1,
3, and 4 below demonstrate the effect of various toughening
modifiers in joining environmentally conditioned cured polymeric
composite articles together to provide cured joined structures. The
amounts are given in parts by weight (pbw), wherein the combined
amounts of all components is between 99 and 102 pbw.
[0143] Example 1 and Comparative Example 1 were prepared as
described in "Preparation of Cured Joined Structures" above using a
250.degree. F. (121.degree. C.) cure cycle and then evaluated at
200.degree. F. (93.degree. C.) for overlap shear strength (OLS).
Examples 2 and 3, and Comparative Examples 2-9, were prepared as
described in "Preparation of Cured Joined Structures" above using a
350.degree. F. (177.degree. C.) cure cycle and then evaluated at
277.degree. F. (136.degree. C.) for overlap shear strength.
TABLE-US-00001 TABLE 1 Formulations Component Ex. 1 Ex. 2 Ex. 3 CE
1 CE 2 CE 3 CE 4 CE 5 CE 6 CE 7 CE 8 CE 9 EPON 828 35.0 15.0 15.7
AF-163-2 11.0 15.0 15.0 15.0 15.0 15.0 15.0 AF-3109-2 DER 332 10.3
5.85 2.0 EPON 13.7 10.0 10.0 10.0 10.0 1004F EPON 10.0 10.0 10.0
1009F EPON 25.0 25.0 25.0 25.0 25.0 25.0 25.0 SU-2.5 EPON 5.12 13.2
SU-8 TACTIX 25.0 25.1 26.4 25.0 25.0 25.0 25.0 25.0 25.0 756 CG
1400 3.9 4.04 0.093 0.092 4.04 4.04 4.04 3.93 3.93 3.93 OMICURE 2.1
U52 DEH 85 18.5 IPDH 4.73 4.73 4.73 4.73 4.61 4.61 4.61 o-TBAF 34.0
33.4 EXL 2691A 14.9 15.0 15.7 3.0 DUOMOD 15.0 5097 DUOMOD 15.0 5047
BOLTORN 15.0 E1 Rubber 8.6 Toughener CTBN #1 15.0 CTBN #2 15.0 VTBN
15.0 P1800 3.0 1.37 1.38 3.0 3.0 3.0 3.0 3.0 3.0 TWARON 1.6 Aramid
Pulp
Moisture Content of Cured Polymeric Composite Articles
[0144] Cured polymeric composite articles were provided in the two
ways described previously. After environmental conditioning, they
were evaluated as described in the test method "Weight Loss." The
designations "Dry", "Ambient" and "Wet" in the tables refer to the
environmental conditions to which the cured polymeric composite
articles were exposed. The results are shown in Table 2 below.
TABLE-US-00002 TABLE 2 Cured Polymeric % Weight Loss Composite
Article Dry Ambient Wet Source 1 0.377 Not Determined 1.334 Source
2 0.267 0.508 1.101 Average 0.322 0.508 1.218
Overlap Shear Strength (OLS) of Cured Joined Structures
[0145] Environmentally conditioned cured polymeric composite
articles were bonded together using the adhesive films of Examples
1-3 and Comparative Examples 1-9 to provide cured joined structures
which were then evaluated for overlap shear strength (OLS). The
designations "Dry" and "Wet" in the tables refer to the
environmental conditions to which the cured polymeric composite
articles were exposed just prior to bonding with the adhesive
films. % Retention was calculated as [OLS (Wet)/OLS
(Dry)].times.100. TABLE-US-00003 TABLE 3 OLS (psi) [MPa] Example
No. Dry Wet % Retention Ex. 1 2100 [14.5] 1032 [7.1] 49 CE 1 3365
[23.2] 531 [3.7] 16
[0146] TABLE-US-00004 TABLE 4 OLS (psi) [MPa] Example No. Dry Wet %
Retention 2 3448 [23.8] 2113 [14.6] 61 3 3603 [24.8] 2441 [16.8] 68
CE 2 3791 [26.1] 956 [6.6] 25 CE 3 3536 [24.4] 1668 [11.5] 47 CE 4
3688 [25.4] 866 [6.0] 23 CE 5 1829* [12.6] 1009* [7.0] 55* CE 6
1560 [10.8] 350 [2.4] 22 CE 7 2398 [16.5] 672 [4.6] 28 CE 8 1790
[12.3] 200 [1.4] 11 CE 9 1590 [11.0] 173 [1.2] 11 *For CE 5, the
resin composition, adhesive film, and cured joined structure
appeared to exhibit gross phase separation of the toughening
modifier, a feature that can compromise overlap shear strength
performance. As a result, the dry OLS value may be low, leading to
an artificially high retention value.
Examples 4 and 5 and Comparative Examples 10 and 11
[0147] Adhesive films were used to prepare cured composite articles
having a cured surfacing layer thereon, which were then evaluated
for general appearance and pin holes, all as described in "Cured
Composite Article with a Surfacing Layer" above. The results are
shown in Table 5 below. AF-325 (CE 11) is an epoxy adhesive film
sold specifically as a composite surfacing film. AF-191 (CE 10) is
a commercially available adhesive film often used for this same
purpose. TABLE-US-00005 TABLE 5 General Example No. Adhesive System
Appearance Pin Holes CE 10 AF-191 9 10 CE 11 AF-325 8 9 4 Example 1
7 5 5 Example 2 9 8
Example 6
[0148] The adhesive film of Example 2 above was used to prepare a
cured composite article having an embedded aluminum mesh therein.
Such a construction has utility as a means of providing lightning
strike protection. The article was prepared as described in "Cured
Composite Article with Lightning Protection" above. The resulting
cured composite article had a surface that was essentially smooth
and had no visible defects, such as pinholes.
[0149] The referenced descriptions contained in the patents, patent
documents, and publications cited herein are incorporated by
reference in their entirety as if each were individually
incorporated. Various unforeseeable modifications and alterations
to this invention will become apparent to those skilled in the art
without departing from the scope and spirit of this invention. It
should be understood that this invention is not intended to be
unduly limited by the illustrative embodiments and examples set
forth herein and that such examples and embodiments are presented
by way of example only with the scope of the invention intended to
be limited only by the claims set forth herein as follows.
* * * * *