CN1723122A - Ballistic resistant and fire resistant composite articles - Google Patents

Abstract

The invention relates to a ballistically resistant and fire resistant composite articles for aircraft interiors and other applications. Composite articles are provided having a flexural modulus of at least about 80,000 lbs/sq. in. (552 MPa) a flexural strength at yield of at least about 800 lbs/sq. in. (5.52 MPa) an areal density of about 0.9 lb/ft<2> (4.40 kg/m<2>) to about 1.5 lb/ft<2> (5.86 kg/m<2>), a fire resistance meeting the requirements of PRG 25.853 Title 14 of the United States Code, Jan. 1, 2002, and a V0 velocity of at least about 1430 ft/sec (427 m/s) when tested by United States Federal Aviation Administration Advisory Circular 25.795.2, Jan. 10, 2002, using .44 Magnum Jacketed Hollow Point (JHP) bullets of 240 grains (15.6 g) mass and using 9 mm Full Metal Jacketed, Round Nose (FMJRN) bullets of 124 grains (8.0 g) mass.

Description

Shock-resistant and refractory composite

Background of invention

1. invention field

The present invention relates to shock-resistant and refractory composite, more particularly, the present invention relates to be used for the shock-resistant and refractory composite of interior of aircraft part and other purposes.

2. the explanation of correlation technique

The material that is used for engine room inside spare is by No. 14 CFR, and the 25th part is stipulated.Up to date, the main focus that relates to this material all is fire resistances.But after September calendar year 2001 suicide genophobia on the 11st molecule hijacking, the protection that other types are threatened receives the more concern of height.Wherein main focus is crew and the cabin safety to firearm.Be used for penetrating and also keeping present refractory standard of the material requirements lightweight of cabin door, anti-pistol cartridge.

The refractory material that is used for interior of aircraft can be referring to United States Patent (USP) 4,780, and 359,5,175,198,5,714,419 and 5,972,512.United States Patent (USP) 6,044,605 structures of having described door " ... available fire-resistant and high impact material is made ... ".

United States Patent (USP) 3,934,066 has described and has been applicable to inflammable and fire-retardant multilayer system heat-sensitive substrate material, and it comprises pliable and tough protective layer and expanding layer, and expanding layer comprises the porous fibre cellulose sheet that has flooded intumescent composition.Described pliable and tough protective layer can be a metal forming.

The material that has fire resistance and resistance to impact simultaneously can be referring to United States Patent (USP) 4,822, and 439,4,842,923,4,929,651,5,167,876,5,215,813 and 5,480,706.

United States Patent (USP) 4,822,439 and 4,929,651 have described and have comprised about 60 composites of weaving aluminosilicate magnesium glass fiber roving to about 75% weight dipping calcium hydroxide and M-phthalic acid thermosetting polyester.

United States Patent (USP) 4,842,923 and 5,167,876 have described the composite that in the phenolic resin cured base material of the surface density of tool at least 2.5 pounds per square foots balance is shot through with multilayer aluminosilicate magnesium glass network of fibers.

United States Patent (USP) 5,167,876 have described the composite that comprises two-layer or multilayer, and one deck is the network of fibers in base material at least, and one deck is the flame-retardant layer that has endothermic nature when being heated at least.

United States Patent (USP) 5,480,706 have described and have comprised a plurality of one or two layers of composite that replaces, and wherein ground floor is included in first kind of high strength combustible fibre network in the base material, and the second layer is included in the fire-retardant organic or inorganic network of fibers in the ignition resistant substrate.

Above-mentioned each composite is being represented the progress towards described target.But, the concrete structure of the present invention that do not had one piece of document description, all needs that also do not have one piece of document to satisfy as the present invention.

The major defect of these early stage composites comprises bigger inorganic material such as the glass fibre of use density.It is unsatisfactory that this material is used for the interior of aircraft part, and excessive weight will cause there is no need and uneconomic Fuel Consumption.On the other hand, composite density may be too low and occupies too much space.Therefore require composite to have intensity, toughness, resistance to impact and fire resistance together with suitable density.

The present invention's summary

The invention provides the composite that shows intensity, toughness, resistance to impact, fire resistance and the unprecedented combination of suitable density.Composite of the present invention has at least about the flexural modulus of 80,000 pounds/square inch (552MPa), the flexural yield strength at least about 800 pounds/square inch (5.52MPa), about 0.9-1.5 pounds per square foot (4.40-5.86kg/m ²) surface density, satisfy No. 14 CFR on January 1st, 2002, the fire resistance that § 25.853 requires, and by the Advisory Circulars 25.795.2 of US Federal Aviation Administration on January 10 (FAA) in 2002, use the 9mm full metal jacket Round nose (FMJRN) that the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality is covered bullet (JHP) and 124 grains (8.0g) quality to test, have V0 speed at least about 1430 feet per seconds (427m/s).

In one embodiment, composite of the present invention comprises multilayer, wherein ground floor comprises metal forming, the second layer comprises the retardant adhesive material, the 3rd layer comprises multilayer, each described layer is included in the flammable polymer fiber network in the base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

Detailed description of the present invention

The invention provides the composite that shows intensity, toughness, resistance to impact, fire resistance and low-density unprecedented combination.Composite of the present invention has at least about the flexural modulus of 80,000 pounds/square inch (552MPa), the flexural yield strength at least about 800 pounds/square inch (5.52MPa), about 0.9-1.5 pounds per square foot (4.40-5.86kg/m ²) surface density, satisfy No. 14 CFR on January 1st, 2002, the fire resistance that § 25.853 requires, and by the Advisory Circulars 25.795.2 of US Federal Aviation Administration on January 10 (FAA) in 2002, use the 9mm full metal jacket Round nose (FMJRN) that the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality is covered bullet (JHP) and 124 grains (8.0g) quality to test, have V0 speed at least about 1430 feet per seconds (427m/s).

Flexural modulus of composite of the present invention (modulus of elasticity in static bending) and flexural yield strength are measured according to the standard test method ASTM D790-00 of ASTM (ASTM).

No. 14 CFR § 25.853 described the flammability standards of engine room inside spare.The internal interval material must satisfy I, the IV of appendix F and the test requirements document that V partly stipulates.

I (a) 1 (i) the part specific requirement interval insulant of No. 14 CFR § 25.853 appendix F must the tool self-extinguishment when erectting test.Specimen is must at least 2 inches (5cm) wide, 12 inches (30cm) is long, and thickness is not more than the qualified minimum thickness that is used for aircraft.Must test three samples and the result is average at least.Sample is exposed under the flame of Bunsen or Tirrill burner, at least 1550 of flame temperatures (843 ℃).Flame is added to sample lower edge center line and moves apart after 60 seconds.The average ignition time that moves apart behind the burning things which may cause a fire disaster can not surpass for 15 seconds.Average burning length can not surpass 6 inches (15cm).If drippage is arranged, then the burning of Di Luo sample behind drippage can not surpass average 3 seconds.

The IV part concrete regulation of No. 14 CFR § 25.853 appendix F in the experimental cabin of particular design, be exposed to photothermal cabin exothermic maximum rate with material.Sample is placed in the radiant heat source, regulates radiant heat source, makes it produce 3.4 watts/cm in the sample test period of last five minute ²Total heat flux.Specimen sample be of a size of 5.91 inches * 5.91 inches (14.9cm * 14.9cm), thickness be used for the identical of aircraft.Sample test under exposed surface is erect.Monitoring is left the combustion product of experimental cabin to calculate heat liberation rate, heat release rate.Obtain exposing total positive heat release of two minutes of beginning with three or more sample average, also that the peak heat liberation rate, heat release rate of sample is average.The average peak heat liberation rate, heat release rate must be no more than 65kW/m ²Situations such as the surface area that exposes if make a difference or the fusion of combustion system, sagging, delamination then must be reported these situations with its time of origin.

The V part concrete regulation of No. 14 CFR § 25.853 appendix F the opium discharge characteristics of cabin material, its detailed test procedure is referring to ASTM F814-83.Three samples of minimum test, and the result is average.(7.62 * 7.62cm) samples are vertically installed in the particular design cabin with 3 * 3 inches.The electric radiation energy is at the sample center of 1.5 inches (3.81cm) diameters average generation 2.2BTU/s-ft ²(2.5W/cm ²) radiation level.Use six pipe burners to apply the equidistant flame of a row along the lower edge in exposed sample district.Concrete optical smoke density (Ds) and greatest optical smoke density value (DsMax) and time thereof when writing down 1.5 minutes and 4 minutes.Average DsMax must be no more than 200.

The V0 speed of composite is the maximal rate that the projectile of regulation does not penetrate composite.The V0 speed of composite of the present invention is by the test method of FAAAC 25.795.2 on the 10th January in 2002, uses the 9mm full metal jacket Round nose that the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality is covered bullet and 124 grains (8.0g) quality to measure.

The speed of projectile is measured by the lumiline screens along projectile trajectory.For every kind of projectile, test board is installed perpendicular to projectile trajectory in four shootings, and twice shooting is installed in vertical plane and becomes 30 °.Cause at each projected angle of impact penetrating wholly or in part of breadboard measured V0 speed by changing the emission dose.V0 speed is the highest partial penetration speed.When using the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality to cover the 9mm full metal jacket Round nose test of bullet and 124 grains (8.0g) quality, composite of the present invention has the V0 speed at least about 1430 feet per seconds (427m/s).

In one embodiment, composite of the present invention comprises the multilayer that is bonded together, wherein ground floor is a metal forming, the second layer is the retardant adhesive material, form by multilayer for the 3rd layer, each described layer is included in the flammable polymer fiber network in the base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

In another embodiment, composite of the present invention comprises the multilayer that is bonded together, wherein ground floor is a metal forming, the second layer is the swollen resin composition, the 3rd layer is the retardant adhesive material, be made up of multilayer for the 4th layer, its each described layer is included in the flammable polymer fiber network in the base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

Preferred composite of the present invention has the layer structure of symmetry, and central core is the flammable polymer fiber network in base material.In a kind of embodiment preferred, described composite comprises five layers that are bonded together, wherein ground floor and layer 5 are metal forming, the second layer and the 4th layer are the retardant adhesive material, the 3rd layer is the flammable polymer fiber network in base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

In another preferred embodiment, described composite comprises seven layers that are bonded together, wherein ground floor and layer 7 are metal forming, the second layer and layer 6 are the swollen resin composition, the 3rd and layer 5 be the retardant adhesive material, the 4th layer at center is the flammable polymer fiber network in base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

The all combination and together bonding of each layer in each embodiment.Preferred described each layer is by heat pressure adhesive.Preferred described be bonded in about 100 to about 150 ℃ temperature and about 15 to about 5,000psi (103-34, carry out under pressure 475kPa) by the bonding time that is enough to each layer is bonded together.More preferably described be bonded in about 120 to about 130 ℃ temperature and about 50 to about 200psi (345-1 carries out about 30 minutes time and carries out under pressure 380kPa).

Preferably the metal forming in each embodiment is for having the aluminium foil of about 0.0005 to about 0.005 inch (12.7-127 micron) thickness.More preferably described metal forming is for having the aluminium foil of about 0.001 to about 0.003 inch (25.4-76.2 micron) thickness.

Preferred described fire-resistant jointing material comprises the polymeric material that is selected from thermoplasticity and thermosetting polymer of at least 10% weight.The thermoplastic polymer that can be used for jointing material of the present invention includes, but is not limited to: polyolefin, polydiene, polyester, formamide, polyvinyl, ionomer, acrylic polymer, acrylic polymer, polysulfones, polyphenylene oxide, acetals, polysiloxane-based, thermoplastic polyurethane, TPI, polyketone class and copolymer and halo derivatives.Useful thermosetting polymer includes, but is not limited to phenol polymer, melamine polymer, epoxides, polysiloxane-based, unsaturated polyester (UP) class and heat-curable urethane class.

The polymer moieties of retardant adhesive material can be that itself is fire-resistant, or gives fire resistance by the blending flame-retardant additive.

Described flame-retardant additive (as containing) can be organic and inorganic or the organic metal additive.The example of the flame-retardant additive that is suitable for includes, but is not limited at " Flame Retardancy ofPolymeric Materials (fire resistance of polymeric material) ", the first volume, and Kuryla and Papa compile, Marcel Dekker, Inc., New York, the additive of listing in 1973.Described additive comprises following organic additive:

P-H Functional group

-OH Functional group

CH ₂=CH- Functional group

(CH ₂＝CHCH ₂O ₃P

(CH ₂＝CHCH ₂OP＝O

-NH Functional group

PCH ₂OH) ₄A

R ₄ P salt

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

n＝1 to 2

P-Cl Functional group

P +S Compound

Functional group

(CH ₃) ₂P-S-S-P(CH ₃) ₂

P +Br Compound

(BrCH ₂CHBrCH ₂O ₃P＝O

(XCH ₂CHXCH ₂O ₃P＝O

X＝Cl，Br

P +Cl Compound

(ClCH ₂CH ₂O ₃P

(ClCH ₂CHClCH ₂O ₃P＝O

(ClCH ₂CH ₂H ₂O ₃P＝O

(CH ₃CHClCH ₂O ₃P＝O

P (phosphite)

(CH ₃O ₃P

(CH ₃CH ₂O ₃P

(C ₈H ₁₇O ₃P

(C ₁₂H ₂₅O ₃P

(C ₁₈H ₃₇O ₃P

(C ₁₈H ₃₇O ₃P

P (phosphate)

(CH ₃O ₃P＝O

(C ₂H ₅O) ₃P＝O

(C ₂H ₅O ₃P＝O

(C ₄H ₉O ₃P＝O

(C ₈H ₁₇O ₃P＝O

(C ₈H ₁₇O ₃P＝O

(C ₄H ₉O-CH ₂CH ₂O ₃P＝O

R＝H，CH ₃

R＝H，(CH ₃) ₂CH

P (phosphonate)

P (multiple)

(n-C ₄H _{9 3}P＝O

(n-C ₈H _{17 3}P＝O

P +S Compound

( _C12H ₂₅S ₃P

(CH ₃CH ₂O ₃P＝S

(C ₈H ₁₇O ₃P＝S

Bromine-based compound:-OH Functional group

(BrCH _{2 3}C-OH

BrCH＝CBr-CH ₂OH

BrCH ₂CH ₂OH

BrCH ₂CHBrCH ₂OH

Chlorine-based compound:-OH Functional group

Cl ₂With

-C ≡ C- Functional group

Cl-CH ₂-C≡C-CH ₂Cl

N-halogen functional group

H ₂C=C- Functional group

CH ₂＝CH-Br

CH ₂＝CH-CH ₂Br

CH ₂＝CCl ₂

CH ₂＝CH-CH ₂Cl

-COOH Functional group

(And NH ₄ ⁺ Salt)

-CHO Functional group

BrCH ₂CHBr-CHO

Cl ₃C-CHO

-NH ₂ Functional group

Non-sense halogen compounds

Bromine-based compound

BrCH ₂Cl

Br ₂CH-CHBr ₂

BrCH ₂CH ₂CHCl

BrCH ₂CHBrCHBrCH ₂Br

(BrCH ₂CHBrCH ₂O) ₂CH ₂

x+y＝5

x+y＝8

Chlorine-based compound

Cl ₃C-CCl ₃

ClCH ₂CHClCH ₂Cl

Cl ₂C＝CCl-CCl＝CCl ₂

Chloro-three (and higher) phenyl

Bromine and chlordiphenyl

X ₆＝Cl

X ₄＝Br

x+y＝8

(x+y＝1-10)

The chloro-naphthalene

Halogenated paraffin

Y＝Br，H

Y＝H，Cl

Y＝H，Cl

The inorganic fire-retarded additive that is fit to comprises: antimony oxide (Sb ₂O ₃), antimony sulfide (Sb ₂OS ₃, Sb ₂S ₃, Sb ₂S ₄), antimony halides (SbCl ₃, SbCl ₅, SbBr ₃, SbBr ₅), sodium antimonate or potassium antimonate be as (NaSBO ₃), ammonium phosphate, sodium phosphate or potassium phosphate be as [(NH ₄) ₃PO ₄, (NH ₄) ₂HPO ₄, (NH ₄) H ₂PO ₄, (NH ₄PO ₃) _x], phosphorus Halides (PCl ₃, PCl ₅, POCl ₃), phosphonitrilic chloride (PNCl ₂) _x, phosphorus pentasulfide (P ₂S ₅), Boratex [Na ₂O (B ₂O ₃) _3.54H ₂O, Na ₂B ₄O ₇10H ₂O], sodium tetrafluoroborate, potassium tetrafluoroborate or ammonium tetrafluoroborate be as (NaBF ₄), line borate or barium borate be as [Ca (BO ₂) ₂, Ca ₃(BO ₃) ₂], lithium tetraborate, sodium tetraborate or dipotassium tetraborate be as (LiB ₄O ₇), boric acid (H ₃BO ₃), boroxine [(CH between trimethoxy ₃OBO) ₃], hydrated alumina [Al ₂O ₃3H ₂O, Al (OH) ₃], aluminum phosphate hydrate [Al ₂O ₃(AlPO ₄) _x(H ₂O) _y], sodium metasilicate [(Na ₂O) _n(SiO ₂) _m], ammonium bromide (NH ₄Br), ammonium sulfate [(NH ₄) ₂SO ₄], lithium metasilicate [LiO ₂(SiO ₂) _5.9, Li ₂O (Na ₂O) _n(SiO ₂) _m], molybdenum oxide (MoO ₃), ammonium paramolybdate [(NH ₄) ₆Mo ₇O ₂₄(H ₂O) _x], molybdenum sulfide (MoS ₂) and sulphamide [(NH ₂) ₂SO ₂].

The organic metal flame-retardant additive that is fit to comprises:

The example that can be used for suitable self flame-retardant polymer of described retardant adhesive material comprises that halogen polymer is such as haloflex, polyvinyl chloride, poly-(1, the 1-dichloroethylene), poly-(chlorotrifluoroethylene), poly-(1,1-two chloro-2-PVFs), poly-(1,2-two chloro-1, the 2-difluoroethylene), poly-(1, the 1-difluoroethylene), poly-(1, the 2-difluoroethylene), poly-(tetrafluoroethene), poly-(trifluoro-ethylene), poly-(pentafluoroethyl group) ethene, poly-(ten tetrafluoro amyl group ethene), poly-(hexafluoropropene), poly-(2,3,3, the 3-tetrafluoeopropene), poly-(3,3, the 3-trifluoro propene), poly-(seven fluoropropyls) ethene, poly-inclined to one side vinylidene fluoride, with poly-tribromo-benzene ethene, the copolymer of the monomer of its mixture and these polymer of formation.

The example that can be used for non-halogenated self flame-retardant polymer of described retardant adhesive material comprises melamine-formaldehyde, melocol, P-F and other phenol polymers and copolymer, the formaldehyde-furfural-resorcinol-phenol product of selling with the bi-component monomeric form with the trade name of FIRE PRF2-1000 such as BordenChemicals and Plastics.

Preferred described retardant adhesive material comprises antimony oxide (Sb ₂O ₃), deca-BDE and many chlorine paraffin is at BOSTIK  14-576-3 by name (Bostik Findley, the blend in polyacrylate resin adhesive Inc.).

The non-polymer part of retardant adhesive material can comprise intumescent composition.Intumescent composition works by the expansion insulating barrier that forms fire proofing under the effect of heat.But expanding material is endothermic decomposition also.

Intumescent composition is charing expanded to be that its original thickness is more than five times.Expanding material prevents base material contact oxygen and/or prevents overheated and therefore prevent or postpone the diffusion of flame.Expansion system is made up of polymer, charcoal or one-tenth carbon skeleton material (" carbonific "), swelling agent (" blowing agent (spumific) ") and acid former usually.Can use organic polyhydroxy compound such as pentaerythrite, dipentaerythritol, tripentaerythritol, starch and sucrose as carbonific.The example of blowing agent has nitrogen-containing compound such as melamine, melamine salt, melamine derivative, urea, dicyandiamide and guanidine.Blowing agent causes the formation of expanding layer by the generation inert gas.Acid former uses phosphoro-amidate, ammonium phosphate, amine phosphate (amine phosphates), ammonium polyphosphate and melamine phosphate usually.

Can be used for intumescent composition of the present invention and be described in for example United States Patent (USP) 6,309 compatible, 746B1,6,228,914B1,5,962 with this paper incorporating this paper by reference into, 603,5,759,692,5,708,065,5,591,791,5,356,568,5,225,464,5185,103,5,130,349,4,857,364,4,442,157,4,542,170,4,380,593,4,198,328 and 3,849,178.

In an embodiment preferred, composite of the present invention comprises one deck swollen resin composition at least.A kind of preferred swollen resin composition is that Borden Chemical phenolic resins FIRE PRF2-1000 and about 8 comprises melamine pyrophosphate (melaminepyrophosphate) (C to about 18% weight ₃H ₆N ₆H ₄P ₂O ₇) and two (melamine pyrophosphate) (bsi (melaminepyrophosphoric) acid) (C ₆H ₁₂N ₁₂H ₄P ₄O ₇) mixture, by Broadview Technologies, Inc. sells with the trade name of MAXICHAR  for it.

Preferred described swollen resin composition comprise in addition about 2 to the glass bubbles of about 35% weight such as the Sodium borosilicate glass aperture of selling with the trade name of 3M  SCOTCHLITE  glass bubbles by Minnesota Mining and Manufacturing Co..Most preferably the size of described glass bubbles makes it stay on No. 80 Unite States Standard sieves (177 microns) less than 5% weight.

One deck at least of preferred composite of the present invention is made up of multilayer, each described layer is the flammable polymer fiber network in base material, and described polymer fiber has at least about the toughness at 25 gram/dawn, at least about the stretch modulus at 900 gram/dawn with at least about the energy to failure of 25 joule/gram.

For the present invention, fiber is the prolate body that length dimension is far longer than the lateral dimension of width and thickness.Therefore, the term fiber comprises long filament with regular and irregular cross section, band, bar etc.Yarn is the endless tow that comprises many fibers or long filament.

Used term " network of fibers " is meant that many fiber architecture become predetermined structure in this, and perhaps many fiber collections form together through twisting or untwisted yarn, and yarn is arranged into predetermined structure.Described network of fibers can have various structures.For example described fiber or yarn can form felt or other adhesive-bonded fabrics, and be knitting or be woven into network by routine techniques.According to a kind of preferred network structure, thereby the fiber in one deck can be unidirectional to directly making it substantially parallel mutually along the normal fiber direction.This unidirectional succeeding layer to fibers straight preferably rotates with respect to front layer.

Flammable fiber is a fiber of supporting burning.Flammable fiber comprises unmodified polyolefin, polyester, polyvinyl alcohol and polyacrylonitrile etc.

Most preferably the fiber network layer of the composite machine direction that is arranged into the unidirectional fibre of each Internet is rotated corresponding to the machine direction of the unidirectional fibre of adjacent layer.Example is five compounds layer by layer, its second, third, the 4th and layer 5 rotate+45 ° ,-45 °, 90 ° and 0 ° with respect to ground floor.More preferred example is 50 compounds layer by layer, and alternating layer is in 0 ° and 90 °.

The flammable fiber that most preferably constitutes composite of the present invention is a high-strength polyethylene fiber.Be used for high-strength polyethylene fiber of the present invention and be having more than or equal to about 17g/d toughness at (gram/dawn), be equal to or greater than the initial tensile modulus of about 500g/d and be equal to or greater than the polyethylene fibre of the energy to failure of about 20J/g.For the present invention, toughness of fibre, initial tensile modulus (elastic modelling quantity) and energy to failure are measured with the yarn form according to ASTM D2256.Preferred fiber is to have toughness more than or equal to about 25g/d, be equal to or greater than the initial tensile modulus of about 900g/d and more than or equal to the fiber of the energy to failure of about 25J/g.Particularly preferred fiber be have toughness more than or equal to about 30g/d, more than or equal to the initial tensile modulus of about 1200g/d with more than or equal to the fiber of the energy to failure of about 30J/g.Most preferred fiber be have toughness more than or equal to about 30g/d, more than or equal to the initial tensile modulus of about 1200g/d with more than or equal to the fiber of the energy to failure of about 40J/g.

This high-strength polyethylene fiber can be as United States Patent (USP) 4,137, and 394 or 4,356, described in 138 at growth from solution, or as German Off.3, described in No. 2051667,004, No. 699 and the GB, and, form gel structure by the solution spinning described in 110 particularly as United States Patent (USP) 4,413.Polyethylene fibre also can pass through as United States Patent (USP) 5,702, the rolling and drawing production described in 657, and it is sold with the trade name of TENSYLON  by ITS Industries Inc..Term polyethylene used herein is meant and is mainly linear polythene material, it can comprise a small amount of side chain or comonomer (per 100 backbone c atoms are no more than 5 modification units), wherein also can comprise fusion in wherein one or more polymeric additives such as alkene-1 polymer that is not more than about 50% weight (low density polyethylene (LDPE) particularly, polypropylene or polybutene), monoolefine is as the copolymer of main monomer, the polyolefin of oxidation, graft polyolefin copolymer and polyformaldehyde, or conventional low molecular weight additives such as the antioxidant that uses, lubricant, the ultraviolet light filtering agent, colouring agent etc.

Amazing is though composite major part of the present invention comprises the flammable fiber network that thin retardant surfaces layer hides, can satisfy the fire-resistant requirement of interior of aircraft part strictness.The concrete one theory that not worked by the present invention, believing that fiber network layer and retardant surfaces layer one work blocks propagation of flame.Outer metal forming and retardant adhesive material blocking oxygen also at first block high temperature and spread to the inside of composite.When the high temperature front end finally penetrated composite outer, combustible fibre shrank, and had produced clearance space and retardance further spreads.Be arranged in embodiment between fiber network layer and composite material surface at the swollen resin composition, this retardance is further enhanced.Total effect is to be met the highly effective flame-retardant composite that the interior of aircraft part of the non-constant width of tool safe space requires.

Following embodiment is used to provide the present invention is more fully understood.The data of its concrete technology, condition, material, ratio and report are used to illustrate principle of the present invention, do not should be understood to limiting the scope of the invention.Particularly, described technology is to be used to prepare sample, uses but be easy to expand on the tinuous production.

Embodiment

The comparative example 1

Be prepared as follows nine layers of composite with symmetrical layers structure:

Ground floor and the 9th layer: 302 type stainless steel foils, 0.001 inch (0.0254mm) is thick;

The second layer and the 8th layer: swollen resin composition;

The 3rd layer and layer 7: the glass fibre that has flooded phenolic resins;

The 4th layer and layer 6: fire-retardant pressure-sensitive film adhesive; With

Layer 5: 50 layers of unidirectional polyethylene fibre network in the epoxy vinyl ester base material.

The swollen resin composition of forming the second layer and the 8th layer is the sheet material that is prepared as follows: preparation is by 60.9% weight bi-component formaldehyde-furfural-resorcinol-phenol monomer (Borden DuriteFIRE PRF2-1000; A component-100pph, B component-24pph), 9.1% weight contain melamine pyrophosphate (C ₃H ₆N ₆H ₄P ₂O ₇) and two (melamine pyrophosphate) (C ₆H ₁₂N ₁₂H ₄P ₄O ₇) expansion additive (Broadview Technologies MAXICHAR ) and the mixture formed of 30% weight glass vesicle (3M K1 type).With mixture smooth thickness of sprawling into 0.020 inch (0.51mm) on the polysiloxanes peeling paper, put another peeling paper on the top.Under the light pressure of about 1psi (7kPa), made mixture solidified become solid sheet material in 30 minutes on the press in about 200 (93 ℃) heating.The edge of straight sheet material, and sheet material is divided into two equal portions and forms the second layer of composite and the 8th layer.

The impregnated glass fiber that constitutes the 3rd layer and layer 7 is that (22 * 21 road numbers/cm) four are organized the E-glass fibre through the satin line to 57 * 54 roads number/inch, 7781 types, with fire retardant LC 194 phenolic resins (Lewcott Corp.) pre-preg, and have the thickness of about 0.095 inch (2.41mm).

Constituting the 4th layer of fire-retardant pressure-sensitive film adhesive with layer 6 is antimony oxide (Sb ₂O ₃), deca-BDE and many chlorine paraffin is at BOSTIK  14-576-3 (Bostik Findley, the blend in acrylate resin adhesiver Inc.).

Middle layer 5 comprises 50 floor height strength polyethylene fibers, unidirectional array in the layer, and the fiber in the adjacent layer is arranged in 90 ° mutually.Described polyethylene fibre is the fiber at 1100 dawn, have the initial stretch modulus of the hot strength of about 3.1GPa, about 107GPa and about 3.3% extension at break, and in the base material (the SPECTRA SHIELD  VE PLUS of Honeywell International Inc.) of the epoxy vinyl ester resin that contains the about 500kpsi of tool (3.5GPa).

In press under the temperature of the pressure of 100psi (690kPa) and 121 ℃ 30 minutes, each layer of composite engaged and together bonding.

The test of the composite that partly carries out according to the IV of No. 14 CFR § 25.853 appendix F shows to have 11kW/m ²Average exothermic maximum rate, and require to being lower than 65kW/m ²But described plate has the 1.84 pounds per square foot (8.99kg/m that are considered to too high ²) surface density.

The comparative example 2

Preparation except the second layer and the 8th layer, nine layers of composite of other each layers and comparative example's 1 identical layer structure.Be prepared as follows the swollen resin composition that constitutes the second layer and the 8th layer:

Bi-component expansion loop epoxy resins (the INTUMAX  EP1115 that will contain melamine pyrophosphate and two (melamine pyrophosphate), Broadview Technologies, Inc.) be mixed and on the polysiloxanes peeling paper the smooth thickness of sprawling into 0.020 inch (0.51mm), put another peeling paper on the top.In this resin, do not comprise the glass vesicle.Under the light pressure of about 1psi (7kPa), made mixture solidified become solid sheet material in 30 minutes on the press in about 200 (93 ℃) heating.The edge of straight sheet material, and sheet material is divided into two equal portions and forms the second layer of composite and the 8th layer.

The remainder layer of composite is identical with comparative example's 1 described equivalent layer.

In press under the temperature of the pressure of 100psi (690kPa) and 121 ℃ 30 minutes, each layer of composite engaged and together bonding.

The test of the composite that partly carries out according to the IV of No. 14 CFR § 25.853 appendix F shows to have 47kW/m ²Average exothermic maximum rate.Though it within the acceptable range, comparison is than the 11kW/m of the composite that contains the glass vesicle of embodiment 1 preparation ²Difference.This composite has improved 1.56 pounds of/square inch (7.62kg/m ²) surface density, think roughly outer rim in acceptability.

Embodiment 1

Be prepared as follows seven layers of composite with symmetrical layers structure:

Ground floor and layer 7: aluminium foil, 0.003 inch (0.076mm) is thick;

The second layer and layer 6: swollen resin composition;

The 3rd layer and layer 5: fire-retardant pressure-sensitive film adhesive; With

The 4th layer: 50 layers of unidirectional polyethylene fibre network in the epoxy vinyl ester base material.

Be prepared as follows the swollen resin composition that constitutes the second layer and layer 6: preparation is by bi-component expansion loop epoxy resins (the INTUMAX  EP1115 of 95.3% weight, BroadviewTechnologies, Inc.) and the mixture formed of 4.7% weight glass vesicle (3M K1 type).With mixture smooth thickness of sprawling into 0.016 inch (0.41mm) on the polysiloxanes peeling paper, put another peeling paper on the top.Under the light pressure of about 1psi (7kPa), made mixture solidified become solid sheet material in 30 minutes on the press in about 200 (93 ℃) heating.The edge of straight sheet material, and sheet material is divided into two equal portions and forms the second layer and the layer 6 of composite.

Constitute the 3rd layer of fire-retardant pressure-sensitive film adhesive and layer 5 and comprise antimony oxide (Sb ₂O ₃), deca-BDE and many chlorine paraffin is at BOSTIK  14-576-3 (Bostik Findley, the blend in acrylate resin adhesiver Inc.).

Middle the 4th layer comprises 50 floor height strength polyethylene fibers, unidirectional array in the layer, and the fiber in the adjacent layer is arranged in 90 ° mutually.Described polyethylene fibre is the fiber at 1100 dawn, initial stretch modulus and about 3.3% extension at break and the energy to failure of about 45J/g with the hot strength of about 3.1GPa, about 107GPa, and in the base material (the SPECTRASHIELD  VE PLUS of Honeywell International Inc.) of the epoxy vinyl ester resin that contains the about 500kpsi of tool (3.5GPa).

30 minutes each layers with composite engage and are together bonding under the temperature of the pressure of 100psi (690kPa) and 121 ℃ in press.

Composite of the present invention has and is considered to acceptable 1.22 pounds per square foot (5.96kg/m ²) surface density.According to No. 14 CFR § 25.853 appendix F on January 1st, 2002 with by the test method of the Advisory Circulars 25.795.2 of US Federal Aviation Administration on the 10th January in 2002, the 9mm full metal jacket Round nose that uses the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality to cover bullet and 124 grains (8.0g) quality is measured with composite.

Measure the flexural modulus (modulus of elasticity in static bending) and the flexural yield strength of composite according to ASTM D790-00 method.The result of these tests all is listed in table 1 together with other embodiment and comparative example's data.The composite of the embodiment of the invention 1 satisfies (comprising flammable polyethylene fibre) all specification requirements of FAA (FAA).

Embodiment 2

Preparation has seven layers of composite with the composite same structure of embodiment 1 in the same manner.This composite has and is considered to acceptable 1.19 pounds per square foot (5.82kg/m ²) surface density.The result of the test of table 1 shows that the composite of embodiment 2 satisfies the specification requirement of all FAA.

Embodiment 3

Be prepared as follows seven layers of composite with symmetrical layers structure:

Ground floor and layer 7: aluminium foil, 0.003 inch (0.076mm) is thick;

The second layer and layer 6: swollen resin composition;

The 3rd layer and layer 5: fire-retardant pressure-sensitive film adhesive; With

The 4th layer: 50 layers of unidirectional polyethylene fibre network in thermoplastic elastic base material (from the SPECTRA SHIELD  PCR PLUS of Honeywell International Inc.).

Be prepared as follows the swollen resin composition that constitutes the second layer and layer 6: preparation is by bi-component formaldehyde-furfural-resorcinol-phenol monomer (Borden Durite FIREPRF2-1000 of 74.2% weight; A component-100pph, B component-24pph), 12.9% weight contain melamine pyrophosphate (C ₃H ₆N ₆H ₄P ₂O ₇) and two (melamine pyrophosphate) (C ₆H ₁₂N ₁₂H ₄P ₄O ₇) expansion additive (Broadview Technologies MAXICHAR ) and the mixture formed of 12.9% weight glass vesicle (3MK1 type).With mixture smooth thickness of sprawling into about 0.016 inch (0.41mm) on the polysiloxanes peeling paper, put another peeling paper on the top.Under the light pressure of about 1psi (7kPa), made mixture solidified become solid sheet material in 30 minutes on the press in about 200 (93 ℃) heating.The edge of straight sheet material, and sheet material is divided into two equal portions and forms the second layer and the layer 6 of composite.

Constitute the 3rd layer of fire-retardant pressure-sensitive film adhesive and layer 5 and comprise antimony oxide (Sb ₂O ₃), deca-BDE and many chlorine paraffin is at BOSTIK  14-576-3 (Bostik Findley, the blend in polyacrylate resin adhesive Inc.).

Form by 50 floor height strength polyethylene fibers for middle the 4th layer, unidirectional array in its middle level, and the fiber in the adjacent layer is arranged in 90 ° mutually.Described polyethylene fibre is the fiber at 1100 dawn, has initial stretch modulus and about 3.3% extension at break and the energy to failure of about 45J/g of the hot strength of about 3.1GPa, about 107GPa.Described high-strength polyethylene fiber network is in the base material (the SPECTRA SHIELD  VE PLUS of Honeywell International Inc.) that the thermoplastic and high-elastic of about 100kpsi (6.9kPa) stretch modulus by tool is formed.

In press under the temperature of the pressure of 100psi (690kPa) and 121 ℃ 30 minutes, each layer of composite engaged and together bonding.

Composite of the present invention has and is considered to acceptable 1.19 pounds per square foot (5.82kg/m ²) surface density.The result of the test of table 1 shows that the composite of embodiment 3 satisfies all specification requirements of FAA (FAA).

Embodiment 4

Be prepared as follows five layers of composite with symmetrical layers structure:

Ground floor and layer 5: aluminium foil, 0.001 inch (0.025mm) is thick;

The second layer and the 4th layer: fire-retardant pressure-sensitive film adhesive (BOSTIK  14-576-3); With

The 3rd layer: 50 layers of unidirectional polyethylene fibre network in thermoplastic elastic base material (from the SPECTRA SHIELD  PCR PLUS of Honeywell International Inc.).

30 minutes each layers with composite engage and are together bonding under the temperature of the pressure of 100psi (690kPa) and 121 ℃ in press.

Composite of the present invention has to be reduced to and is considered to acceptable 1.0 pounds per square foot (4.89kg/m ²) surface density.The result of the test of table 1 shows that the composite of embodiment 4 satisfies all specification requirements of FAA.

Embodiment 5

Except the 3rd layer of central core, prepare five layers of composite with embodiment 4 identical symmetrical layers structures.In this embodiment, central core comprises 50 floor height strength polyethylene fibers, unidirectional array in the layer, and the fiber in the adjacent layer is arranged in 90 ° mutually.Described polyethylene fibre is the fiber at 1100 dawn, have the initial stretch modulus of the hot strength of about 3.1GPa, about 107GPa and about 3.3% extension at break, and other yarn physical properties, and in the base material (the SPECTRA SHIELD  VE PLUS of HoneywellInternational Inc.) of the epoxy vinyl ester resin that contains the about 500kpsi of tool (3.5GPa) stretch modulus.

In press under the temperature of the pressure of 100psi (690kPa) and 121 ℃ 30 minutes, each layer of composite engaged and together bonding.

The composite of embodiment 5 also has and is considered to acceptable 1.0 pounds per square foot (4.89kg/m ²) surface density.The result of the test of table 1 shows that the composite of embodiment 5 satisfies all specification requirements of FAA.

Though the present invention has quite at length been set forth in the front, it should be understood that these details do not need to strictly observe, those skilled in the art can propose many changes and modification, and all of these changes and modifications are all in the scope of the invention of appended claims definition.

									Erect combustion test
														Comparative example and embodiment numbering	Composite material surface	The swollen resin composition	Glass vesicle (%) in the resin	SPECTRA SHIELD  shock plate type	Flexural modulus psi	Flexural yield strength psi	Heat liberation rate, heat release rate kW/m 2	Smoke density DSmax	Burning time sec	Maximum combustion length inch	The longest burning particles sec of maximum	Surface density psf	The V0 feet per second
The FAA specification requirement							＜65	＜200	＜15	＜6	＜5		＞1430
														The comparative example 1	SS	Phenolic aldehyde	30	VE Plus	n.a.	n.a.	11	95	0	1.5	0	1.84	n.a.
The comparative example 2	SS	Epoxy	0	VE Plus	n.a.	n.a.	47	n.a.	n.a.	n.a.	n.a.	1.56	n.a.
														1	Al	Epoxy	47	VE Plus	n.a.	n.a.	0	n.a.	n.a.	n.a.	n.a.	1.22	＞1430
2	Al	Epoxy	4.7	VE Plus	676000	3344	0	16	0	0.2	0	1.19	＞1430
														3	Al	Phenolic aldehyde	12.9	PCR Plus	87930	937	1	9	0	0.8	0	1.19	＞1430
4	Al	Do not have	0	PCR Plus	n.a.	n.a.	0	35	0	1.5	0	1.00	＞1430
														5	Al	Do not have	0	VE Plus	n.a.	n.a.	0	3	0	1.5	0	1.00	＞1430

The n.a.-free of data

Claims (17)

1. composite, described composite have at least about the flexural modulus of 80,000 pounds/square inch (552MPa), at least about the flexural yield strength, about 0.9 of 800 pounds/square inch (5.52MPa) to about 1.5 pounds per square foot (4.40-5.86kg/m ²) surface density, satisfy No. 14 CFR on January 1st, 2002, the fire resistance that § 25.853 requires, and by the Advisory Circulars 25.795.2 of US Federal Aviation Administration on the 10th January in 2002, use the 9mm full metal jacket Round nose (FMJRN) that the empty sharp metal backing of .44Magnum of 240 grains (15.6g) quality is covered bullet (JHP) and 124 grains (8.0g) quality to test, have V0 speed at least about 1430 feet per seconds (427m/s).

2. composite that comprises the multilayer that is bonded together, wherein ground floor comprises metal forming, the second layer comprises the retardant adhesive material, the 3rd layer comprises multilayer, each described layer is included in the flammable polymer fiber network in the base material, and described polymer fiber has at least about the toughness at 17 gram/dawn, at least about the stretch modulus at 500 gram/dawn with at least about the energy to failure of 20 joule/gram.

3. the layer 5 that the 4th layer of comprising also that the retardant adhesive material constitutes of the composite of claim 2, described composite and metal forming constitute.

4. the composite of claim 2, described composite also is included in the swollen resin composition between the described ground floor and the second layer.

5. the composite of claim 4, described composite also comprise the layer 5 that is made of the swollen resin composition, the layer 6 that is made of the retardant adhesive material and the layer 7 that is made of metal forming.

6. the composite of claim 2 or claim 4, wherein said metal forming is for having the aluminium foil of about 0.0005 to about 0.005 inch (12.7-127 micron) thickness.

7. the composite of claim 2 or claim 4, wherein said retardant adhesive material comprises polymer adhesive, described polymer adhesive is selected from polyolefin, polydiene, polyester, polyamide, polyvinyl, ionomer, acrylic polymer, acrylic polymer, polysulfones, polyphenylene oxide, acetals, polysiloxane-based, thermoplastic polyurethane, TPI, the polyketone class, phenol polymer, the melamine polymer, epoxides, polysiloxane-based, unsaturated polyester (UP) class and heat-curable urethane class, with its copolymer and halo derivatives, and list in " Flame Retardancy of Polymeric Materials (fire resistance of polymeric material) ", the 1st volume, Kuryla and Papa compile, Marcel Dekker, Inc., New York, the 1-111 page or leaf, at least a fire retardant in 1973.

8. the composite of claim 2 or claim 4, wherein said fire retardant jointing material is antimony oxide (Sb ₂O ₃), deca-BDE and the blend of many chlorine paraffin in the polyacrylate resin adhesive.

9. the composite of claim 2 or claim 4, wherein said flammable polymer fiber is a polyethylene.

10. the composite of claim 9, wherein said polyethylene fibre one-way orientation in layer, and wherein at the fiber of adjacent layer mutually with about 90 ° of orientations.

11. the composite of claim 2 or claim 4, the elastomer of wherein said base material for having the initial tensile modulus that is lower than about 6000psi (41.4MPa) through ASTM D638 measurement.

12. the composite of claim 11, wherein said base material are the elastomer that comprises the block copolymer of conjugated diene and vi-ny l aromatic monomers.

13. the composite of claim 2 or claim 4, wherein said base material is for having the thermosetting resin at least about the stretch modulus of 300kpsi (2.1GPa).

14. the composite of claim 13, wherein said base material are epoxy vinyl ester resin.

15. the composite of claim 3, wherein said swollen resin composition comprises the blowing agent that is selected from melamine, melamine salt, melamine derivative, urea, dicyandiamide and guanidine, and described blowing agent is scattered in the resin that is selected from phenol polymer, melamine polymer, epoxy resin, polysiloxanes, unsaturated polyester (UP) and heat-curable urethane.

16. comprising, the composite of claim 4, wherein said swollen resin composition be selected from melamine pyrophosphate (C ₃H ₆N ₆H ₄P ₂O ₇) and two (melamine pyrophosphate) (C ₆H ₁₂N ₁₂H ₄P ₄O ₇) at least a and be selected from a kind of of formaldehyde-furfural-resorcinol-phenolic resin and epoxy resin.

17. the composite of claim 12, wherein said swollen resin composition also comprise the about 2 glass vesicles to about 35% weight.