1. Field of Invention
This invention covers composite thermal laminates having flame resistant properties. The invention also covers use of the composite laminate in a thermal and acoustic blanket as may be found in an aircraft fuselage or a turbine engine compartment.
2. Background of the Invention
U.S. Pat. No. 6,322,022 to Fay et al. discloses burnthrough resistant systems for transportation especially aircraft.
U.S. Pat. No. 6,670,291 to Tomkins and Vogel-Martin describes a laminate sheet material for fire barrier applications.
There remains an ongoing need for thermal and acoustic blankets for aircraft structures having reduced weight and improved flame spread resistance.
This invention is directed to a composite laminate comprising in order (a) a polymeric moisture barrier having a thickness from 6.0 to 25.0 micrometers and a UL 94 flame classification of V-0, (b) an inorganic platelet layer having a thickness from 7.0 to 76.0 micrometers and a UL 94 flame classification of V-0 wherein the platelets comprising the platelet layer have an aspect ratio of from 100 to 20,000, and (c) a thermoplastic film layer having a thickness no greater than 25 micrometers, an average elongation to break no greater than 150% and a UL 94 flame classification of V-0. The invention is also directed to a thermal insulation and acoustic blanket comprising an inorganic or organic core surrounded by the above composite laminate wherein the thermoplastic film layer of the composite laminate contacts and encapsulates the core.
Moisture Barrier Layer
By moisture barrier is meant that the polymeric layer has an inability to pass liquids but has some ability to pass vapor. Typically, a 25 micrometer thick sample of the barrier material when tested by the water method of ASTM E96/E 96M-05 has a water vapor permeability not exceeding 60 g/(m2·24 h). An additional requirement is that the barrier should have a UL 94 flame classification of V-0. UL 94 flame classification is an Underwriters Laboratory test, The Standard for Flammability of Plastic Materials for Parts in Devices and Appliances, which measures a material's tendency either to extinguish or to spread the flame once the specimen has been ignited. V-0 indicates that the material is tested in a vertical position and self-extinguished within ten seconds after the ignition source is removed. A further requirement of the moisture barrier is that it should have a thickness in the range of from 6.0 to 25 micrometers. More preferably the thickness range should be from 6.0 to 20.0 micrometers and most preferably in the range from 6 to 10 micrometers. The barrier layer further provides mechanical strength and stiffness to the laminate as well as protecting the inorganic platelet layer. Preferred film materials are fluoropolymer, polyimide, polyetheretherketone (PEEK) and polyetherketoneketone (PEKK) all of which are commercially available. A suitable fluoropolymer is available from E.I. du Pont de Nemours, Wilmington, Del. under the tradename Tedlar. The surface of the barrier layer in contact with the inorganic platelet layer may optionally be treated to improve wetability and/or adhesion with the inorganic platelet layer. Suitable surface treatment methods include, but are not limited to, corona etching and washing with coupling agents such as ammonium, phosphonium or sulfonium salts. The outer surface of the barrier layer i.e. the surface not in contact with the inorganic platelet layer may optionally be coated with polyterafluoroethylene (PTFE) or may be metalized.
Platelet Layer
The thickness of an individual platelet typically ranges from about 5 Angstroms to about 5,000 Angstroms more preferably from about 10 Angstroms to about 4,200 Angstroms. The mean value of the maximum width of a platelet typically ranges from about 10,000 Angstroms to about 30,000 Angstroms The aspect ratio of an individual platelet typically ranges from 100 to 20,000.
In one embodiment of this invention, the inorganic platelet layer contains 100% platelets i.e. there is no carrier material such as resin, adhesive, cloth or paper. However, there may be some residual dispersant arising from incomplete drying of the platelet dispersion.
In another embodiment of this invention, a lightweight open weave fabric scrim is embedded into or laid onto the inorganic platelet layer to provide additional mechanical strength to the layer. The scrim can be made from natural, organic or inorganic fibers with glass, cotton, nylon or polyester being typical examples. A glass fiber scrim is particularly preferred for embedding into the platelet layer. The scrim may be a woven or knit structure and has a typical areal weight not exceeding 40 grams per square meter. The scrim is positioned into the platelet layer either after the platelet material has been coated onto the moisture barrier layer or while the platelet material is being coated onto the moisture barrier layer.
It is a requirement that the thickness of the platelet layer, without scrim, is from 7.0 to 76 micrometers and more preferably from 7.0 to 50 micrometers. A further requirement is that the platelet layer has a UL 94 flame classification of V-0. The function of the platelet layer, in which adjacent platelets overlap, is to provide a flame and hot gas impermeable barrier. The inorganic platelets may be clay, such as montmorillonite, vermiculite, mica, talc and combinations thereof. Preferably, the inorganic oxide platelets are stable (i.e., do not burn, melt or decompose) at about 600 degrees C., more preferably at about 800 degrees C. and most preferably at about 1000 degrees C. Vermiculite is the preferred platelet material for this invention. Vermiculite is a hydrated magnesium aluminosilicate micaceous mineral found in nature as a multilayer crystal. Vermiculite typically comprises by (dry) weight, on a theoretical oxide basis, about 38-46% SiO2, about 16-24% MgO, about 11-16% Al2O3, about 8-13% Fe2O3 and the remainder generally oxides of K, Ca, Ti, Mn, Cr, Na, and Ba. “Exfoliated” vermiculite refers to vermiculite that has been treated, chemically or with heat, to expand and separate the layers of the crystal, yielding high aspect ratio vermiculite platelets. Suitable vermiculite materials are available from W. R. Grace of Cambridge, Mass., under the trade designations MicroLite 963 and MicroLite HTS-XE.
Film Layer
It is a requirement that the thermoplastic film layer has a thickness no greater than 25 micrometers. In a preferred embodiment, the thermoplastic film layer has a thickness no greater than 15 micrometers. More preferably the thickness is no greater than 10 micrometers. An additional requirement is that the thermoplastic film layer also has a UL 94 flame classification of V-0. A further requirement of this film layer is that the average elongation to break of the film is no greater than 150% and more preferably no greater than 125%. By average elongation we mean the average value of the elongation as measured in the machine direction and in the transverse direction which is a direction orthogonal to the machine direction. Preferably the film layer must also be capable of softening. By softening we mean that the film layer can soften sufficiently to bond to another thermoplastic film layer without completely melting. Preferred thermoplastic materials are polyketone, polyimide, polysulfone, polyarylene sulfide, fluoropolymers, liquid crystal polymers and polycarbonate. Examples of polyketone are polyetheretherketone (PEEK) and polyetherketoneketone (PEKK). Polyethersulfone and polyphenylsulfone are examples of polysulfone. Poly(p-phenylene sulfide is a suitable polyarylene sulfide for use in this invention. Polyvinylfluoride (PVF) and polyvinylidinefluoride (PVDF) are suitable examples of fluoropolymers. Polyarylate is an example of a suitable liquid crystal polymer. Some of these films may also be coated with a second polymeric material. For example, a polyimide film, Kapton®, may be coated with fluorinated ethylene propylene, FEP and used in this invention.
In a preferred embodiment, the moisture barrier membrane layer is polyimide and the thermoplastic film layer is PEKK.
Acoustic Blanket
The composite laminate as described above may be used as a component in a thermal insulation and acoustic blanket. A thermal insulation and acoustic blanket of this invention comprises:
(1) a polymeric moisture barrier having a thickness from 6.0 to 25.0 micrometers and a UL 94 flame classification of V-0,
(2) an inorganic platelet layer having a thickness from 7.0 to 76.0 micrometers and a UL 94 flame classification of V-0 wherein the platelets comprising the platelet layer have an aspect ratio of from 100 to 20,000, and
(3) a thermoplastic film layer having a thickness no greater than 25 micrometers, an average elongation to break no greater than 150% and a UL 94 flame classification of V-0,
wherein the thermoplastic film layer of the composite laminate contacts and encapsulates the core.
It is a requirement for the core 14 to meet the following flammability requirements. In a vertical test (60 seconds ignition), when tested according to Federal Aviation Regulation, Section 25, Appendix F, Part1, the core must be self extinguishing in no greater than 10 seconds and must have a maximum burn length of no greater than 102 mm. In a 45 Degree Angle Test, when tested according to BSS7230, the self extinguishing time must be no greater than 5 seconds and the afterglow no greater than 10 seconds.
The core may be foam or an organic or inorganic fibrous material. A suitable foam material is polyimide available under the tradename INSULMIDE from Johns Manville Insulations Group, Denver, Colo. or SOLIMIDE from Inspec Foams, Allen, Tex. Suitable non-metallic fibers include, but are not limited to, glass fibers, aramid fibers, crystalline ceramic oxide (including quartz) fibers, silicon nitride fibers, silicon carbide fibers, oxidized polyacrylonitrile fibers, carbon fibers, and combinations thereof.
Glass fiber is a preferred material with E-glass, a low alkali borosilicate glass, being particularly suitable. Ceramic oxide materials are typically metal oxides that have been consolidated by the action of heat. Ceramic oxide fibers generally refer to a class of fibers typically containing one or more oxides of aluminum, silicon, and boron. Many other additives may also be present (e.g., oxides of sodium, calcium, magnesium, and phosphorus) within the fibers, although the fibers include primarily metal oxides. Typically, the ceramic oxide fibers are crystalline ceramics and/or a mixture of crystalline ceramic and glass (i.e., a fiber that contains both crystalline ceramic and glass phases). Preferred ceramic oxide fibers are aluminosilicate, aluminoborosilicate, and alumina fibers, and may be in the form of yarns or in the form of staple fibers. The preferred form of non-metallic fiber is a batting which is a soft bulky assembly of fibers, usually carded. Battings have a typical density range of from 5.5 to 24.0 kg./m3. Suitable glass batting is available under the MICROLITE AA tradename from Johns Manville OEM Insulations Division, Denver, Colo. The core may comprise more than one layer of material. The materials in different layers of the core need not be the same.
The core is encapsulated by the composite laminate. This is achieved by wrapping the composite laminate around the core 14 such that the thermoplastic film layer 13 is adjacent to the core. The composite laminate is subjected to sufficient heat to partially soften and fuse together the two thermoplastic film layers, as shown at 15 in
Test Methods
Burnthrough time was measured on a modified thermal protective performance (TPP) instrument as specified in Section 8.2 of NFPA 2112: Standard on Flame-Resistant Garments for Protection of Industrial Personnel Against Flash Fire, 2007 Edition. This is further explained by reference to
In the following examples, all parts and percentages are by weight and all degrees in centigrade unless otherwise indicated. Examples prepared according to the current invention are indicated by numerical values. Control or Comparative Examples are indicated by letters. Data and test results relating to the Comparative and Inventive Examples are shown in Table 1.
Example A was a 127 micron thick sample of Nomex® Type 418™ paper having an areal weight of 149 g/m2. Nomex® Type 418™ is paper produced by blending about 50% mica platelets with short fibers (floc) and filmy particles (fibrids) of a synthetic m-aramid polymer followed by calendaring the paper at elevated temperature and pressure. Nomex® Type 418™ paper is available from E.I. DuPont de Nemours, Wilmington, Del. The use of Nomex® Type 418™ as a burnthrough barrier paper for aircraft thermal blanket applications is further described in U.S. Pat. Nos. 6,627,561 and 6,670,291 as well as in PCT patent application WO2006/028666. Three samples of this paper were submitted to the burnthrough test and gave burn times in the range of 1.05 to 2.28 minutes with an average burn time of 1.61 minutes. The end of test times were the same as the burn though times. The grade of a paper tested is compliant with FAR 25.856(b).
Example 1 was prepared in the following manner. A 7.6 micron layer of polyimide film available from DuPont under the tradename Kapton was used as the moisture barrier. The polyimide film had an areal weight of 12.2 g/m2. An aqueous dispersion of MicroLite® 963 grade vermiculite platelets were used as received and coated onto the polyimide film using an adjustable micrometer film applicator from the Paul N. Gardner Company Inc., Pompano Beach, Fla. The coated vermiculite film was dried overnight at room temperature to remove residual dispersant. The vermiculite layer had an areal weight of 37.9 g/m2. A 6.0 micrometer thick layer of PEKK having an areal weight of 9.2 g/m2 and an average elongation to break of 120% was used as the thermoplastic film layer and was placed onto the vermiculite layer. The composite assembly was then placed in a press at a temperature of 180° C. for 40 seconds to consolidate the layers together into a laminate weighing 59.3 g/m2. The consolidated composite laminate was subjected to the burnthrough test. There was no burnthrough after 5 minutes when the test was stopped. The composite laminate weighed only 40% of that of the Nomex® Type 418™ comparator yet had a far superior burnthrough resistance.
Example 2 was prepared in the following manner. A 6.0 micrometer thick layer of PEKK having an areal weight of 9.2 g/m2 was used as the moisture barrier. Platelets of MicroLite®963 grade were coated onto the PEKK film as in Example 1. The coated film was dried overnight at room temperature to remove residual traces of dispersant. The vermiculite layer had an areal weight of 51.1 g/m2. A 6.0 micrometer thick layer of PEKK having an areal weight of 9.2 g/m2 and an average elongation to break of 120% was used as the thermoplastic film layer and was placed onto the vermiculite layer. The composite assembly was then placed in a press at a temperature of 180° C. for 40 seconds to consolidate the layers together into a laminate weighing 69.5 g/m2. The consolidated composite laminate was subjected to the burnthrough test. There was no burnthrough after 5 minutes when the test was stopped. The composite laminate weighed only 47% of that of the Nomex® Type 418™ comparator yet had a far superior burnthrough resistance.
It is contemplated that the composite laminate of Examples 1 or 2 can be combined with a core of fiberglass batting such as a 25.4 mm thick sheet of Microlite® AA having a density of 6.7 Kg/m3. In such a combination, a sheet of composite laminate is placed over both outer surfaces of the batting such that the thermoplastic film layer of the laminate is adjacent to, and in contact with, the outer surfaces of the batting. Furthermore, the composite laminates are of a larger area than the batting and extend over the four edges of the batting. The batting is encapsulated by crimping together the ends of the composite laminates that extend over the batting and, by applying heat in the crimp zone to soften and fuse the two laminates together, the batting is encapsulated.
It is also contemplated that the composite laminate of Examples 1 or 2 can be combined with a core of polyimide foam such as a 25.4 mm thick sheet of Solimide® TA-301 having a density of 6.4 Kg/m3. In such a combination, a sheet of composite laminate is placed over both outer surfaces of the foam such that the thermoplastic film layer of the laminate is adjacent to, and in contact with, the outer surfaces of the foam. Furthermore, the composite laminates are of a larger area than the foam and extend over the four edges of the foam. The foam is encapsulated by crimping together the ends of the composite laminates that extend over the foam and, by applying heat in the crimp zone to soften and fuse the two laminates together, the foam is encapsulated.
Number | Name | Date | Kind |
---|---|---|---|
3325340 | Walker | Jun 1967 | A |
3346219 | Salyer et al. | Oct 1967 | A |
3434917 | Kraus et al. | Mar 1969 | A |
3841954 | Lawler | Oct 1974 | A |
4655842 | Ou et al. | Apr 1987 | A |
4698267 | Tokarsky | Oct 1987 | A |
4729921 | Tokarsky | Mar 1988 | A |
4780147 | Ou et al. | Oct 1988 | A |
4810565 | Wasitis et al. | Mar 1989 | A |
4940112 | O'neill | Jul 1990 | A |
5026456 | Hesler et al. | Jun 1991 | A |
5030518 | Keller | Jul 1991 | A |
5084136 | Haines et al. | Jan 1992 | A |
5126013 | Wiker et al. | Jun 1992 | A |
5223094 | Kirayoglu et al. | Jun 1993 | A |
5244729 | Harrison | Sep 1993 | A |
5314742 | Kirayoglu et al. | May 1994 | A |
5336348 | Mindler | Aug 1994 | A |
5373038 | Horacek | Dec 1994 | A |
5595817 | Sch afer et al. | Jan 1997 | A |
5760146 | von Gentzkow et al. | Jun 1998 | A |
5765318 | Michelsen | Jun 1998 | A |
5888610 | Fournier et al. | Mar 1999 | A |
6244729 | Waldmann | Jun 2001 | B1 |
6291053 | Peiffer et al. | Sep 2001 | B1 |
6322022 | Fay et al. | Nov 2001 | B1 |
6443257 | Wiker et al. | Sep 2002 | B1 |
6565040 | Fay et al. | May 2003 | B2 |
6627561 | Wulliman et al. | Sep 2003 | B1 |
6670291 | Tompkins et al. | Dec 2003 | B1 |
7767597 | Garvey | Aug 2010 | B2 |
8292027 | Richardson, III et al. | Oct 2012 | B2 |
8387748 | Richardson, III et al. | Mar 2013 | B2 |
8607926 | Richardson, III et al. | Dec 2013 | B2 |
8607927 | Richardson, III et al. | Dec 2013 | B2 |
8607928 | Richardson, III et al. | Dec 2013 | B2 |
8678133 | Clausi et al. | Mar 2014 | B2 |
8869933 | McKnight et al. | Oct 2014 | B1 |
9056666 | Richardson, III et al. | Jun 2015 | B2 |
9242717 | Richardson, III et al. | Jan 2016 | B2 |
20030170418 | Mormont | Sep 2003 | A1 |
20040211506 | Wang et al. | Oct 2004 | A1 |
20050173780 | Sethumadhavan et al. | Aug 2005 | A1 |
20060046598 | Shah | Mar 2006 | A1 |
20060128866 | Diakoumakos et al. | Jun 2006 | A1 |
20070155265 | Anderson | Jul 2007 | A1 |
20080153373 | Hall et al. | Jun 2008 | A1 |
20080156367 | Uschold et al. | Jul 2008 | A1 |
20080189840 | Knoff et al. | Aug 2008 | A1 |
20080254313 | Kennedy et al. | Oct 2008 | A1 |
20090094754 | Hall et al. | Apr 2009 | A1 |
20090269565 | Peng | Oct 2009 | A1 |
20090314480 | Grinbergs et al. | Dec 2009 | A1 |
20100024969 | Wang et al. | Feb 2010 | A1 |
20100056687 | Diakoumakos et al. | Mar 2010 | A1 |
20100065368 | Tazian | Mar 2010 | A1 |
20100133039 | Liguore | Jun 2010 | A1 |
20100159221 | Kourtakis et al. | Jun 2010 | A1 |
20100173152 | Beraud et al. | Jul 2010 | A1 |
20100209679 | Tompkins | Aug 2010 | A1 |
20100243807 | Hossain et al. | Sep 2010 | A1 |
20110094826 | Richardson, III et al. | Apr 2011 | A1 |
20110114342 | Ono et al. | May 2011 | A1 |
20120003451 | Weigel et al. | Jan 2012 | A1 |
20120128959 | Fernando | May 2012 | A1 |
20120273618 | Fernando | Nov 2012 | A1 |
20120321848 | Richardson, III et al. | Dec 2012 | A1 |
20120321849 | Richardson, III et al. | Dec 2012 | A1 |
20120321868 | Richardson, III et al. | Dec 2012 | A1 |
20120321883 | Richardson, III et al. | Dec 2012 | A1 |
20130068555 | Cherniak et al. | Mar 2013 | A1 |
20130092321 | Fernando et al. | Apr 2013 | A1 |
20130196136 | Contzen et al. | Aug 2013 | A1 |
20130240291 | Tinianov | Sep 2013 | A1 |
20140008145 | Lin et al. | Jan 2014 | A1 |
20140011006 | Guinaldo Fernandez et al. | Jan 2014 | A1 |
20140065357 | Richardson, III et al. | Mar 2014 | A1 |
20140072762 | Richardson, III et al. | Mar 2014 | A1 |
20140072763 | Richardson, III et al. | Mar 2014 | A1 |
20140144723 | Kim et al. | May 2014 | A1 |
20140272252 | Golden | Sep 2014 | A1 |
Number | Date | Country |
---|---|---|
905985 | Apr 1987 | BE |
1141866 | Feb 1997 | CN |
0044162 | Jan 1982 | EP |
0501271 | Sep 1992 | EP |
0601877 | Jun 1994 | EP |
1326745 | Nov 2006 | EP |
2421750 | Jan 2013 | EP |
200198434 | Dec 2001 | WO |
2002032663 | Apr 2002 | WO |
2006028666 | Mar 2006 | WO |
2008136875 | Nov 2008 | WO |
2009052015 | Apr 2009 | WO |
2014018107 | Jan 2014 | WO |
Entry |
---|
Khang D. Tran, Light Weight Fire Barrier Materials for Aircraft Fuselage Thermal/ Acoustical Insulation; The Mexmil Company, Santa Ana, California, USA—Date Unavailable. |
U.S. Appl. No. 14/081,010, filed Nov. 15, 2013, Richardson, III et al. |
U.S. Appl. No. 14/081,022, filed Nov. 15, 2013, Richardson, III et al. |
U.S. Appl. No. 14/077,394, filed Nov. 12, 2013, Richardson, III et al. |
HT4795EP/EPT EPO Communication with Jehier Brief (English Translation)—Oct. 23, 2013. |
HT4795EP/EPT EPO Communication with COGEBI Opposition Brief—Oct. 23, 2013. |
HT4795EPEPT DuPont Reply Brief—May 21, 2014. |
Jacques, A. et al., Development of A Thermal/Acoustic Insulating Blanket Responding to the Far 25.856 by the Integration of Mica Flame Barrier, Fire and Cabin Safety Research Conference, Lisbon, pp. 1-9, Nov. 18, 2004. |
Gilmer, Carter T., et al., Polymer Mechanical Properties via a New Laboratory Tensile Tester, Journal of Chemical Education, vol. 73, No. 11, pp. 1062-1065, Nov. 1996. |
DOT/FAA/AR-00/12, Aircraft Materials Fire Test Handbook, Office of Aviation Research, Washington, D.C. 20591, Apr. 2000. |
ASTM D882-09, Standard Test Method for Tensile Properties of Thin Plastic Sheeting, ASTM International, Feb. 7, 2014. |
ASTM-F501-93, Standard Test Method for Aerospace Materials Response to Flame, With Vertical Test Specimen (for Aerospace Vehicles Standard Conditions), American Society for Testing and Materials, Mar. 11, 2014. |
ASTM E96/E96M-05. |
FAR 25.853, Oct. 15, 2004. |
FAR 25.856(b). |
FAR 25, Appendix F, Part 1—Jul. 14, 2003. |
NFPA 2112: Section 8.2. |
Affidavit—A signed statement by Mr. Dogan Ogreten, R&D Manager at JEHIER SAS, the company marketing the product Terflame 29—Oct. 15, 2013 (Translation provided in HT4795EP/EPT EPO Communication with Jehier Brief cited above). |
A description of the product Terflame 29 qualified by Airbus since Jun. 2008 and marketed since May 2008—Oct. 16, 2013 (Translation provided in HT4795EP/EPT EPO Communication with Jehier Brief cited above). |
HT4795WOPCT—International Search Report and Written Opinion (PCT/US2010/031377—dated Jul. 27, 2010. |
HT4795WOPCT—International Preliminary Report on Patentability (PCT/US2010/031377—dated Oct. 25, 2011. |
(U.S. Appl. No. 12/759,741)—Non-Final Office Action dated Feb. 1, 2012. |
(U.S. Appl. No. 12/759,741)—Response to Non-Final Office Action dated Apr. 18, 2012. |
(U.S. Appl. No. 12/759,741)—Final Office Action dated Jun. 4, 2012. |
(U.S. Appl. No. 12/759,741)—Response to Final Office Action dated Jun. 22, 2012. |
(U.S. Appl. No. 13/325,741)—Non-Final Office Action dated Mar. 26, 2013. |
(U.S. Appl. No. 13/325,741)—Response to Non-Final Office Action dated Jul. 25, 2013. |
(U.S. Appl. No. 13/325,770)—Non-Final Office Action dated Mar. 26, 2013. |
(U.S. Appl. No. 13/325,770)—Response to Non-Final Office Action dated Jul. 25, 2013. |
(U.S. Appl. No. 13/325,804)—Non-Final Office Action dated Mar. 26, 2013. |
(U.S. Appl. No. 13/325,804)—Response to Non-Final Office Action dated Jul. 25, 2013. |
(U.S. Appl. No. 14/077,394)—Non-Final Office Action dated Sep. 3, 2014. |
Report on Filing of an Action Regarding a Patent (U.S. Pat. No. 8,607,926), Oct. 1, 2014, Delaware. |
Complaint (U.S. Pat. No. 8,607,926), Oct. 1, 2014, Delaware. |
Answer, Affirmative Defenses, Counterclaims (U.S. Pat. No. 8,607,926), Nov. 21, 2014, Delaware. |
Defendant's First Amended Answer (U.S. Pat. No. 8,607,926), Dec. 19, 2014, Delaware. |
Protective Order (U.S. Pat. No. 8,607,926), Mar. 23, 2015, Delaware. |
Defendant's Invalidity Contentions (Redacted) (U.S. Pat. No. 8,607,926), May 18, 2015, Delaware. |
Memorandum Order re Motion to Dismiss (U.S. Pat. No. 8,607,926), Aug. 5, 2015, Delaware. |
Plaintiff's Brief in Support of Motion to Dismiss (U.S. Pat. No. 8,607,926), Jan. 9, 2015, Delaware. |
Answer Brief in Opposition to Plaintiff's Motion to Dismiss (U.S. Pat. No. 8,607,926), Feb. 2, 2015, Delaware. |
Plaintiff's Reply in Support of Motion to Dismiss (U.S. Pat. No. 8,607,926), Feb. 12, 2015, Delaware. |
Defendant's Letter to Judge Andrews re addl authority (U.S. Pat. No. 8,607,926), Mar. 3, 2015, Delaware. |
Plaintiff's Response to Subsequent Authority (U.S. Pat. No. 8,607,926), Mar. 6, 2015, Delaware. |
Dow Corning 280A Adhesive, 2001 (no month). |
(U.S. Appl. No. 14/081,010)—Final Office Action dated Mar. 12, 2015. |
(U.S. Appl. No. 14/081,010)—Reply to Final Office Action dated May 18, 2015. |
(U.S. Appl. No. 14/081,022)—Final Office Action dated Mar. 12, 2015. |
(U.S. Appl. No. 14/081,022)—Reply to Final Office Action dated May 28, 2015. |
(U.S. Appl. No. 14/515,4386)—Non-Final Office Action dated May 29, 2015. |
Unifrax's Discovery Letter, Redacted (U.S. Pat. No. 8,607,926), May 27, 2016, Delaware. |
DuPont's Discovery Letter, Redacted (U.S. Pat. No. 8,607,926), May 27, 2016, Delaware. |
Unifrax's Discovery Response, Redacted (U.S. Pat. No. 8,607,926), May 31, 2016, Delaware. |
DuPont's Discovery Response, Redacted (U.S. Pat. No. 8,607,926), May 31, 2016, Delaware. |
Order RE Discovery Dispute (U.S. Pat. No. 8,607,926), Jun. 14, 2016, Delaware. |
Unifrax's Supplemental Discovery Letter, Redacted (U.S. Pat. No. 8,607,926), Jun. 17, 2016, Delaware. |
Expert Report of Thomas J. Nosker, Ph.D. (U.S. Pat. No. 8,607,926), Jun. 17, 2016, Delaware. |
DuPont's Supplemental Discovery Letter, Redacted (U.S. Pat. No. 8,607,926), Jun. 21, 2016, Delaware. |
Unifrax's Initial Invalidity Contentions (U.S. Pat. No. 8,607,926), May 18, 2015, Delaware. |
Revised Joint Claim Construction Chart (U.S. Pat. No. 8,607,926), Sep. 30, 2015, Delaware. |
Markman Joint Claim Construction Brief (U.S. Pat. No. 8,607,926), Nov. 16, 2015, Delaware. |
Markman Hearing Transcript (U.S. Pat. No. 8,607,926), Dec. 14, 2015, Delaware. |
Unifrax's Second Amended Answer, Affirmative Defenses, and Counterclaims, Redacted (U.S. Pat. No. 8,607,926), Dec. 22, 2015, Delaware |
Plaintiff DuPont's Answer to Defendant Unifrax's Second Amended Answer, Defenses, and Counterclaims, Redacted (U.S. Pat. No. 8,607,926), Jan. 12, 2016, Delaware. |
Markman Claim Construction Decision (U.S. Pat. No. 8,607,926), Jan. 13, 2016, Delaware. |
Letter to Judge Andrews RE: Proposed Claim Construction Orders (U.S. Pat. No. 8,607,926), Jan. 19, 2016, Delaware. |
Claim Construction Order (U.S. Pat. No. 8,607,926), Jan. 20, 2016, Delaware. |
Defendant Unifrax's Supplemental Invalidity Contentions, Redacted (U.S. Pat. No. 8,607,926), Mar. 25, 2016, Delaware. |
Stipulation and Order of Dismissal of Defendant Unifrax's Counterclaim III Without Prejudice (U.S. Pat. No. 8,607,926), Apr. 22, 2016, Delaware. |
Unifrax's Motion for Leave, Redacted (U.S. Pat. No. 8,607,926), Jul. 15, 2016, Delaware. |
DuPont's Opposition to Unifrax's Motion for Leave, Redacted (U.S. Pat. No. 8,607,926), Jul. 29, 2016, Delaware. |
Unifrax's Motion for Leave, Redacted (U.S. Pat. No. 8,607,926), Aug. 11, 2016, Delaware. |
Khang D. Tran, Light Weight Fire Barrier Materials for Aircraft Fuselage Thermal/ Acoustical Insulation; The Mexmil Company, Santa Ana, California, USA. |
Number | Date | Country | |
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61171163 | Apr 2009 | US |
Number | Date | Country | |
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Parent | 12759741 | Apr 2010 | US |
Child | 14515267 | US |