CN101479558B - Multilayered material sheet and process for its preparation - Google Patents
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- CN101479558B CN101479558B CN200780024030.4A CN200780024030A CN101479558B CN 101479558 B CN101479558 B CN 101479558B CN 200780024030 A CN200780024030 A CN 200780024030A CN 101479558 B CN101479558 B CN 101479558B
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Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
Abstract
The invention relates to a multilayered material sheet comprising a consolidated stack of unidirectional monolayers of drawn polymer. The draw direction of two subsequent monolayers in the stack differs. Moreover the strength to thickness ratio of at least one monolayer is larger than 4.5.10<13> N/m<3>. The invention also relates to a ballistic resistant article comprising the multilayered material sheet and to a process for the preparation of the ballistic resistant article.
Description
The present invention relates to a kind of multilayered material sheet, it comprises a fixed folded one-way single-layer of being made by strained polymer, and relates to the manufacture method of above-mentioned multilayered material sheet.The invention still further relates to the ballistic-resistant article that contains multilayered material sheet.
By the known a kind of multilayered material sheet of EP 1627719, this multilayered material sheet comprises a fixed folded one-way single-layer of being made by strained polymer.This piece of disclosed multilayered material sheet of publication comprises a plurality of one-way single-layers that are comprised of ultra-high molecular weight polyethylene, there is no adhesive matrix, and wherein, in lamination, the draw direction of two adjacent monolayer is different.Individual layer in EP 1627719 in disclosed multilayer material is manufactured by the following: a plurality of tapes of ultra high molecular weight polyethylene are disposed adjacent one another, and wherein each band of adjacent layout is overlapping at least partly along their lateral margin (side edge).There is no lap, cannot produce known multilayer material.And in order to obtain better ballistic performance, the plate of material in EP1627719A1 is become by ultrahigh molecular weight polyethylene specially, there is no adhesive matrix.
Although have gratifying ballistic performance according to the multilayered material sheet of EP 1627719A1, this performance can further be improved.
The object of this invention is to provide a kind of multilayered material sheet, this multilayered material sheet has and at least similarly ballistic performance and easily manufacture of known materials.
Object according to the present invention is by providing following multilayered material sheet to realize, described multilayered material sheet comprises a fixed folded one-way single-layer of being made by strained polymer, wherein, in described lamination, the draw direction of two adjacent monolayer is different, wherein at least one individual layer comprises the unidirectional tape that at least one is made by strained polymer, each band comprises longitudinal edge, next-door neighbour and along most of length of described longitudinal edge wherein, and described individual layer does not have overlapping or there is no an areas of elevated thickness.Preferably, next-door neighbour and along at least 50%, 60%, 70%, 80%, 90% or 95% length of the longitudinal edge of described at least one unidirectional tape, does not have overlapping or there is no an areas of elevated thickness in described individual layer.Most preferably, along and the whole length of the longitudinal edge of described at least one unidirectional tape of next-door neighbour, in described individual layer, do not have overlapping or there is no an areas of elevated thickness.
The individual layer forming does not have overlapping or excessive binder, and this can make individual layer more easily stacking and be more easily compressed into the multilayered material sheet with uniform surface density, thereby causes the ballistic performance on described multi-layer sheet more even.
In an embodiment of the invention, above-mentioned purpose realizes by a kind of multilayered material sheet with for the manufacture of the method for this multilayered material sheet, described sheet material comprises a fixed folded one-way single-layer of being made by strained polymer, wherein, in described lamination, the draw direction of two adjacent monolayer is different, wherein at least one individual layer comprises a plurality of unidirectional tape of being made, being arranged with equidirectional by strained polymer, and wherein adjacent band is not overlapping.
Result, according to multilayered material sheet of the present invention, i.e. next-door neighbour and for example, along the plate that there is no areas of elevated thickness (there is no the band that band is longitudinally overlapping or do not combined by overlapping jointing material on a large scale) on the longitudinal edge of unidirectional tape wherein, not only improved the ballistic performance of this sheet material, and the degree of improving is high unexpectedly.Preferably, in above-mentioned individual layer not along (non-laterally stride across) and be close to the areas of elevated thickness that the longitudinal edge of at least one unidirectional tape extends.Compare with the caused areas of elevated thickness of lateral overlap by unidirectional tape (for example, when unidirectional tape is arranged viewed situation while forming braiding structure), along and the uniform fixed lamination of the more difficult formation of appearance of the areas of elevated thickness of the longitudinal edge of next-door neighbour's unidirectional tape.
Particularly preferred multilayered material sheet according to the present invention comprises a folded individual layer, and wherein, each individual layer consists of a plurality of unidirectional tape of being made, being arranged with equidirectional by strained polymer, and in each individual layer, adjacent band is not overlapping.Plate of material of the present invention is more even than known material sheet will.In fact, in lap position, known material sheet will has the region that surface density increases.In plate of material of the present invention, there is not or occur these regions in less degree.This feature has shockingly been improved ballistic performance.
In multilayered material sheet of the present invention, individual layer is preferably manufactured by the following: by a plurality of bands so that their longitudinal edge each other the close as far as possible mode mode of adjacency (preferably with) arrange.Yet in order to manufacture individual layer in commercial scale with economic speed, allow to exist between adjacent ribbons gap (be that in individual layer, adjacent ribbons does not contact along their longitudinal edge, gap is greater than 0%).Preferably, material according to the invention plate there is following feature: the gap in individual layer between adjacent ribbons be less than adjacent unidirectional tapes width 10%, even be more preferably less than adjacent unidirectional tapes width 5%, be even more preferably less than adjacent unidirectional tapes width 3%.Most preferably, in individual layer the gap between adjacent ribbons be less than adjacent unidirectional tapes width 1%.
The plate of material of this preferred embodiment is easily manufactured and ballistic performance level and plate of material very close to each other are similar.Although individual layer according to the present invention is preferably manufactured by the following: a plurality of bands are abutted one another and arranged along their longitudinal edges, but the individual layer that the band that only has enough width by (enough wide) is made also falls within the scope of the invention, because next-door neighbour and do not occur areas of elevated thickness in the length of the longitudinal edge of at least one unidirectional tape in this individual layer.
Thereby by a plurality of drawn polymer tapes of arranging, make each band and adjacent ribbons is parallel-oriented and make the adjacent band of most of amount (at least 90%) not overlapping, can obtain the ballistic performance of comparing improvement with known materials.According to the prior art of describing in EP 1627719 A1, one-way single-layer comprises many unidirectional polyethylene bands of high strength, and it is parallel-oriented but partly overlap in a plane, described overlay region field width 5mm to 40mm.According to another embodiment, wide approximately 5 to 20mm narrow polymeric membrane is placed on two contact areas between adjacent ribbons.According in the preferred embodiment of the present invention, another advantage of multilayered material sheet is, in order to obtain good ballistic performance without above-mentioned extra polymeric membrane.And, adopt as defined herein the band there is no areas of elevated thickness, under pressure, pile subsequently the multilayered material sheet that the fixed a plurality of individual layers of superimposition obtain and compared with prior art there is more uniform surface density and thickness.
The particularly preferred embodiment of multilayered material sheet of the present invention has following feature: the polymer of manufacturing multilayered material sheet is selected from polyolefin, polyester, polyvinyl alcohol, polyacrylonitrile, polyamide (especially poly-(p-phenylene terephthalamide)), liquid crystal polymer and scalariform polymer (such as polybenzimidazoles or polybenzoxazole, especially gather (1,4-phenylene-2,6-Ben Bing bis-oxazole) or poly-(2,6-diimidazole also [4,5-b-4 ', 5 '-e] pyridine-1,4-(2,5-dihydroxy) phenylene)).The unidirectional tape of being made by these polymer and individual layer are preferably for example, by various material forms (film) being stretched under proper temperature height-oriented." unidirectional tape and individual layer " means in the application's context, and (on draw direction) has band and the individual layer of the polymer chain of preferred orientation in one direction.Above-mentioned band and individual layer can, by stretching, preferably by simple tension, be manufactured, and have anisotropic mechanical performance.
Multilayered material sheet of the present invention allows to use has relatively low intensive strained polymer, thereby does not need ultra-high molecular weight polyethylene to obtain good ballistic performance.Yet the preferred embodiment of the present invention comprises ultra-high molecular weight polyethylene.Ultra-high molecular weight polyethylene can be linear or branching, but preferably uses linear polyethylene.Linear polyethylene is understood to imply herein, on every 100 carbon atoms, has the polyethylene that is less than 1 side chain, preferably on every 300 carbon atoms, has the polyethylene that is less than 1 side chain; Wherein side chain or side chain comprise at least 10 carbon atoms conventionally.For example, described in EP0269151, by FTIR, can be suitably on the thick compacting film of 2mm, side chain be measured.Linear polyethylene can further comprise at the most 5mol% can with one or more other alkene of ethylene copolymer, for example propylene, butylene, amylene, 4-methylpentene, octene.Preferably, linear polyethylene has high molecular weight, and its inherent viscosity (IV measures decahydronaphthalenes solution at 135 ℃) is at least 4dl/g, and more preferably 8dl/g at least, most preferably is at least 10dl/g.Above-mentioned polyethylene is also referred to as ultra-high molecular weight polyethylene.Inherent viscosity is measuring of molecular weight, and it is more easily measured than actual molar mass parameters (as Mn and Mw).Such polyethylene film has particularly advantageous ballistic performance.
According to band of the present invention, can make the form of film.The method for optimizing that is used to form above-mentioned film or band comprises: polymeric powder is fed in raw material between the endless belt (endless belt) of combination, at the temperature lower than described polymeric powder fusing point, to it, carry out compression molded, and the polymer that rolling gained is compression molded, then stretches.For example in EP0 733 460 A2, described said method, above-mentioned patent documentation inserts herein by reference.If necessary, before reinforced and compression molded polymer powder, polymer powder can mix with suitable liquid organic compound, and the boiling point of these liquid organic compound is higher than the fusing point of described polymer.Compression molded can also enforcement by the following: temporarily polymer powder is retained between endless belt, carries them simultaneously.This for example can be by providing the compression cylinder and/or the roller that are connected with endless belt to realize.The UHMWPE polymer using in this method need to be stretchable under solid-state.
Another method for optimizing that is used to form film comprises: polymer is fed in extruder to extruded film at the temperature higher than described melting point polymer, and the polymeric membrane that stretches and extrude.If necessary, polymer is added in extruder before, polymer can mix for example to form gel with suitable liquid organic compound, such as preferred this situation when using ultra-high molecular weight polyethylene.
Can to made film, stretch by manner known in the art, preferably carry out simple tension.Described mode comprises, extruding and stretching and extend stretching in suitable draw unit.In order to obtain mechanical strength and the rigidity (stiffness) of raising, can carry out multi-step tension.The in the situation that of preferred ultra high molecular weight polyethylene films, conventionally implement the simple tension of a plurality of stretching step.The first stretching step for example can comprise, being stretched to draw ratio is 3.Multi-step tension can obtain conventionally, for the draft temperature draw ratio 9 up to 120 ℃, for the draft temperature draw ratio 25 up to 140 ℃, for the draft temperature draw ratio 50 up to higher than 150 ℃.By carrying out multi-step tension at the temperature constantly raising, draw ratio can reach approximately 50 or larger.This obtains high strength tapes, wherein for tapes of ultra high molecular weight polyethylene, can obtain 1.50GPa to 1.8GPa and higher intensity.
Gained drawn polymer tapes can be used as it is to manufacture individual layer, or can be cut to required width, or is rived along draw direction.Preferably, individual layer is made by the band of not riving.The width of the unidirectional tape of making thus is only exposed for the restriction of the width of the film of manufacturing band.The width of band is preferably greater than 2mm, more preferably greater than 5mm, is most preferably greater than 30mm.The surface density of band or individual layer can change in wide region, for example 5 to 200g/m
2between change.Preferred surface density between 10 to 120g/m
2between, more preferably between 15 to 80g/m
2between, most preferably between 20 to 60g/m
2between.
In another particularly preferred multilayered material sheet of the present invention, at least one individual layer forms as follows, and preferred all individual layers all form as follows, and described individual layer is made, arranged by strained polymer the unidirectional tape that forms textile structural and formed by a plurality of.Above-mentioned band can be manufactured by the following: to the little fillet of being made by strained polymer (small strip) but not conventionally carried out fiber is applied to weaving technology, such as weaving, braiding etc.Although the little fillet of polymer has areas of elevated thickness in this embodiment, said fillet partly overlaps at crosspoint place, the horizontal longitudinal edge to unidirectional tape of areas of elevated thickness, but not along and be close to longitudinal edge and extend.Each band (being the textile fabric of little fillet) is arranged, thereby between the adjacent ribbons that makes to arrange with equidirectional, do not had overlapping.By making the jointing line stacking band of mode interlaced with each other in different individual layers, can further improve ballistic performance.
In some embodiments, individual layer can comprise binding agent, its by local application with in conjunction with, stablize a plurality of unidirectional tape, thereby in processing and manufacturing one-way slabs process, keep the structure of individual layer.For example in EP 0191306 B1, EP 1170925 A1, EP 0683374 B1 and EP 1144740 A1, suitable binding agent has been described.Can apply binding agent with various forms and mode, for example, as horizontal stick (across unidirectional tape).In the forming process of individual layer, apply binding agent and be conducive to the stable of band, thereby can realize the shorter production cycle, avoid occurring between adjacent ribbons overlapping simultaneously.
In one embodiment, along the longitudinal edge of unidirectional tape, apply binding agent, thereby adjacent unidirectional tapes is stably close to.Because the effect of binding agent is temporarily retain in the process of processing and manufacture one-way slabs and stablize a plurality of unidirectional tape, so preferably part applies binding agent.It is to be restricted near near applying longitudinal edge that part applies binding agent, can comprise that intermittent part applies (edge point-like applies along the longitudinal).
Preferably, binding agent apply make the maximum of individual layer increase thickness (chimb) be form individual layer unidirectional tape average thickness 150%.More preferably, binding agent apply make maximum increase thickness be form individual layer a plurality of unidirectional tape average thickness 120%, 110% or 105%.In another embodiment, the increase of thickness in monolayer that the applying of binding agent makes to be close to the longitudinal edge of unidirectional tape is less than 4 microns, is more preferably less than 3,2 or 1 microns.
In intermittent part, apply in the embodiment of binding agent, the ratio of the longitudinal edge that contains binding agent is preferably less than 50%, 30%, 20%, 10%, 5% or 2%.Similarly, the ratio of the longitudinal edge (or next-door neighbour longitudinal edge region) of projection owing to applying binding agent of unidirectional tape is preferably less than 50%, 30%, 20%, 10%, 5% or 2%.Preferably, binding agent account for below 20% of individual layer or fixed lamination weight, below 10%, below 5%, below 2%, below 1%, below 0.5% or below 0.2%.
In other embodiments, thus can use associated methods such as ultra-sonic welded with intermittent mode, make adjacent elastic ribbon longitudinal edge some partial fusion together.
For in individual layer with intermittent mode the adjacent monolayer band along next-door neighbour's longitudinal edge combination, adjacent unidirectional tapes keeps with parallel arrangement mode.Applying of binding agent can make adjacent unidirectional tapes closely close, and between next-door neighbour's longitudinal edge, there is no overlapping.The localized variation of thickness in monolayer has advantageously been reduced (comparing with the conventional monolayers that has an overlapping longitudinal edge or have an overlapping continuously polymeric adhesive fillet), this makes the fixed folded individual layer of gained have more uniform thickness, thereby has more uniform stress distribution.
Can in wide region, to the thickness of the individual layer of multilayered material sheet or band, select in principle.Yet preferably, multilayered material sheet according to the present invention has following feature: the thickness of at least one individual layer is no more than 120 μ m, more preferably no more than 50 μ m, most preferably between 5 to 29 μ m.If the thickness of all individual layers is no more than 120 μ m in lamination, more preferably no more than 50 μ m, most preferably, between 3 to 29 μ m, obtain so particularly advantageous ballistic performance.According to the multilayer material of present invention further optimization, there is following feature: the thickness of at least one individual layer is greater than 10 μ m, but be no more than 50 μ m, be preferably no more than 100 μ m, more preferably no more than 120 μ m.By the thickness of at least one individual layer in lamination is defined as to thickness required for protection, even adopt the quite limited individual layer of intensity also can shockingly obtain enough ballistic performances.
In multilayered material sheet, the intensity of each band mainly depends on and manufactures the polymer of these bands and the draw ratio of these bands (unidirectional).The intensity of band (and individual layer) is at least 0.75GPa, is preferably at least 0.9GPa, more preferably 1.2GPa at least, 1.5GPa at least even more preferably, 1.8GPa at least even more preferably, even more preferably 2.1GPa at least, most preferably is at least 3GPa.One-way single-layer is preferably connected to each other each other fully, this means that one-way single-layer for example, under normal service condition (room temperature) can layering.
Multilayered material sheet according to the present invention preferably includes at least 2 one-way single-layers, preferably includes at least 4 one-way single-layers, more preferably comprises at least 6 one-way single-layers, even more preferably comprises at least 8 one-way single-layers, most preferably comprises at least 10 one-way single-layers.The quantity that increases one-way single-layer in multilayered material sheet of the present invention will be simplified the process of being manufactured goods (for example manufacturing armour) by these plate of material.
In an embodiment of the invention, provide a kind of method for the manufacture of multilayered material sheet, described method comprises:
(a) at least one first strained polymer unidirectional tape is arranged on moving substrate, thereby forms the first individual layer, wherein, next-door neighbour and along most of length of the longitudinal edge of described at least one unidirectional tape, described individual layer does not have areas of elevated thickness;
(b) described the first individual layer is remained on described moving substrate;
(c) at least one second strained polymer unidirectional tape is arranged on described the first individual layer, thereby forms the second individual layer, wherein, the direction of described the second individual layer is with respect to the angled α of described the first individual layer; And
(d) lamination that compression forms thus, thus make its single-layer, consolidated.
Fixed single layer stack compared with prior art has more uniform thickness/surface density, reason is, in individual layer (preferably in each individual layer), along and be close to the areas of elevated thickness of longitudinal edge of at least one unidirectional tape reduced or there is not above-mentioned areas of elevated thickness.
In the preferred embodiment of the present invention, provide a kind of method for the manufacture of thering is multilayered material sheet required for protection.Described method of the present invention comprises the steps:
(a) provide a plurality of drawn polymer tapes, arrange described band so that each band and adjacent ribbons are parallel-oriented, and adjacent ribbons substantially can be not overlapping;
(b) described a plurality of drawn polymer tapes are arranged on moving substrate, thereby form the first individual layer;
(c) described the first individual layer is remained on described moving substrate;
(d) a plurality of strained polymer unidirectional tape are arranged on described the first individual layer, thereby form the second individual layer, wherein, the direction of described the second individual layer is with respect to the angled α of described the first individual layer; And
(e) lamination that compression forms thus, thus make its single-layer, consolidated.
Step (a) is optional to be comprised and applies binding agent or engagement means to keep or stabilize adjacent band, thereby improves accessible throughput rate.Adopt method required for protection easily to manufacture and there is no overlapping region (region that there is no high areal density) multilayered material sheet.The plate of material of manufacturing thus has the ballistic performance of improvement with respect to the plate of material with overlapping region.
Preferably, a plurality of drawn polymer tapes are untied from uncoiler (unwinding station), and on himself, carried out step (d) by a plurality of drawn polymer tapes are folded at least partly.More preferably, a plurality of drawn polymer tapes are arranged, thereby make the first individual layer with respect to the angled β of moving direction of described substrate, thereby and fold the moving direction of broken line and described substrate is extended substantially in parallel.The method according to this invention has following further feature: angle beta is between 40 to 50 degree, and most preferred angle beta is about 45 degree.
Another method for optimizing according to the present invention has following feature: described the second individual layer sticks on described the first individual layer at least partly.This can be for example by ultra-sonic welded, by adding low melting point film, binding agent or easily realizing by other method that each layer combined.Described the second individual layer is preferably enough strong to the adhesiveness of described the first individual layer, thereby can be so that do not have independent band and/or individual layer to occur significantly to relatively move in the transportation of individual layer assembly.
The method according to this invention, manufactures multilayered material sheet, wherein, and the draw direction difference angle α of two adjacent monolayer in described lamination.The method for optimizing extending substantially in parallel for the moving direction of broken line and described substrate, angle [alpha]=2 β.Although can be in wide region selected angle α, angle [alpha] is preferably between 45 to 135 °, more preferably between 65 to 115 °, most preferably between 80 to 100 °.In further preferred scope, particularly preferred angle [alpha] is about 90 °.According to the material of this preferred embodiment manufacture, in this area, be called as cross-ply (cross-ply).
Multilayered material sheet according to the present invention is particularly suitable for manufacturing ballistic-resistant article, for example vest or armour plate.Armor application comprises, resists the application of several projectile bodies (comprise and resist armoe-piercing cartridge, so-called AP bullet and grit, such as shell fragment and shrapnel) impact threat.
Ballistic-resistant article according to the present invention comprises at least 2 one-way single-layers, preferably includes at least 10 one-way single-layers, more preferably comprises at least 20 one-way single-layers, even more preferably comprises at least 30 one-way single-layers, most preferably comprises at least 40 one-way single-layers.The draw direction difference angle α of two adjacent monolayer in lamination.Described angle [alpha] is preferably between 45 to 135 °, more preferably between 65 to 115 °, most preferably between 80 to 100 °.
Preferably, ballistic-resistant article according to the present invention comprises other inorganic material plate, and described inorganic material is selected from pottery; Metal, is preferably aluminium, magnesium, titanium, nickel, chromium and iron or their alloy; Glass; Graphite or its combination.Particularly preferably be metal.In these cases, the described metal in metallic plate preferably has at least 350 ℃, more preferably at least 500 ℃, the fusing point of at least 600 ℃ most preferably.Suitable metal comprises aluminium, magnesium, titanium, copper, nickel, chromium, beryllium, iron and copper, the alloy that comprises them, for example steel and stainless steel, the alloy of aluminium and magnesium (so-called 5000 is aluminium), the alloy of the alloy of aluminium and zinc and magnesium or aluminium and zinc, magnesium and copper (so-called 7000 is aluminium).In described alloy, for example the content of aluminium, magnesium, titanium and iron is preferably at least 50wt%.Preferred metallic plate comprises aluminium, magnesium, titanium, nickel, chromium, beryllium, iron (alloy that comprises them).More preferably, metallic plate be take aluminium, magnesium, titanium, nickel, chromium, iron and their alloy as basis.This makes lightweight bulletproof goods have good durability.Even more preferably, the iron in metallic plate and alloy thereof have at least 500 Brinell hardness.Most preferably, metallic plate be take aluminium, magnesium, titanium and their alloy as basis.This obtains having the lightest ballistic-resistant article of the highest durability.In the application, durability means, the life-span of composite under the condition that is exposed to heat, moisture, light and UV radiation.Although other plate of material can be arranged in the optional position in single layer stack, preferred ballistic-resistant article has following feature: other plate of material is positioned at the outside of single layer stack, is most preferably at least positioned at the surface of a wound that is subject to of described single layer stack.
Ballistic-resistant article according to the present invention preferably includes, and thickness is 100mm at the most, other plate of being made by above-mentioned inorganic material.Preferably, the maximum ga(u)ge of other inorganic material plate is 75mm, and more preferably 50mm, most preferably is 25mm.This has obtained the optimum balance between weight and ballistic performance.Preferably, in the situation that other inorganic material plate is metallic plate, the thickness of described metallic plate is 0.25mm at least, and more preferably 0.5mm at least, most preferably is at least 0.75mm.This has obtained even better ballistic performance.
In order to improve the adhesiveness of other inorganic material plate and multilayered material sheet, optional it is carried out to pretreatment.Suitable pretreatment to other plate comprises: mechanical treatment, for example, by polishing or grinding roughening or clean surface; Chemical etching, for example, adopt nitric acid to carry out chemical etching; And laminated with polyethylene film.
In another embodiment of ballistic-resistant article, can between other plate and multilayered material sheet, apply binder course, for example adhesive.Above-mentioned adhesive can comprise epoxy resin, mylar, polyurethane resin or vinyl ester resin.Another preferred embodiment in, binder course may further include textle layers or the nonwoven layers of inorfil (for example glass fibre or carbon fiber).Can also be by fixing such as screw, bolt is fixed and snap close is fixed (snap fit) mechanical system is connected to other layer on multilayered material sheet.In the situation that ballistic-resistant article according to the present invention resists with running into therein the ballisticimpact application that AP bullet, fragment or interim apparatus to cause bursting threaten, other plate preferably includes the metallic plate being covered by ceramic layer.By this way, obtain having the ballistic-resistant article of following hierarchy: ceramic layer/metal/at least two one-way slabs, the angled α of machine direction in wherein said one-way slabs in the direction of fiber and adjacent one-way plate.Suitable ceramic material for example comprises aluminium oxide, titanium oxide, silica, carborundum and boron carbide.The thickness of ceramic layer depends on the level of ballistic threat, but conventionally between 2mm to 30mm, changes.Preferably this ballistic-resistant article is arranged to thereby ceramic layer is in the face of ballistic threat.
In an embodiment of the invention, a kind of method for the manufacture of ballistic-resistant article is provided, described method comprises: (a) stacked at least 2 simple tension polymer monolayers and the plate of material that is selected from pottery, steel, aluminium, titanium, glass and graphite or its combination, each polymer monolayers comprises at least one unidirectional tape, the draw direction of two adjacent monolayer in wherein said lamination is different, at least one individual layer along and most of length of being close to the longitudinal edge of at least one unidirectional tape there is no areas of elevated thickness; (b) fixed laminated plate under uniform temperature and pressure.
In the preferred embodiment of the present invention, a kind of method for the manufacture of ballistic-resistant article is provided, described method comprises the steps: (a) stacked at least 2 simple tension polymer monolayers and is selected from other inorganic material plate of pottery, steel, aluminium, titanium, glass and graphite or its combination, the draw direction of two adjacent monolayer in wherein said lamination is different, at least one individual layer (preferred all individual layers) comprises a plurality of unidirectional tape that formed, arranged with equidirectional by strained polymer, and adjacent ribbons is not overlapping; (b) fixed laminated plate under uniform temperature and pressure.
In other method, in above-described independent method for example, manufacture the lamination of at least 2 simple tension polymer monolayers.Then with the step (a) of this method, the lamination of preproduction and other plate of material that is selected from pottery, steel, aluminium, titanium, glass and graphite or its combination are combined.
Be suitable for carrying out above-mentioned methodical consolidation step in hydraulic press.Fixed meaning, thus individual layer is relatively firmly connected to a unit of formation on another individual layer.Conventionally adopt the temperature of press to control the temperature in consolidation process.Thereby conventionally select minimum temperature to obtain rational consolidation rate.Aspect this, suitable lowest temperature is 80 ℃, and this lower limit is preferably at least 100 ℃, more preferably at least 120 ℃, most preferably is at least 140 ℃.The temperature that selected maximum temperature is lost its high-mechanical property lower than drawn polymer monolayer due to for example melting.Preferably, this temperature is lower at least 10 ℃ than the melt temperature of drawn polymer monolayer, preferably low at least 15 ℃, even more preferably low at least 20 ℃.In the situation that drawn polymer monolayer does not have clear and definite melt temperature, should read the temperature that drawn polymer monolayer starts to lose its mechanical performance and substitute melt temperature.The in the situation that of preferred ultra-high molecular weight polyethylene, selected temperature is lower than 145 ℃.Pressure in consolidation process is preferably at least 7MPa, 15MPa at least more preferably, and even more preferably 20MPa at least, most preferably is at least 35MPa.By this way, obtain unbending ballistic-resistant article.Fixed Best Times is conventionally in the scope of 5 to 120 minutes, and this depends on the condition such as temperature, pressure and component thickness, and can examine by normal experiment.In the situation that manufacture crooked ballistic-resistant article, first other plate of material is preformed into required form, then with individual layer and/or multilayered material sheet fixed be favourable.
Preferably, in order to obtain high ballistic performance, at high temperature compression molded rear under pressure, implement equally cooling.It is enough low that preferred pressure at least remains to temperature, thereby prevent from relaxing.Those skilled in the art can determine this temperature.When ballistic-resistant article that manufacture contains ultra-high molecular weight polyethylene individual layer, compression temperature is in the scope of 90 to 150 ℃, preferably in the scope of 115 to 130 ℃ conventionally.Conventionally compression pressure is in 100 to 300bar scope, preferably in 100 to 180bar scope, more preferably in 120 to 160bar scope.And compression time is conventionally between 40 to 180 minutes.
Multilayered material sheet of the present invention is compared advantageous particularly with ballistic-resistant article with the bullet resistant material of previously known; because they provide at least identical with known articles level of protection under significantly lower weight, or comparing the ballistic performance that improvement is provided under equal weight with known articles.Raw material is inexpensive, and manufacturing process is relatively short, thereby cost efficiency is higher.Because can use different polymers manufacturings multilayered material sheet of the present invention, therefore according to application-specific, optimize character separately.Except bullet-proof, other character is such as comprising heat endurance, pot-life, deformation resistance, the ability of being combined with other plate of material, formability etc.
By following Fig. 1-4, further explain the present invention now, but the present invention is not limited thereto.
Fig. 1 schematically shows the embodiment of the equipment of implementing the inventive method.
Fig. 2 schematically shows multilayered material sheet.
Fig. 3 schematically shows monolayer of woven tapes.
Fig. 4 schematically shows multilayered material sheet.
With reference to Fig. 1, show for the manufacture of the equipment 1 with the multilayered material sheet of claimed type.This equipment comprises for the device 2 of a plurality of drawn polymer tapes 10 is provided.This device 2 for example can comprise the uncoiler for polymeric tapes 10 volumes.Thereby arranged polymeric tapes 10 each band 10 are parallel-oriented with adjacent band 10.Equipment 1 also comprises moving substrate (movingsubstrate) 3, and in the embodiment shown, it is the belt being driven by two cylindrical rolls 4.Belt 3 moves along the direction shown in arrow with speed V3.Make band 10 by one group of mip rolls (niproller) (5a, 5b) thus a plurality of bands 10 are arranged on substrate 3.A plurality of bands 10 by maintenance equipment (for example, by boring a hole on substrate 3 and space 6 being provided) thus remain on substrate 3, can make by the pump 7 below substrate 3 described space 6 under vacuum.After movable substrate 3, place belt press, described belt press comprises two areas of heating surface (21,22) that driven by cylindrical roll 23
The method according to this invention comprises, a plurality of simple tension polymeric tapes 10 are untied from uncoiler 2 with speed V1.Thereby band 10 is arranged and made the adjacent ribbons substantially can be not overlapping, and between adjacent ribbons, there is no gap (being conventionally less than 2mm).Then by mip rolls group (5a, 5b), provide band 10.As described in Figure 1, the assembly of uncoiler 2 and mip rolls group (5a, 5b) with speed V2 transversely direction cross back and forth substrate 3.Vacuum belt substrate 3 moves along the direction that is substantially perpendicular to horizontal direction with speed V3.Ratio to V2 and V3 is selected, thereby a plurality of band 10 is arranged on moving substrate 3 into about miter angle with the moving direction with respect to substrate 3, thereby forms the first individual layer.The suction producing by vacuum plant (6,7) remains on moving substrate 3 described the first individual layer.When uncoiler 2 arrives the opposite side of moving substrates 3, its moving direction that overturns, and mobile uncoiler 2 in the opposite direction.Thereby a plurality of drawn polymer tapes 10 are folded on himself at least partly.More specifically, folding a plurality of drawn polymer tapes 10, thus the moving direction of broken line and substrate 3 is extended substantially in parallel.Thereby the second individual layer is arranged on described the first individual layer, the direction of wherein said the second individual layer is the angle into about 90 degree with respect to described the first individual layer.In order to ensure transporting the assembly of the first individual layer and the second individual layer, do not have independent band and/or individual layer to relatively move, described the second band individual layer adheres on described the first individual layer at least partly.Any other method that the suitable means that are applicable to above-mentioned steps include, but not limited to ultra-sonic welded, add low melt film, adhesive, heat fusing thing or each layer combined.
Finally, the individual layer assembly forming is thus fed on belt press or calender 20, thus final fixed described multilayered material sheet.In belt press or calender 20, the combination at the temperature of fusing point that approaches described band of stacking a plurality of bands.In said embodiment, gained multilayer material is the two layers of material of the cross folding made by band, wherein, the direction of band with respect to the moving direction of substrate 3 into about miter angle.
On device 2, the width of a plurality of bands 10 is decided by the width that is placed on the multilayer material on the belt press or calender of label 20, on substrate 3.In the situation that band is 45 degree with respect to the moving direction angulation β of substrate 3, the width of a plurality of bands 10 equals
the width of * multilayer material.
With reference to Fig. 2, show the diagram presentation graphs according to multilayered material sheet of the present invention, described multilayered material sheet comprises fixed folded 2 one-way single-layers of being made by strained polymer, wherein, the draw direction 90-degree rotation of two adjacent monolayer in lamination, wherein, each individual layer comprises the unidirectional tape of a plurality of strained polymers by arranging with equidirectional, and wherein adjacent ribbons can be not overlapping.For clear, each band extends out in the edge of multilayered material sheet.
With reference to Fig. 3, show the diagram presentation graphs according to individual layer of the present invention, wherein, the unidirectional tape that described individual layer forms the strained polymer of textile structural by a plurality of arrangements forms.
With reference to Fig. 4, show the diagram presentation graphs according to multilayered material sheet of the present invention, described multilayered material sheet comprises Fig. 3 individual layer (solid line represents) that label 1 represents, second individual layer (dotted line represents) of its lower textile strip for label 2 expressions.The second individual layer is arranged, thereby the jointing line of each individual layer is arranged in mode interlaced with each other.
Method of testing related in the application is as follows:
According to method PTC-179 (Hercules Inc.Rev.Apr.29,1982) measure inherent viscosity, test condition is: at 135 ℃, in decahydronaphthalenes, dissolution time is 16 hours, adopt consumption be the DBPC of 2g/l solution as antioxidant, wherein the viscosity extrapolation of measuring is obtained to the viscosity under zero-dose under variable concentrations.
Tensile property (measuring at 25 ℃): according to the regulation of ASTM D885M, the crosshead speed of the fiber that is 500mm by nominal calibrated length, 50%/min defines and measure hot strength (or intensity), stretch modulus (or modulus) and the elongation at break (or eab) of multifilament yarn.On the basis of the load-deformation curve of measuring, by the slope between 0.3-1% strain, determine modulus.In order to calculate modulus and intensity, by measured tensile force, divided by fiber number, this fiber number is determined by the 10 meters of long fibers of weighing; Assumed density is 0.97g/cm
3the unit of calculating is the value of GPa.The tensile property of film is measured according to ISO1184 (H).
Claims (30)
1. a multilayered material sheet, described multilayered material sheet comprises a fixed folded one-way single-layer of being made by strained polymer, wherein, in described lamination, the draw direction of two adjacent monolayer is different, wherein at least one individual layer comprises the unidirectional tape that at least one is made by strained polymer, each band comprises longitudinal edge, next-door neighbour and along most of length of the described longitudinal edge of described at least one unidirectional tape wherein, described individual layer does not have areas of elevated thickness, wherein when described at least one individual layer is made by strained polymer by a plurality of, the unidirectional tape of arranging with equidirectional forms, described adjacent band is not overlapping, wherein, fixed described lamination under uniform temperature and pressure, and selected temperature is lost the temperature of its high-mechanical property lower than drawn polymer monolayer.
2. multilayered material sheet as claimed in claim 1, wherein, along and the whole length of the described longitudinal edge of described at least one unidirectional tape of next-door neighbour, described at least one individual layer does not have areas of elevated thickness.
3. multilayered material sheet as claimed in claim 1, wherein, described at least one individual layer comprises a plurality of unidirectional tape of being made by strained polymer, wherein, the gap between adjacent ribbons be less than adjacent unidirectional tapes width 10%.
4. multilayered material sheet as claimed in claim 3, wherein, the gap between adjacent ribbons be less than adjacent unidirectional tapes width 5%.
5. multilayered material sheet as claimed in claim 1, wherein, the longitudinal edge of described adjacent ribbons each other at least partly near.
6. multilayered material sheet as claimed in claim 5, wherein, described adjacent ribbons is next-door neighbour stably at least partly each other.
7. multilayered material sheet as claimed in claim 1, wherein, the thickness of at least one individual layer can be over 100 microns.
8. multilayered material sheet as claimed in claim 7, wherein, the thickness of at least one individual layer can be over 29 microns.
9. multilayered material sheet as claimed in claim 7, wherein, the thickness of described at least one individual layer is greater than 10 microns.
10. multilayered material sheet as claimed in claim 7, wherein, the intensity of at least one individual layer is 0.9GPa at least.
11. multilayered material sheets as claimed in claim 10, wherein, the intensity of at least one individual layer is 1.5GPa at least.
12. multilayered material sheets as claimed in claim 1, wherein, described polymer is selected from polyolefin; Polyester; Polyvinyl alcohol; Polyacrylonitrile; Polyamide; Liquid crystal polymer and polybenzimidazoles or polybenzoxazole.
13. multilayered material sheets as claimed in claim 12, wherein, described polyolefin comprises ultra-high molecular weight polyethylene.
14. 1 kinds of methods for the manufacture of multilayered material sheet described in any one in claim 1 to 13, described method comprises:
(a) provide a plurality of drawn polymer tapes, arrange described band so that each band and adjacent ribbons are parallel-oriented, and adjacent ribbons is not overlapping;
(b) described a plurality of drawn polymer tapes are arranged on moving substrate, thereby form the first individual layer;
(c) described the first individual layer is remained on described moving substrate;
(d) a plurality of strained polymer unidirectional tape are arranged on described the first individual layer, thereby form the second individual layer, wherein, the direction of described the second individual layer is with respect to the angled α of described the first individual layer; And
(e) lamination that compression forms thus, thus make its single-layer, consolidated.
15. methods as claimed in claim 14, wherein, step (a) further comprises, adhesive or adhesive means are applied to the step in adjacent ribbons.
16. methods as described in claims 14 or 15, wherein, untie described a plurality of drawn polymer tapes from uncoiler, by described a plurality of drawn polymer tapes are folded at least partly, carry out step (d) on himself.
17. methods as claimed in claim 14, wherein, described a plurality of drawn polymer tapes are arranged, thereby make described the first individual layer with respect to the angled β of moving direction of described substrate, thereby and fold the moving direction of broken line and described substrate is extended substantially in parallel.
18. methods as claimed in claim 17, wherein, described angle beta is between 40 to 50 degree.
19. methods as claimed in claim 14, wherein, described the second individual layer adheres on described the first individual layer at least partly.
20. 1 kinds of methods for the manufacture of ballistic-resistant article, described method comprises:
(a) stacked at least 2 simple tension polymer monolayers and the plate of material that is selected from pottery, steel, aluminium, titanium, glass and graphite or its combination, wherein the draw direction of two adjacent monolayer in lamination is different, at least one individual layer comprises a plurality of strained polymer unidirectional tape of arranging along equidirectional, and adjacent ribbons is not overlapping; With
(b) fixed laminated plate under uniform temperature and pressure,
Wherein, selected temperature is lost the temperature of its high-mechanical property lower than drawn polymer monolayer.
21. 1 kinds of ballistic-resistant articles, described ballistic-resistant article comprises the multilayered material sheet described in any one in claim 1 to 13.
22. ballistic-resistant articles as claimed in claim 21, described ballistic-resistant article comprises at least 40 one-way single-layers.
23. ballistic-resistant articles as claimed in claim 21, described ballistic-resistant article comprises other inorganic material plate, described inorganic material is selected from pottery, steel, aluminium, magnesium, titanium, nickel, chromium and iron or their alloy, glass and graphite or its combination.
24. ballistic-resistant articles as claimed in claim 23, wherein, other inorganic material plate is positioned at the outside of single layer stack.
25. ballistic-resistant articles as claimed in claim 23, wherein, the thickness of described other inorganic material plate is 50mm at the most.
, wherein, there is binder course between the plate of material in other inorganic material plate and claim 1 to 13 described in any one in 26. ballistic-resistant articles as described in any one in claim 23 to 25, described binder course comprises textle layers or the nonwoven layers of inorfil.
27. 1 kinds of methods for the manufacture of ballistic-resistant article, described method comprises:
(a) stack at least 2 simple tension polymer monolayers and the plate of material that is selected from pottery, steel, aluminium, titanium, glass and graphite or its combination, each individual layer comprises at least one unidirectional tape, the draw direction of two adjacent monolayer in wherein said lamination is different, and wherein, next-door neighbour and along most of length of the longitudinal edge of described at least one unidirectional tape, at least one individual layer does not have areas of elevated thickness: and
(b) fixed laminated plate under uniform temperature and pressure,
Wherein, selected temperature is lost the temperature of its high-mechanical property lower than drawn polymer monolayer.
28. multilayered material sheets as claimed in claim 12, wherein said polymer is poly-(p-phenylene terephthalamide).
29. multilayered material sheets as claimed in claim 12, wherein said polymer is poly-(Isosorbide-5-Nitrae-phenylene-2,6-Ben Bing bis-oxazole) or poly-(2,6-diimidazole is [4,5-b-4', 5'-e] pyridine-Isosorbide-5-Nitrae-(2,5-dihydroxy) phenylene also).
30. ballistic-resistant articles as claimed in claim 24, wherein other inorganic material plate is positioned at the surface of a wound that is subject to of single layer stack.
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| US87654506P | 2006-12-22 | 2006-12-22 | |
| US60/876,545 | 2006-12-22 | ||
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| EP06026723.4 | 2006-12-22 | ||
| PCT/EP2007/003684 WO2007122009A1 (en) | 2006-04-26 | 2007-04-26 | Multilayered material sheet and process for its preparation |
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| CN101479558A CN101479558A (en) | 2009-07-08 |
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| CN200780023860.5A Active CN101479556B (en) | 2006-04-26 | 2007-04-26 | Multilayered material sheet and manufacture method thereof |
| CN2007800239788A Active CN101479557B (en) | 2006-04-26 | 2007-04-26 | Multilayered material sheet and process for its preparation |
| CN200780024030.4A Active CN101479558B (en) | 2006-04-26 | 2007-04-26 | Multilayered material sheet and process for its preparation |
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| CN2007800239788A Active CN101479557B (en) | 2006-04-26 | 2007-04-26 | Multilayered material sheet and process for its preparation |
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| CN101881582B (en) * | 2009-12-09 | 2015-03-25 | 湖南中泰特种装备有限责任公司 | Stabproof bulletproof material and preparation method |
| CN102538590B (en) * | 2011-12-16 | 2014-11-19 | 宁波荣溢化纤科技有限公司 | Preparation method of polyethylene/aluminum oxide composite bulletproof plate with super-high molecular weight |
| KR20150123943A (en) * | 2013-03-13 | 2015-11-04 | 디에스엠 아이피 어셋츠 비.브이. | Light-weight semi-rigid composite anti-ballistic systems with engineered compliance and rate-sensitive impact response |
| CN104228062A (en) * | 2013-06-20 | 2014-12-24 | 郑州中远防务材料有限公司 | Unidirectional fabric, non-woven fabric, preparation methods of fabrics and non-woven fabric product |
| CN103724758B (en) * | 2013-12-05 | 2015-08-26 | 王庆昭 | The melt extruding of ultrahigh molecular weight polyethylene(UHMWPE) film, be drawn into film production process and production equipment thereof |
| JP6080876B2 (en) * | 2015-02-04 | 2017-02-15 | 日新製鋼株式会社 | Composite body in which painted metal base material and cloth containing chemical fiber are joined, and method for producing the same |
| KR102635788B1 (en) * | 2017-12-18 | 2024-02-13 | 디에스엠 아이피 어셋츠 비.브이. | bulletproof molded product |
| CN108340633B (en) * | 2018-03-13 | 2024-02-27 | 华侨大学 | Adhesive-fixed laminated crack-stop section bar |
| CN110759730A (en) * | 2018-07-25 | 2020-02-07 | 比亚迪股份有限公司 | Preparation method of composite ceramic and composite ceramic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931126A (en) * | 1989-04-14 | 1990-06-05 | The Boeing Company | Apparatus and method for joining a plurality of thermoplastic tapes |
| EP1627719A1 (en) * | 2004-08-16 | 2006-02-22 | FMS Enterprises Migun Ltd. | Multilayered polyethylene material and ballistic resistant articles manufactured therefrom |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4663101A (en) * | 1985-01-11 | 1987-05-05 | Allied Corporation | Shaped polyethylene articles of intermediate molecular weight and high modulus |
| US6846548B2 (en) * | 1999-02-19 | 2005-01-25 | Honeywell International Inc. | Flexible fabric from fibrous web and discontinuous domain matrix |
| US6448359B1 (en) * | 2000-03-27 | 2002-09-10 | Honeywell International Inc. | High tenacity, high modulus filament |
| IT1317268B1 (en) * | 2000-04-17 | 2003-05-27 | Citterio Flli Spa | REINFORCED MULTILAYER FABRIC AND PROCEDURE FOR ITS REALIZATION |
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2007
- 2007-04-25 CN CNA2007800238709A patent/CN101479101A/en active Pending
- 2007-04-26 CN CN200780023860.5A patent/CN101479556B/en active Active
- 2007-04-26 CN CN2007800239788A patent/CN101479557B/en active Active
- 2007-04-26 CN CN200780024030.4A patent/CN101479558B/en active Active
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2008
- 2008-11-05 ZA ZA200809461A patent/ZA200809461B/en unknown
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931126A (en) * | 1989-04-14 | 1990-06-05 | The Boeing Company | Apparatus and method for joining a plurality of thermoplastic tapes |
| EP1627719A1 (en) * | 2004-08-16 | 2006-02-22 | FMS Enterprises Migun Ltd. | Multilayered polyethylene material and ballistic resistant articles manufactured therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200809461B (en) | 2009-11-25 |
| CN101479557B (en) | 2013-09-18 |
| CN101479556B (en) | 2015-10-21 |
| ZA200809460B (en) | 2010-04-28 |
| CN101479556A (en) | 2009-07-08 |
| ZA200809459B (en) | 2009-11-25 |
| CN101479557A (en) | 2009-07-08 |
| CN101479558A (en) | 2009-07-08 |
| CN101479101A (en) | 2009-07-08 |
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