U.S. patent application number 10/935857 was filed with the patent office on 2009-07-02 for preformed compositions in shaped form comprising polymer blends.
Invention is credited to Adrian K. Balladares, Michael A. Cosman.
Application Number | 20090170999 10/935857 |
Document ID | / |
Family ID | 40793498 |
Filed Date | 2009-07-02 |
United States Patent
Application |
20090170999 |
Kind Code |
A1 |
Cosman; Michael A. ; et
al. |
July 2, 2009 |
PREFORMED COMPOSITIONS IN SHAPED FORM COMPRISING POLYMER BLENDS
Abstract
Preformed compositions in shaped form comprising polymer blends,
and the use of these preformed compositions in shaped form to seal
apertures are disclosed. In certain embodiments, the preformed
compositions are electrically conductive and are capable of
shielding EMI/RFI radiation. The polymer blend includes a
polysulfide component and a polythioether component.
Inventors: |
Cosman; Michael A.;
(Valencia, CA) ; Balladares; Adrian K.; (El
Segundo, CA) |
Correspondence
Address: |
PPG Industries, Inc.
One PPG Place
Pittsburgh
PA
15272
US
|
Family ID: |
40793498 |
Appl. No.: |
10/935857 |
Filed: |
September 8, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10837337 |
Apr 30, 2004 |
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10935857 |
|
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|
10355813 |
Jan 30, 2003 |
7067612 |
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10837337 |
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Current U.S.
Class: |
524/449 ;
427/385.5 |
Current CPC
Class: |
C08K 9/02 20130101; C08L
77/00 20130101; C08L 81/02 20130101; C08K 7/06 20130101; C08L 81/04
20130101; C08L 81/02 20130101; C08L 2666/14 20130101; C08L 81/04
20130101; C08L 2666/14 20130101 |
Class at
Publication: |
524/449 ;
427/385.5 |
International
Class: |
C08K 3/34 20060101
C08K003/34; B05D 3/10 20060101 B05D003/10 |
Claims
1. A preformed composition in shaped form comprising a polymer
blend, comprising: a) at least one polysulfide component, b) at
least one polythioether component, and c) a blend of fillers
comprising mica and polyamide.
2. The preformed composition of claim 1, wherein the ratio of a:b
in the polymer blend is from 10:90 to 90:10.
3. The preformed composition of claim 2, wherein the ratio of a:b
in the polymer blend is 50:50.
4. The preformed composition of claim 1 further comprising a curing
agent for the polymer blend.
5. The preformed composition of claim 4, wherein the curing agent
comprises an oxidizing agent.
6. The preformed composition of claim 5, wherein the curing agent
comprises manganese dioxide.
7. The preformed composition of claim 4, wherein the curing agent
is reactive at a temperature ranging from 10.degree. C. to
80.degree. C.
8. The preformed composition of claim 1, wherein the polymer blend
is present in an amount ranging from 20 percent by weight to 30
percent by weight of the total weight of the preformed
composition.
9. The preformed composition of claim 4, wherein the curing agent
is present in an amount ranging from 5 percent by weight to 20
percent by weight of the total weight of the preformed
composition.
10. The preformed composition of claim 1, wherein the preformed
composition is curable at a temperature ranging from 10.degree. C.
to 30.degree. C.
11-12. (canceled)
13. The preformed composition of claim 1 further comprising a
plasticizer.
14. A method for sealing an aperture comprising: a) covering the
aperture with the preformed composition of claim 1; and b) curing
the composition so as to seal the aperture.
15. The method of claim 14, wherein the surface is a surface of a
removable panel.
16. The method of claim 14, wherein the aperture is a space between
the surface adjacent to an opening and the surface of a removable
panel.
17. The method of claim 14, wherein the aperture is on an
aircraft.
18. The method of claim 14, wherein an adhesion promoter is applied
to at least one surface defining the aperture prior to application
of the preformed composition.
19. The method of claim 14, wherein a release agent is applied to
at least one surface defining the aperture prior to application of
the preformed composition, claims 20-39. (canceled)
40. The preformed composition of claim 1 further comprising one or
more additives selected from fillers, adhesion promoters, solvents,
plasticizers, pigments, thixotropes, retardants, catalysts and
masking agents.
41. (canceled)
42. The preformed composition of claim 1, wherein the mica is
present in an amount ranging from 5 percent by weight to 25 percent
by weight of the total weight of the preformed composition.
43. The preformed composition of claim 1, wherein the polyamide is
present in an amount ranging from 5 percent by weight to 25 percent
by weight of the total weight of the preformed composition.
44. The preformed composition of claim 1, wherein the combination
of mica and polyamide is present in an amount ranging from 10
percent by weight to 50 percent by weight of the total weight of
the preformed composition, and wherein the mica and the polyamide
are present at substantially equal amounts in the preformed
composition.
45. The preformed composition of claim 1, wherein the mica
comprises natural muscovite, phlogopite, biotite, synthetic
fluorophlogopite, barium disilicic, and combinations thereof.
46. The preformed composition of claim 1, wherein the polyamide has
a number average molecular weight of at least 10,000 Daltons.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of Ser. No.
10/837,337 filed Apr. 30, 2004, and a continuation-in-part of Ser.
No. 10/355,813, filed Jan. 30, 2003.
FIELD OF THE INVENTION
[0002] The present invention relates to preformed compositions in
shaped form and the use of preformed compositions for sealing
apertures.
BACKGROUND OF THE INVENTION
[0003] Electromagnetic interference can be defined as undesired
conducted or radiated electrical disturbances from an electrical or
electronic source, including transients, that can interfere with
the operation of other electrical or electronic apparatus. Such
disturbances can occur at frequencies throughout the
electromagnetic spectrum. Radio frequency interference ("RFI") is
often used interchangeably with electromagnetic interference
("EMI"), although RFI more properly refers to the radio frequency
portion of the electromagnetic spectrum usually defined as 10
kilohertz (KHz) to 100 gigahertz (GHz).
[0004] Electronic equipment is typically enclosed in a housing. The
housing not only serves as a physical barrier to protect the
equipment from the environment, but also can serve to shield
EMI/RFI radiation. Enclosures having the ability to absorb and/or
reflect EMI/RFI energy may be employed to confine the EMI/RFI
energy within the source device, and to insulate the device or
other external devices from other EMI/RFI sources. To maintain
accessibility to the internal components, most enclosures are
provided with openable or removable accesses such as doors,
hatches, panels, or covers. Gaps typically exist between the
accesses and the corresponding mating surfaces that reduce the
efficiency of the electromagnetic shielding by presenting openings
through which radiant energy may be emitted. Such gaps also present
discontinuities in the surface and ground conductivity of the
housing, and in some cases may generate a secondary source of
EMI/RFI radiation by functioning as a slot antenna.
[0005] For filing gaps between the mating surfaces of the housing
and removable accesses, gaskets and other seals are used to
maintain electrical continuity across the structure, and to exclude
environmental degradants such as particulates, moisture, and
corrosive species. Such seals are bonded or mechanically attached
to one or both of the mating surfaces and function to establish a
continuous conductive path by conforming to surface irregularities
under an applied pressure.
[0006] Conventional processes for manufacturing EMI/RFI shielding
gaskets include extrusion, molding, and die-cutting. Molding
involves the compression or injection molding of an uncured or
thermoplastic resin into a certain configuration. Die-cutting
involves the forming of a gasket from a cured polymeric material,
which is cut or stamped into a certain configuration using a die.
Form-in-place ("FIP") processes are also used for forming EMI/RFI
shielding gaskets wherein the process involves the application of a
bead of a viscous, curable, electrically-conductive composition in
a fluent state to a surface that is subsequently cured-in-place by
the application of heat, atmospheric moisture, or ultraviolet
radiation to form an electrically-conductive, EMI/RFI shielding
gasket.
[0007] Electrical conductivity and EMI/RFI shielding effectiveness
is typically imparted to polymeric gaskets by incorporating
conductive materials within the polymer matrix. The conductive
elements can include metal or metal-plated particles, fabrics,
meshes, and fibers. The metal can be in the form of, for example,
filaments, particles, flakes, or spheres. Examples of metals
include copper, nickel, silver, aluminum, tin, and steel. Other
conductive materials that are used to impart EMI/RFI shielding
effectiveness to polymer compositions include conductive particles
or fibers comprising carbon or graphite. Conductive polymers such
as polythiophenes, polypyrroles, polyaniline,
poly(p-phenylene)vinylene, polyphenylene sulfide, polyphenylene,
and polyacetylene may also be used.
[0008] In addition to shielding EMI/RFI radiation, in certain
applications it is also desirable that the seal be transparent to
incident broad spectrum radiation used for detection, location, or
recognition purposes. For example, microwave radiation from 5-18
GHz, 35 GHz, 94 GHz, 140 GHz and 220 GHz has useful military
significance. Electromagnetic radiation incident on a surface will
be partly reflected and partly absorbed by the material and the sum
of these effects determines the shielding effectiveness. The
shielding effectiveness depends on several factors including the
frequency of the electromagnetic radiation, the conductivity of the
shielding material, the thickness and permeability of the shielding
material, and the distance between the radiating source and the
EMI/RFI shield. At high frequencies, above about 10 GHz, shielding
effectiveness is primarily determined by the ability of the
shielding material to absorb the incident radiation. Ferromagnetic
particles with high permeability such as iron, carbonyl iron,
cobalt metal alloys, and nickel metal alloys are used as radar
absorbing materials.
[0009] In addition to providing continuous electrical conductivity
and EMI/RFI shielding effectiveness, in certain applications it is
desirable that gasket or seals to surfaces exposed to the
environment, such as in aviation and aerospace vehicles, not lead
to corrosion of the metal surfaces. When dissimilar metal and/or
conductive composite materials are joined in the presence of an
electrolyte, a galvanic potential is established at the interface
between the dissimilar conductors. When the interfacial seal is
exposed to the environment, particularly under severe environmental
conditions such as salt fog or salt fog containing a high
concentration of SO.sub.2, corrosion of the least noble of the
conductive surfaces will occur. Corrosion may lead to a degradation
in the EMI/RFI shielding effectiveness of the seal. Mechanisms
other than galvanic potentials, e.g. crevice corrosion, may also
compromise the electrical and mechanical integrity of the
enclosure.
[0010] Polysulfide polymers are known in the art. The production of
polysulfide polymers is characterized by Fettes and Jorzak,
Industrial Engineering Chemistry, November, 1950, on pages 2,217 to
2,223. The commercial use of polysulfide polymers in the
manufacture of sealants for aerospace applications has long been
known and commercially used. Polysulfide sealants have been used to
seal aircraft exterior fuselage because of the high tensile
strength, high tear strength, thermal resistance, and resistance to
high ultraviolet light. Polysulfide sealants have been used to seal
aircraft fuel tanks because of the resistance to fuel and adhesion
upon exposure to fuel.
[0011] Polysulfide sealants are generally applied by extrusion
using a gun. Extruding a sealant to seal apertures in airframe such
as those associated with access doors or panels can require a
significant amount of effort. The interior perimeter of the access
door opening is masked and the exterior perimeter of the access
door is coated with a release agent to avoid sealing an access door
shut. The sealant is extruded and the access door is put in place
and clamped down to force the excess sealant around the access
door. The sealant is allowed to cure and the excess sealant is
trimmed away. This process is time intensive and can add
significant labor demands for servicing aircraft with many access
doors. Some aircraft can have as many as a hundred or more access
doors that are used to cover sensitive electronic equipment or
fittings that must be periodically accessed.
[0012] Accordingly, it is desirable to provide compositions and
methods for sealing access doors, for example those in an airframe
of an aviation or aerospace vehicle, that are not as labor and time
intensive as the conventional extrusion method for sealing the
access doors. It is also desirable to provide such compositions and
methods that further provide effective EMI/RFI shielding and cause
minimal corrosion to conductive surfaces.
SUMMARY OF THE INVENTION
[0013] The present invention is directed to preformed compositions
in shaped form, comprising a polymer blend that comprises at least
one polysulfide component and at least one polythioether
component.
[0014] The present invention is further directed to methods for
sealing an aperture comprising: (a) covering the aperture with the
preformed composition of the present invention in shaped form; and
(b) curing the composition so as to seal the aperture.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention is directed to a preformed composition
in shaped form comprising a polymer blend comprising at least one
polysulfide component and at least one polythioether component. The
term "preformed" refers to a composition that can be made into a
particular shape for ease of packaging, storage, and/or
application. A composition that is preformed can be reshaped into
any shape, either intentionally, or as a result of shipping and/or
handling. The term "shaped form" refers to a configuration such
that the thickness of the preformed composition is substantially
less than the lateral dimension and includes but is not limited to
tapes, sheets and cut-out or gasket forms. The "shaped form" can be
in the form of a tape meaning a narrow shape, strip, or band that
can be stored as rolls, coils, or strips. The "shaped form" can
also be die-cut to the dimensions of the aperture to be sealed.
[0016] "Sealant" and like terms refer to compositions that have the
ability to resist atmospheric conditions such as moisture and/or
temperature and/or at least partially block the transmission of
materials such as water, fuel, and/or other liquids and gasses.
Sealants often have adhesive properties, as well. "Aperture" refers
to a hole, gap, slit or other opening. The term "elongated
aperture" refers to such an opening in which the length is at least
three-times the width. "Shielding" and like terms refer to the
ability to divert, route, and/or reflect incident electromagnetic
energy. Shielding effectiveness represents the ratio of the
electromagnetic energy passing through a shield to the
electromagnetic energy striking the shield.
[0017] The polymer blend of the present invention comprises at
least one polysulfide component and at least one polythioether
component. The "polysulfide component" of the present invention
comprises a polysulfide polymer that contains multiple
sulfur-sulfur linkages, i.e., --[S--S]--, in the polymer backbone
and/or in the terminal or pendant positions on the polymer chain.
Typically, the polysulfide polymers in the present invention will
have two or more sulfur-sulfur linkages. Suitable polysulfides are
commercially available from Akzo Nobel under the name THIOPLAST.
THIOPLAST products are available in a wide range of molecular
weights ranging, for example, from less than 1100 to over 8000,
with molecular weight being the average molecular weight in grams
per mole. Particularly suitable as a number average molecular
weight of 1000 to 4000. The crosslink density of these products
also varies, depending on the amount of crosslinking agent
used.
[0018] The "--SH" content, i.e. the mercaptan content, of these
products can also vary. The mercaptan content and molecular weight
of the polysulfide can affect the cure speed of the blend, with
cure speed increasing with molecular weight.
[0019] In some embodiments, it is desired to use a combination of
polysulfides to achieve the desired molecular weight and/or
crosslink density in the polymer blend. Different molecular weights
and/or crosslink densities can contribute different characteristics
to the blend and compositions incorporating the blend. For example,
blends wherein the polysulfide component comprises more than one
polysulfide polymer and one of the polysulfide polymers has a
molecular weight of approximately 1000 have desirable
non-crystallization properties.
[0020] The second component in the polymer blend of the present
invention is a polythioether. The "polythioether component" of the
present invention is a polymer comprising at least one
polythioether linkage, i.e.,
--[--CH.sub.2--CH.sub.2--S--CH.sub.2--CH.sub.2--]--. Typical
polythioethers have from 8 to 200 of these linkages. Polythioethers
suitable for use in the present invention include those described
in U.S. Pat. No. 6,372,849. Suitable polythioethers typically have
a number average molecular weight of 1000 to 10,000, such as 2,000
to 5,000, or 3,000 to 4,000. In some embodiments, the polythioether
component will be terminated with non-reactive groups, such as
alkyl, and in other embodiments will contain reactive groups in the
terminal or pendant positions. Typical reactive groups are thiol,
hydroxyl, amino, vinyl and epoxy. For a polythioether component
that contains reactive functional groups, the average functionality
typically ranges from 2.05 to 3.0, such as from 2.1 to 2.6. A
specific average functionality can be achieved by suitable
selection of reactive ingredients. Examples of suitable
polythioethers are available from PRC-Desoto International, Inc.,
under the trademark PERMAPOL, such as PERMAPOL P-3.1E or PERMAPOL
P-3. As with the polysulfide component, combinations of
polythioethers can be used to prepare the polythioether component
according to the present invention.
[0021] The polymer blends of the present invention can be prepared
according to any standard means known in the art, such as by mixing
the polysulfide component and polythioether component and blending
in a standard mixer such as a cowls mixer or planetary mixer. The
ratio of polysulfide component to polythioether component in the
blend can range from 10:90 to 90:10. A 50:50 ratio is particularly
suitable for some embodiments. The molecular weight of the present
polymer blend is typically from 1000 to 8000, such as 3500 to 4500,
as measured theoretically or using GPC. The Tg of the polymer blend
is typically -70.degree. C. or lower, such as -60.degree. C. or
lower. The viscosity of the blend will typically be lower than the
viscosity of a polysulfide having a comparable molecular weight;
this contributes to the ease of handling of the present
compositions and may minimize if not eliminate the need for
solvents.
[0022] The polymer blend in the present compositions typically
comprises 10 to 50 weight percent, such as 20 to 30 weight percent,
with weight percent based on the weight of the total preformed
composition.
[0023] In certain embodiments, the preformed composition of the
present invention further comprises a suitable curing agent. The
term "curing agent" refers to any material that can be added to
accelerate the curing or gelling of the polymer blend. In some
embodiments, the curing agent is reactive at 10.degree. C. to
80.degree. C. The term "reactive" means capable of chemical
reaction and includes any level of reaction from partial to
complete reaction of a reactant. In certain embodiments, a curing
agent is reactive when it provides for cross-linking or gelling of
a sulfur-containing polymer. "Cure" refers to the point at which
the composition achieves a cure hardness of 30 Durometer "A" as
measured according to ASTM D2240.
[0024] In certain embodiments, the preformed composition comprises
a curing agent that contains oxidizing agents that oxidize terminal
mercaptan groups in the polymer blend. Useful curing agents include
lead dioxide, manganese dioxide, calcium dioxide, sodium perborate
monohydrate, calcium peroxide, zinc peroxide, dichromate and epoxy.
Other suitable curing agents may contain reactive functional groups
that are reactive with the functional groups in the polymer blend.
Examples include but are not limited to polythiols, such as
polythioethers; polyisocyanates such as isophorone diisocyanate,
hexamethylene diisocyanate, and mixtures and isocyanurate
derivatives thereof; and polyepoxides. Examples of polyepoxides
include hydantoin diepoxide, Bisphenol-A epoxides, Bisphenol-F
epoxides, Novolac-type epoxides, aliphatic polyepoxides, and
epoxidized unsaturated and phenolic resins. The term "polyepoxide"
refers to a material having a 1,2-epoxy equivalent greater than one
and includes monomers, oligomers, and polymers. Cure accelerators
or retardants can also be used, such as a
dimethylene/thiuram/polysulfide mixture cure accelerator or a
stearic acid cure retarder, which will retard the rate of cure
thereby extending the "pot life" of the composition. To control the
properties of the composition, one or more materials capable of at
least partially removing moisture from the composition, such as
molecular sieve powder.
[0025] The preformed compositions of the present invention can also
comprise one or more additives. "Additives" refer to non-reactive
components in the preformed composition that provides a desired
property. Examples of additives include but are not limited to
fillers, adhesion promoters, and plasticizers. Fillers useful in
the present compositions, especially for aerospace applications,
include those commonly used in the art, such as carbon black,
calcium carbonate (CaCO.sub.3), silica, nylon and the like. Potting
compound fillers illustratively include high band gap materials
such as zinc sulfide and inorganic barium compounds. In one
embodiment, the compositions include about 10 to about 70 weight
percent of the selected filler or combination of fillers, such as
about 10 to 50 weight percent based upon the total weight of the
composition. In one embodiment, a combination of mica and polyamide
are used as the filler component.
[0026] Mica is a silicate characterized by basal cleavage that
imparts flexibility to laminas. Micas include natural muscovite,
phlogopite, and biotite, as well as synthetic fluorophlogopite and
barium disilicic. Preparation of synthetic micas is described in
Encyclopedia of Chemical Technology, Vol. 13, pp. 398-424, John
Wiley & Sons (1967). Mica provides flexibility and pliability
to the preformed composition and reduces the tack. Polyamide powder
provides viscosity and reduces the tack of the preformed
composition. Polyamide resins can be produced by the condensation
reaction of dimerized fatty acids, such as dimerized linoleic acid,
with lower aliphatic polyamines, such as for example, ethylene
diamine or diethylene triamine, so that the final product has
multiple amide groups in the resin backbone. A process for the
manufacture of polyamide resins is disclosed in U.S. Pat. No.
2,450,940. Polyamide resins suitable for the preformed composition
are solid at use temperature and typically have a number average
molecular weight of at least 10,000 Daltons.
[0027] In certain embodiments, mica and polyamide together form 10
percent by weight to 50 percent by weight of the total weight of
the preformed composition with substantially equal amounts of mica
and polyamide. "Substantially equal" means that the amount of mica
and the amount of polyamide are present in an amount of less than 5
percent of each other. The amount of mica can range from 5 percent
by weight to 25 percent by weight and the amount of polyamide from
5 percent by weight to 25 percent by weight. In one embodiment, the
amount of mica ranges from 10 percent by weight to 20 percent by
weight and the amount of polyamide ranges from 10 percent by weight
to 20 percent by weight of the total weight of the preformed
composition.
[0028] One or more adhesion promoters can also be used. Suitable
adhesion promoters include phenolics such as METHYLON phenolic
resin available from Occidental Chemicals, organosilanes such as
epoxy, mercapto or amino functional silanes such as A-187 and
A-1100 available from Osi Specialties. An adhesion promoter can be
used in an amount from 0.1 to 15 weight percent based upon total
weight of the formulation.
[0029] A plasticizer can be used in the present compositions in an
amount ranging from 1 to 8 weight percent based upon total weight
of the formulation. Useful plasticizers include phthalate esters,
chlorinated paraffins, hydrogenated terphenyls, etc.
[0030] The formulation can further comprise one or more organic
solvents, such as isopropyl alcohol, in an amount ranging from 0 to
15 percent by weight on a basis of total weight of the formulation,
such as less than 15 weight percent or less than 10 weight
percent.
[0031] Compositions of the present invention can also optionally
include other additives standard in the art, such as pigments;
thixotropes; retardants; catalysts; and masking agents.
[0032] Useful pigments include those conventional in the art, such
as carbon black and metal oxides. Pigments can be present in an
amount from about 0.1 to about 10 weight percent based upon total
weight of the formulation.
[0033] Thixotropes, for example fumed silica or carbon black, can
be used in an amount from about 0.1 to about 5 weight percent based
upon total weight of the formulation.
[0034] The curing agent will generally comprise 2 to 30 weight
percent of the total composition such as 5 to 20 weight percent,
with weight percent based on the total weight of the composition.
In general, the equivalent ratio of curing agent to polymer blend
may range from 0.5:1 to 2.0:1. A cure accelerator, if used, can be
present in an amount ranging from 1 to 7 weight percent, a cure
retarder, if used, in an amount ranging from 0.1 to 1 weight
percent, and a moisture remover, if used, in an amount ranging from
0.1 to 1.5 weight percent, with weight percent based on the total
weight of the curing agent composition.
[0035] When used, additives can comprise up to 50 weight percent of
the total weight of the preformed composition.
[0036] In certain embodiments, the preformed compositions of the
present invention are prepared as two pack or "2K" systems, in
which the polymer blend is in one component, referred to herein as
the base composition, and the curing agent is in the other
component, referred to herein as the curing agent composition. The
base composition and curing agent composition are mixed just prior
to use.
[0037] The present invention is also directed to a preformed
composition in shaped form comprising a polymer blend comprising at
least one polyepoxide component and at least one polythioether
component, and at least one electrically conductive filler. An
"electrically conductive filler" is a filler that, when added to a
formulation, imparts electrical conductivity and/or EMI and/or RFI
shielding to the formulation. Examples of such fillers include
electrically conductive noble metal-based fillers such as pure
silver; noble metal-plated noble metals such as silver-plated gold;
noble metal-plated non-noble metals such as silver plated cooper,
nickel or aluminum, for example, silver-plated aluminum core
particles or platinum-plated copper particles; noble-metal plated
glass, plastic or ceramics such as silver-plated glass
microspheres, noble-metal plated aluminum or noble-metal plated
plastic microspheres; noble-metal plated mica; and other such
noble-metal conductive fillers. Non-noble metal-based materials can
also be suitable including non-noble metal-plated non-noble metals
such as copper-coated iron particles or nickel plated copper;
non-noble metals, e.g., copper, aluminum, nickel, cobalt; and
non-noble-metal-plated-non metals, e.g., nickel-plated graphite and
non-metal materials such as carbon black and graphite. Combinations
of the conductive fillers can also be used to meet the desired
conductivity, EMI/RFI shielding effectiveness, hardness and other
properties suitable for a particular application.
[0038] The shape and size of the electrically conductive fillers is
not critical to preformed compositions of the invention. The
fillers may be of any shape generally used in the manufacture of
conductive materials, including spherical, flake, platelet,
irregular or fibrous, such as milled or chopped fibers. In making
preformed compositions in shaped form, in accordance with certain
embodiments of the invention, the composition may comprise
conductive fillers and radar absorbing materials having various
shapes. For example, the shape of the conductive fillers may be
spherical, substantially spherical, or irregular.
[0039] Carbon fibers, particularly graphitized carbon fibers, can
be used to impart electrical conductivity to preformed compositions
of the invention. Carbon fibers formed by vapor phase pyrolysis
methods and graphitized by heat treatment and which are hollow or
solid with a fiber diameter of from 0.1 micron to several microns
have high electrical conductivity. As disclosed in U.S. Pat. No.
6,184,280, carbon microfibers, nanotubes or carbon fibrils having
an outer diameter of less than 0.1 micron to tens of nanometers can
be used as electrically conductive fillers. An example of
graphitized carbon fiber suitable for conductive preformed
compositions of the invention is PANEX 30MF, a 0.921 micron
diameter round fiber having an electrical resistivity of 0.00055
.OMEGA.-centimeter (cm).
[0040] The average particle size of the electrically conductive
fillers can be within the range normally used for fillers in
conductive materials. In certain embodiments, the particle size of
the one or more fillers is from about 0.25 microns to about 250
microns, and in other embodiments from about 0.25 microns to about
75 microns, and in still other embodiments from about 0.25 microns
to about 60 microns. In certain embodiments, the preformed
composition of the invention comprises Ketjen Black EC-600 JD (Akzo
Nobel), a conductive carbon black characterized by an iodine
absorption of 1000-11500 mg/g (J0/84-5 test method), and a pore
volume of 480-510 cm3/100 gm (DBP absorption, KTM 81-3504). In
other embodiments, the carbon black filler is Black Pearls 2000
(Cabot Corporation).
[0041] In certain embodiments, electrically conductive polymers can
be used to impart or modify the electrical conductivity of
preformed compositions of the invention. Polymers having sulfur
atoms incorporated into aromatic groups or adjacent to double
bonds, such as in: polyphenylene sulfide and polythiophene, are
known to be electrically conductive. Other electrically conductive
polymers include polypyrroles, polyaniline, poly(p-phenylene)
vinylene, and polyacetylene. All of these can be used according to
the present invention.
[0042] In certain embodiments, electrically conductive preformed
compositions of the invention comprise electrically conductive
materials ranging from 2 percent to 50 percent by weight of the
total weight of the electrically conductive preformed
composition.
[0043] Galvanic corrosion of dissimilar metal surfaces and the
electrically conductive compositions of the invention can be
minimized or prevented by adding corrosion inhibitors to the
composition, and/or by selecting appropriate conductive fillers.
Corrosion inhibitors include, for example, strontium chromate,
calcium chromate, magnesium chromate, and combinations thereof,
aromatic triazoles and a sacrificial oxygen scavenger such as Zn;
other suitable corrosion inhibitors are known in the art. In
certain embodiments, the corrosion inhibitor comprises less than 10
percent by weight of the total weight of the electrically
conductive preformed composition. In other embodiments, the
corrosion inhibitor comprises an amount ranging from 2 percent to
15 percent by weight of the total weight of the electrically
conductive preformed composition. Corrosion between dissimilar
metal surfaces can also be minimized or prevented by the selection
of the type, amount, and properties of the conductive fillers
comprising the preformed composition.
[0044] In certain embodiments, a base composition can be prepared
by batch mixing at least one polysulfide, at least one
polythioether, additives, and/or fillers in a double planetary
mixer under vacuum. Other suitable mixing equipment includes a
kneader extruder, sigma mixer, or double "A" arm mixer. For
example, a base composition can be prepared by mixing at least one
polysulfide, at least one polythioether polymer, plasticizer, and
phenolic adhesion promoter. After the mixture is thoroughly
blended, additional constituents can be separately added and mixed
using a high shear grinding blade, such as a Cowls blade, until cut
it. Examples of additional constituents that can be added to a base
composition include corrosion inhibitors, non-conductive fillers,
electrically conductive fiber, electrically conductive flake, and
silane adhesion promoters. The mixture can then be mixed for an
additional 15 to 20 minutes under a vacuum of 27 inches of mercury
or greater to reduce or remove entrapped air and/or gases. The base
composition can then be extruded from the mixer using a
high-pressure piston ram.
[0045] The curing agent composition can be prepared by batch mixing
the curing agent and other additives. In certain embodiments, 75
percent of the total plasticizer such as partially hydrogenated
terphenyl and an accelerant such as a
dipentamethylene/thiuram/polysulfide mixture are mixed in a
single-shaft anchor mixer. Molecular sieve powder is then added and
mixed for 2 to 3 minutes. Fifty percent of the total manganese
dioxide is then mixed until cut in. Stearic acid, sodium stearate,
and the remaining plasticizer are then mixed until cut in followed
by the remaining 50 percent of the manganese dioxide which is mixed
until cut in. Fumed silica is then mixed until cut in. If the
mixture is too thick, a surfactant may be added to increase
wetting. The curing agent composition is then mixed for 2 to 3
minutes, passed over a three-roll paint mill to achieve a grind,
and returned to the single-shaft anchor mixer and mixed for an
additional 5 to 10 minutes. The curing agent composition can then
be removed from the mixer with a piston ram and placed into storage
containers and aged for at least five days prior to combining with
a base composition.
[0046] The base composition and curing agent composition are mixed
together to form the preformed composition just prior to use. Any
suitable means for mixing can be employed. For example, the base
composition and curing agent composition can be combined in the
desired ratio using meter mix equipment fitted with a dynamic mix
head. Pressure from the meter mix equipment forces the base and
curing agent compositions through the dynamic mix head and an
extrusion die. In certain embodiments the preformed composition is
extruded into a laminar form including a tape or sheet. The
preformed composition in sheet form can be cut to any desired shape
such as the shape defined by the dimensions of an aperture to be
sealed. In certain embodiments, the shaped form can be coiled with
release paper separating each ring for packaging purposes. The
shaped form is then refrigerated by placing the shaped form on a
bed of dry ice and placing another layer of dry ice on the top of
the shaped form. The shaped form is refrigerated immediately after
mixing the base composition and the curing agent composition. The
shaped form remains exposed to the dry ice for 5 to 15 minutes and
is then placed at a storage temperature of -40.degree. C. or lower.
The term "refrigerated" refers to reducing the temperature of the
preformed composition so as to retard and/or stop the curing of the
preformed composition. Typically, the preformed composition in
shaped form is refrigerated below -40.degree. C.
[0047] In certain embodiments, the temperature of the preformed
composition is raised to a use temperature ranging from 4.degree.
C. to 32.degree. C. (40.degree. F. to 90.degree. F.) prior to
application. This is done such that the preformed composition
reaches use temperature for no more than 10 minutes prior to
application.
[0048] In certain embodiments the preformed composition in shaped
form can be used to seal an aperture between a removable access
panel and the surface adjacent to the perimeter of an opening in an
aircraft fuselage. Adhesion promoter is first brushed on the
perimeter of the access panel opening after the surface has been
cleaned with a cleaning solvent such as DESOCLEAN. The surface of
the access panel is then cleaned and coated with a release agent
prior to applying the preformed composition. The preformed
composition in shaped form is manually applied to the surface
adjacent to the perimeter of the access panel opening, to the
surface adjacent to the perimeter of the access panel, or to both.
The access panel is then put in place and clamped down forcing the
excess preformed composition around the edges of the access panel.
Excess preformed composition is easily removed by using, for
example, a flat surface. Excess preformed composition can be
removed either prior to curing or after the preformed composition
has cured, and preferably after the preformed composition
cures.
[0049] The integrity, moisture resistance and fuel resistance of
the seal resulting from application of preformed compositions of
the present invention can be evaluated by performing the tests
identified in specification MMS 332. An acceptable seal will be
tight and resistant to moisture and aircraft fuel.
[0050] In addition to ease of handling and use, the present
compositions may cause minimal corrosion to conductive surfaces in
the environments encountered in aviation and aerospace
applications. Because the present polymer blends have both a
polysulfide and a polythioether component, they are compatible with
other sealants or coating layers having one or the other of these
technologies. They also exhibit good solvent resistance.
[0051] It is noted that, as used in this specification and the
appended claims, the singular forms "a", "an", and, "the" include
plural referents unless expressly and unequivocally limited to one
referent. Thus, for example, reference to "a filler" includes one
or more fillers. Also it is noted that, as used herein, the term
"polymer" is meant to refer to prepolymers, polymers, oligomers,
homopolymers, and copolymers.
[0052] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities of
ingredients or percentages or proportions of other materials,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about". Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should at least be construed in
light of the number of reported significant digits and by applying
ordinary rounding techniques.
[0053] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains certain errors necessarily resulting from the
standard deviation found in their respective testing measurements.
Moreover, all ranges disclosed herein are to be understood to
encompass any and all sub-ranges subsumed therein. For example, a
range of "10 to 50" includes any and all sub-ranges between (and
including) the minimum value of 10 and the maximum value of 50,
that is, any and all sub-ranges having a minimum value of equal to
or greater than 10 and a maximum value of equal to or less than 50,
e.g., 25 to 50.
EXAMPLE
[0054] The following example is intended to illustrate the
invention, and should not be construed as limiting the invention in
any way.
Example 1
[0055] Example 1 provides an electrically conductive preformed
composition in shaped form exhibiting EMI/RFI shielding
effectiveness. The following materials were mixed in the
proportions according to Table I to provide an electrically
conductive base composition: PERMAPOL P 3.1 polythioether polymer
from PRC-DeSoto International, Inc., THIOPLAST G4 polysulfide
polymer from Akcros Chemicals (New Brunswick, N.J.), phenolic resin
adhesion promoter from PRC-DeSoto International, Inc., and HB-40
modified polyphenyl plasticizer from Solutia, Inc. (St. Louis,
Mo.). Using a high shear grinding blade (Cowls blade), the
following materials were individually added and blended until cut
in: calcium chromate corrosion inhibitor (Wayne Pigment Corp.,
Milwaukee, Wis.), hydrophobic fumed silica (R202, from
Aerosil/Degussa, Diamond Bar, Calif.), Ni fiber (30 .mu.m diameter,
500 .mu.m length; from Intramicron, Birmingham, Ala.), Ni-coated
graphite (I) (60% Ni-coated graphite; from Novamet, Wyckoff, N.J.),
Ni-coated graphite (II) (60% Ni-coated graphite; from Sulzer
Metco/Ambeon, Switzerland), mercapto silane adhesion promoter
(Silane A189; GE Specialty Materials, Wilton, CN), and epoxy silane
adhesion promoter (Silane A187; GE Specialty Materials, Wilton,
CN).
TABLE-US-00001 TABLE I Material Weight Percentage PERMAPOL P 3.1
Polythioether Polymer 11.92 THIOPLAST G4 Polysulfide Polymer 12.04
Sulfur-containing phenolic resin 0.63 HB-40 Plasticizer 1.14
Calcium Chromate 3.69 Silica 5.23 Ni Fiber 6.98 Ni-coated Graphite
(I) 29.08 Ni-coated Graphite (II) 29.08 Silane Adhesion Promoter
(mercapto) 0.10 Silane Adhesion Promoter (epoxy) 0.10
[0056] Separately, the following materials were mixed in the
amounts according to Table II to form a curing agent composition:
manganese dioxide from EaglePicher (Phoenix, Ariz.), partially
hydrogenated terphenyl, stearic acid, fumed silica, sodium stearate
from Witco Chemicals, molecular sieve powder to remove excess
moisture from the curing agent, and
dipentamethylene/thiuram/polysulfide mixture from Akrochem
Corporation (Akron, Ohio) to accelerate the cure. The curing agent
composition was allowed to set or age from at least five days
before combining with the base composition.
TABLE-US-00002 TABLE II Material Weight Percentage Manganese
Dioxide 54.59 Partially Hydrogenated Terphenyl 35.92 Stearic Acid
0.60 Fumed Silica 2.00 Sodium Stearate 0.73 Molecular Sieve Powder
0.70 Dipentamethylene/Thiuram/Polysulfide 5.46 Mixture
[0057] One hundred parts by weight of the electrically conductive
base composition according to Table I, and 10 parts by weight of
the curing agent composition of Table II Were combined to prepare
the electrically conductive preformed composition. After thorough
mixing and degassing, the electrically conductive preformed
composition thus formed was extruded into a tape form and
refrigerated at -40.degree. C.
[0058] The surface adjacent to the perimeter of an aircraft access
panel was first coated with low VOC epoxy primer according to
specification MMS-423 and cured. The surface was cleaned and then
coated with adhesion promoters PR-148 or PR-184 from PRC-DeSoto
International, Inc. The access panel was made from titanium alloy
conforming to AMS-T-9046. After the refrigerated electrically
conductive preformed composition equilibrated to use temperature,
4.degree. C. to 32.degree. C. (40.degree. F. to 90.degree. F.), the
electrically conductive preformed composition in tape form was
manually applied to the surface adjacent to the perimeter of the
access panel. The access panel was put in place to cover the access
opening and clamped down, forcing the excess electrically
conductive preformed composition around the edges of the access
panel to fill the aperture. Excess electrically conductive
preformed composition was easily removed. After 3 to 4 hours at a
temperature of 4.degree. C. to 32.degree. C. (40.degree. F. to
90.degree. F.), a tight seal, resistant to moisture and aircraft
fuel, resulted.
[0059] The cured sealant exhibited a sheet resistance (four-point
probe) of less than 0.50 .OMEGA./cm.sup.2. Seals to apertures
between an aluminum test fixture and a carbon/epoxy lid exhibited
shielding effectiveness from 1 MHz to 200 MHz when tested in an
anechoic chamber. Similarly sealed apertures also exhibited
shielding effectiveness from 0.1 GHz to 18 GHz when tested in a
stirred mode chamber.
[0060] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art that numerous variations of the details of
the present invention may be made without departing from the
invention as defined in the appended claims.
* * * * *