U.S. patent application number 14/399454 was filed with the patent office on 2015-06-11 for self-healing material.
The applicant listed for this patent is PEN Inc.. Invention is credited to Richard Lee Fink, Dongsheng Mao, Zvi Yaniv.
Application Number | 20150159316 14/399454 |
Document ID | / |
Family ID | 50068673 |
Filed Date | 2015-06-11 |
United States Patent
Application |
20150159316 |
Kind Code |
A1 |
Mao; Dongsheng ; et
al. |
June 11, 2015 |
SELF-HEALING MATERIAL
Abstract
A glass fiber-reinforced polymer composite includes a polymer
matrix, a plurality of glass fibers embedded within the polymer
matrix, a first hollow glass fiber containing a resin embedded
within the polymer matrix, a second hollow glass fiber containing a
catalyst suitable for curing the resin embedded within the polymer
matrix. When damage occurs to such a composite, the glass fibers
containing the resin and the catalyst are ruptured, resulting in
their mixing together so that the resin is cured for repairing the
ruptured location.
Inventors: |
Mao; Dongsheng; (Austin,
TX) ; Fink; Richard Lee; (Austin, TX) ; Yaniv;
Zvi; (Austin, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PEN Inc. |
Deerfield Beach |
FL |
US |
|
|
Family ID: |
50068673 |
Appl. No.: |
14/399454 |
Filed: |
May 16, 2013 |
PCT Filed: |
May 16, 2013 |
PCT NO: |
PCT/US2013/041326 |
371 Date: |
November 6, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61648306 |
May 17, 2012 |
|
|
|
Current U.S.
Class: |
442/173 ;
442/175; 442/180 |
Current CPC
Class: |
Y10T 442/2934 20150401;
C08J 5/08 20130101; D06M 2101/00 20130101; C08J 2331/00 20130101;
D06M 15/507 20130101; C08J 5/24 20130101; C08J 5/043 20130101; Y10T
442/2951 20150401; C08J 2363/00 20130101; Y10T 442/2992
20150401 |
International
Class: |
D06M 15/507 20060101
D06M015/507 |
Claims
1. A glass fiber-reinforced polymer composite comprising: a polymer
matrix; a plurality of glass fibers embedded within the polymer
matrix; a first hollow glass fiber embedded within the polymer
matrix, the first hollow glass fiber containing a resin; and a
second hollow glass fiber embedded within the polymer matrix, the
second hollow glass fiber containing a catalyst suitable for curing
the resin.
2. The glass fiber-reinforced polymer composite as recited in claim
1, wherein the resin comprises a vinyl ester.
3. The glass fiber-reinforced polymer composite as recited in claim
1, wherein the resin comprises polyester.
4. The glass fiber-reinforced polymer composite as recited in claim
1, wherein the catalyst comprises methyl ethyl ketone peroxide.
5. The glass fiber-reinforced polymer composite as recited in claim
2, wherein the vinyl ester has a viscosity lower than 2,000
centipoises at room temperature.
6. The glass fiber-reinforced polymer composite as recited in claim
3, wherein the polyester has a viscosity lower than 2,000
centipoises at room temperature.
7. The glass fiber-reinforced polymer composite as recited in claim
4, wherein the methyl ethyl ketone peroxide has a viscosity lower
than 2,000 centipoises at mom temperature.
8. The glass fiber-reinforced polymer composite as recited in claim
1, wherein the polymer matrix comprises a thermosetting resin.
9. The glass fiber-reinforced polymer composite as recited in claim
1, wherein the polymer matrix is selected from the group consisting
of polyester, vinyl ester, and epoxy.
10. The glass fiber-reinforced polymer composite as recited in
claim 1, wherein the polymer matrix is a thermosetting resin
reinforced with a filler.
11. The glass fiber-reinforced polymer composite as recited in
claim 10, wherein the filler comprises carbon nanotubes.
12. The glass fiber-reinforced polymer composite as recited in
claim 10, wherein the filler comprises ceramic particles.
13. The glass fiber-reinforced polymer composite as recited in
claim 10, wherein the filler comprises graphite particles.
14. The glass fiber-reinforced polymer composite as recited in
claim 10, wherein the filler comprises graphene particles.
Description
[0001] This application claims priority to U.S. Provisional Patent
Application Ser. No. 61/648,306, which is hereby incorporated by
reference herein.
BACKGROUND INFORMATION
[0002] Composite materials are ideal for structural applications
where high strength-to-weight and stiffness-to-weight ratios are
important. Weight sensitive applications, such as construction,
aircraft, and space vehicles, are primary consumers of composites,
especially fiber-reinforced polymer matrix composites. However,
their use is limited due to the difficulty in damage detection and
repair, as well as lack of extended fatigue and impact resistance.
One way to protect material degradation is through the
incorporation of a self-healing ability.
[0003] To date, there has been significant research in self-healing
polymeric materials, and numerous studies, specifically in
fiber-reinforced polymers. Polymer composites have been attractive
candidates to introduce the autonomic healing concept into modern
day engineering materials. A breakthrough in the study of
self-healing materials was reported in 2001 by a research group at
University of Illinois (see S. R. White et al., "Autonomic healing
of polymer composites," Nature 409, pp. 794-797 (2001), which is
hereby incorporated by reference herein). White et al. first
introduced the incorporation of microcapsules containing a polymer
precursor into the matrix material of a non-fiber-reinforced
polymer composite for self-healing purposes. The polymer precursor
was contained in microcapsules and embedded into the matrix. The
matrix contained a randomly dispersed catalyst that was supposed to
react with the precursor flowing through any crack formed due to
damage and initiate polymerization. The polymer was then supposed
to bond the crack face closed. The investigators overcame several
challenges in developing microcapsules that were weak enough to be
ruptured by a crack but strong enough not to break during
manufacture of the composite system. The researchers showed that it
was possible to recover up to 75% of the maximum tensile strength
of the virgin composites. Successful work was done by Prof Bond's
group. The use of functional repair components stored in hollow
glass fibers ("HGF") placed with glass fiber/epoxy and carbon
fiber/epoxy laminates can effectively mitigate damage occurrence
and restore mechanical strength (see R. S. Trask, G. J. Williams
and I. P. Bond, "Bioinspired self-healing of advanced composite
structures using hollow glass fibres," J. R. Soc. Interface 4, pp.
363-371 (2007), which is hereby incorporated by reference herein).
If successful incorporation of the self-healing material into the
fiber-reinforced composites ("FRP") can be achieved, the benefit is
quite obvious. Those composites can serve longer with better
performance. Self-healing materials embedded in the FRP composite
or laminate showed considerable restoration of mechanical
properties such as flexural strength, compressive strength, impact
resistance, and a highly efficient recovery of matrix strength (see
G. Williams, R. S. Trask and I. P. Bond, "Self-healing sandwich
panels: Restoration of compressive strength after impact,"
Composites Science and Technology 68, pp. 3171-3177 (2008) G.
Williams, R. S. Trask and I. P. Bond, "A self-healing carbon
fiber-reinforced polymer for aerospace application," Composites
38(6), pp. 1525-1532 (2007), which are hereby incorporated by
reference herein).
[0004] Even though several methods have been suggested in autonomic
healing materials, the concept of repair by bleeding of enclosed
functional agents has garnered wide attention by the scientific
community. The concept of bleeding is also being considered for
commercial purposes in the aerospace industry. Achievements in the
field of self-healing polymers and polymer composites are far from
satisfactory. Working out the solutions would certainly push
polymer sciences and engineering forward.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1A illustrates a hollow glass fiber.
[0006] FIG. 1B illustrates a hollow glass fiber filled with a
self-healing agent.
[0007] FIG. 1C illustrates a hollow glass fiber filled with as
catalyst.
[0008] FIG. 2 illustrates an embodiment configured in accordance
with the present invention.
[0009] FIG. 3 illustrates a testing procedure performed on an
embodiment of the present invention.
[0010] FIG. 4 illustrates another testing procedure performed on an
embodiment of the present invention.
[0011] FIG. 5 shows digital images of GFRP specimens produced in
accordance with embodiments of the present invention.
DETAILED DESCRIPTION
[0012] The inventors discovered that a vinyl ester resin and a
methyl ethyl ketone peroxide ("MEKP") catalyst can serve well as a
self-healing material system for FRP composites due, at least in
part, to the following advantages:
[0013] 1. The vinyl ester can be cured at room temperature when
contacted or mixed with a MEKP catalyst.
[0014] 2. The viscosity of both the vinyl ester resin and the MEKP
catalyst is very low (<2,000 centipoises), which allows hollow
glass fibers or microcapsules to be easily filled with each.
[0015] It was found that the vinyl ester resin/MEKP catalyst
self-healing system can increase the service life of the panel and
recover performance soon after initial damage.
[0016] According to aspects of the present invention, an example is
hereinafter described,
[0017] Part I. Base materials
[0018] 1. Self-Healing Agent:
[0019] A vinyl ester resin (e.g., product designation Derakane
411-350) was commercially obtained from Ashland, Inc. The MEKP
catalyst was commercially obtained from Crompton Corporation. Other
resin systems, such as polyester and an appropriate catalyst may be
used instead.
[0020] 2. Hollow Glass Fiber:
[0021] FIG. 1A illustrates a cross-section of a hollow glass fiber
101. Large diameter hollow glass fibers were commercially obtained
from Sutter Instrument. The hollow glass fibers may be
approximately 4 inches long with an inner diameter ("1D") of
approximately 860 microns and an outer diameter ("OD") of
approximately 1500 microns, which yields a hollowness fraction of
approximately 33%. Other hollow glass fibers with different
dimensions or microcapsulates may be filled with self-healing
agents instead.
[0022] 3. Silicone Sealant:
[0023] Silicone sealant (e.g., commercially obtained from Master
Bond, Inc.) may be used to seal the hollow glass fibers.
[0024] 4. Fiberglass Fabric:
[0025] Product designation Hybon 2006 used to fabricate glass
fiber-reinforced polymer ("GFRP") panels was commercially obtained
from PPG Industries. Other types of fibers, such as carbon fibers
and synthetic fibers, may be used instead.
[0026] 5. Polyester Matrix:
[0027] The polyester matrix used to fabricate the GFRP panels was
commercially obtained from Hexion (e.g., Hexion's 712 type
polyester resin). Other thermosetting resins, such as epoxy, vinyl
ester, etc. may be used instead to perform the duty of the polymer
matrix. The polymer matrix may be enhanced with other polymers or
fillers, such as carbon nanotubes, ceramic particles, graphite or
graphene particles, etc.
[0028] Part 2. Fabricating GFRP Panels
[0029] 1. Filling Hollow Glass Fibers with Self Healing Agent:
[0030] Referring to FIGS. 1B-1C, the hollow glass fibers 101 were
first sealed at one end with silicone sealant 102. They were then
immersed into the vinyl ester liquid in a vacuum chamber to allow
the vinyl ester 203 (i.e., self-healing agent or resin) to be drawn
into the hollow glass fibers 101. Then the other ends of the hollow
glass fibers were also sealed with silicone sealant 102. The same
process was also utilized to fill separate hollow glass fibers 101
with the MEKP catalyst 204.
[0031] 2. Fabricating the GFRP Panels with Self-Healing Agent:
[0032] 12''.times.12''.times.1/2'' GFRP panels were made based on
two formulations. Formulation 1 had a loading of 2.5% self-healing
agent/catalyst compared to the total polyester matrix in the GFRP
panels. Formulation 2 had a loading of 5% self-healing
agent/catalyst compared to the total polyester matrix in the GFRP
panels. Five panels of each formulation were fabricated, Each panel
contained 22 layers of e-glass fiber fabric. For each panel, the
hollow glass fibers filled with self-healing agent were placed
between the fourth and fifth, and eighteenth and nineteenth layers
of the e-glass fiber fabric.
[0033] FIG. 2 illustrates an example of a GFRP panel 200 configured
in accordance with embodiments of the present invention. GFRP panel
200 is shown in a cross-section view of a GFRP composite integrated
with hollow glass fibers filled with self-healing agent 203 and
catalyst 204. Others of glass fibers 201 typically used to make
such composites are also shown embedded within the polymer (resin)
matrix 201 of the GFRP composite. When damage occurs to such a
panel, the glass fibers containing the self-healing agent and the
catalyst are ruptured, resulting in their mixing together so that
the agent is cued for repairing the ruptured location.
[0034] Part 3. Ballistic Testing of the GFRP Panels with
Self-Healing Agent
[0035] The GFRP panels were made by a hot pressing process. The
polyester resin mixed with MEKP catalyst (1.5%) was poured onto
each layer of the e-glass fiber fabric and put together to form a
laminated structure. It was pressed at a temperature of
approximately 250.degree. F. degree for approximately 30 minutes
and cooled down to room temperature. They were then made ready for
V50 ballistic testing.
[0036] FIG. 3 shows a sketch of a typical panel and the planner
placement of each shot for V50 ballistic testing. V50 tests were
performed with a 0.30 caliber FSP. V50 ballistic testing is the
velocity at which 50 percent of the shots go through and 50 percent
are stopped by an armor. U.S. military standard MIL-STD-662F V50
Ballistic Test defines a commonly used procedure for this
measurement.
[0037] Test Protocol
[0038] 1. First Round of Shots: For each set, there were 3 shots
per panel (15 total shots per set). All of these were used to
establish a V50 test result (referred to as V50-A). The locations
of these shots were near the dots marked "X" in FIG. 3.
[0039] 2. Second Round of Shots: Within approximately 1 hour of the
first round of shots, two panels were shot 3 more times and one
panel was shot 2 more times near (approximately 1'' from) the
original shots (this was done for both sets of panels). The purpose
was to test the ballistic performance of the panels before the
vinyl ester cured. Those 8 secondary shots were referred to as
V50-B. Note, only 8 total shots were used for this test, as the
remaining 7 shots were used in the third round of V50 testing
(described hereinafter).
[0040] 3. Third Round of Shots: After approximately 1 week of the
first round of shots (V50-A), the remaining 7 shots were made near
(approximately 1'' from) the remaining original shots. The purpose
was to allow the vinyl ester to be fully cured. Those 7 shots were
used for another V50 test (referred to as V50-C) Thus all initial
shots had a neighboring shot approximately 1'' from the original.
Each parcel had 6 shots 3 original and 3 for either V50-B or V50-C
testing.
[0041] Table 1 shows the V50 ballistic testing, results of the
self-healing GFRP panels. The configuration for placement of hollow
glass fibers (HGF) is shown below the table, where GF=glass fiber
fabric.
TABLE-US-00001 TABLE 1 Loading of self- healing agent % (V50-A)
(V50-B) (V50-C) 2.5 1585 1540 1614 5 1621 1544 1607
[0042] Placement of HGF:
GF/GF/GF/GF/HGF/GF/GF/GF/GF/GF/GF/GF/GF/GF/GF/GF/GF/GF/GF/HGF/GF/GF/GF/GF
[0043] In summary:
[0044] 1. V50-A is higher than V50-B. It was expected that after
the first ballistic shot, the panel would be weakened;
[0045] 2. V50-C is higher than V50-B and very close to the V50-A,
which means that the self-healing agent/catalyst effectively heals
the damaged area of the panels after the first ballistic shot.
[0046] Another example now described showed that the mechanical
properties of the GFRP composites can be recovered if the
self-healing agent is embedded in the matrix. This example
investigated the mechanical behavior before and after the
self-healing agent is cured after impact testing. Compression
strength after impact for the GFRP panels integrated with
self-healing agents was performed. The dimension of the specimens
for compression strength after impact testing is shown in FIG. 4
(based on ASTM D7136 and ASTM D7137 testing). The panel thickness
was approximately 0.2 inches, with 4 plies of the e-glass fiber
fabric utilized. The self-healing layer will be placed in the
middle of the specimens Polyester resin (Hexion's 712 type
polyester resin) and e-glass fiber (PPG's Hybon 2006 direct draw
roving, 24 oz) were used as base GFRP panel matrix materials for
experimentation. Vinyl ester was used as the self-healing agent and
MEKP as catalyst. The GFRP specimens were fabricated by being
integrated with self-healing agent based on 2.5 wt. % loading of
the self-healing agent to resin matrix. The hollow glass fibers
filled with self-healing agent and catalyst are placed in between
the second and third plies of the e-glass fiber fabric. For
comparison, also prepared were control GFRP panels for
experimentation. FIG. 5 shows GFRP specimens used in the
experimentation.
[0047] Fabricated were 4 GFRP samples. Each of the samples
contained 12 GFRP specimens. For the samples with self-healing
agent, 6 specimens of each sample were tested with impact. Then the
compression strength after impact was performed within an hour. The
remaining 6 specimens of each sample were performed with
compression strength after impact a week after the impact testing.
The average data was given after each testing. For comparison and
determining the self-healing efficiency, the compression strength
of the GFRP specimens (with no self-healing agent) without impact
was also tested.
[0048] When the impact was performed, the hollow glass fibers were
broken and the self-healing agent and the catalyst were expelled
from the fibers to react with each other. The self-healing agent
would barely react with the catalyst within the first hour.
However, the reaction would be completed in a week.
[0049] A fully instrumented low velocity impact (Instron) machine
was used to perform the impact at energy of 30 J.
[0050] The compression strength of the samples was the
following:
[0051] GFRP samples without self-healing agent: [0052] Compression
strength (before impact): 50.0 MPa [0053] Compression strength
after impact: 38.3 MPa
[0054] GFRP samples with 2.5% self-healing agent: [0055]
Compression strength 1 hour after impact: 35.2 MPa [0056]
Compression strength 1 week after impact: 48.1 MPa It can be seen
that the compression strength observed one week after impact (48.1
MPa) is significantly better than those tested within an hour after
impact (35.2 MPa), showing that the self-healing agent plays an
important role in healing the GFRP panels after damage. The
self-healing efficiency in this case is 96% and it almost recovers
to the compression strength of the undamaged GFRP (50.0 MPa), which
is almost fully recovered. Optimizing the loading of the
self-healing agent may improve the self-healing efficiency.
* * * * *