CN102131636A - 具有高压缩模量的折叠芯和由其制成的制品 - Google Patents
具有高压缩模量的折叠芯和由其制成的制品 Download PDFInfo
- Publication number
- CN102131636A CN102131636A CN2009801326655A CN200980132665A CN102131636A CN 102131636 A CN102131636 A CN 102131636A CN 2009801326655 A CN2009801326655 A CN 2009801326655A CN 200980132665 A CN200980132665 A CN 200980132665A CN 102131636 A CN102131636 A CN 102131636A
- Authority
- CN
- China
- Prior art keywords
- nonwoven sheet
- resin
- cured resin
- fiber
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000006835 compression Effects 0.000 title abstract description 13
- 238000007906 compression Methods 0.000 title abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000000835 fiber Substances 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000011343 solid material Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000004760 aramid Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract 3
- 239000000463 material Substances 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000002023 wood Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000003490 calendering Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920000271 Kevlar® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920003261 Durez Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229920003369 Kevlar® 49 Polymers 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 229920000508 Vectran Polymers 0.000 description 1
- 239000004979 Vectran Substances 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- -1 shaping assistant Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
- D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
- D21H25/14—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod the body being a casting drum, a heated roll or a calender
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
- Y10T442/2893—Coated or impregnated polyamide fiber fabric
- Y10T442/2902—Aromatic polyamide fiber fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/654—Including a free metal or alloy constituent
- Y10T442/656—Preformed metallic film or foil or sheet [film or foil or sheet had structural integrity prior to association with the nonwoven fabric]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonwoven Fabrics (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
本发明涉及具有高压缩模量的折叠的棋盘格状芯结构,所述芯结构包含非织造片材和固化树脂,所述固化树脂的量使得固化树脂和非织造片材的合并重量中固化树脂的百分比为至少50%,所述非织造片材还包含具有至少200克/旦尼尔(180克/分特)的模量和至少10克/旦尼尔(9克/分特)的韧度的纤维,其中所述非织造片材在用树脂浸渍前具有通过以下公式计算的表观密度:Dp=K×((dr×(100-%r)/%r)/(1+dr/ds×(100-%r)/%r),其中Dp是所述片材在浸渍前的表观密度,dr是固化树脂的密度,ds是在浸渍前片材中固体材料的密度,%r是最终的芯结构中固化树脂的重量百分比含量,K是值为1.0至1.5的数字。此外,在用树脂浸渍前,非织造片材的Gurley孔隙率不大于30秒/100毫升。本发明还涉及包括这种折叠芯的复合结构。
Description
发明背景
1.发明领域。
本发明涉及高压缩模量的折叠芯结构。
2.背景技术。
由高模量高强度纤维非织造片材制成的用于夹心板的芯结构(大多数呈蜂窝结构形式)用于不同的应用中,但主要用于航空和航天工业中,其中强度与重量或硬度与重量的比率具有极高的值。例如,授予Lin的美国专利5,137,768描述了一种由高密度湿法成网的非织造材料制成的蜂窝结构芯,所述非织造材料包含50重量%或更多的对位芳族聚酰胺纤维,其中该组合物的其余部分为粘合剂和其它添加剂。
可商购获得的用于制备芯结构的高模量高强度纤维非织造片材是由E.I.DuPont de Nemours and Company,Wilmington,DE出售的KEVLARN636纸材。最轻等级(1.4N636)的纸材密度在0.68-0.82g/cm3的范围内。就其它三类等级(1.8N636、2.8N636和3.9N636)而言,其密度在0.78-0.92g/cm3的范围内。
与传统的蜂窝结构相比,折叠芯结构可用经济得多的方法来制备。在一些应用中,增强压缩性能非常重要。这对于用于飞机、火车等的地板的夹心板尤其如此。对压缩模量(硬度)和/或剪切强度作出优化的折叠芯潜在地可提供额外重量并节约成本。因此,需要具有改善的压缩模量的折叠芯。
发明简述
本发明涉及具有高压缩模量的折叠芯结构。所述芯结构包括多个折叠的棋盘格状构型,所述棋盘格状构型还包含非织造片材和固化树脂,所述固化树脂的量使得固化树脂在所述固化树脂和非织造片材的合并重量中的重量百分比为至少50%,所述非织造片材还包含具有至少200克/旦尼尔(180克/分特)的模量和至少10克/旦尼尔(9克/分特)的韧度的纤维,其中所述非织造片材在用树脂浸渍前具有通过以下公式计算的表观密度:Dp=K×((dr×(100-%r)/%r)/(1+dr/ds×(100-%r)/%r),其中Dp是所述片材在浸渍前的表观密度,dr是固化树脂的密度,ds是在浸渍前片材中固体材料的密度,%r是最终的芯结构中固化树脂的重量百分比含量,K是值为1.0至1.5的数字。此外,在用树脂浸渍前,非织造片材的Gurley孔隙率不大于30秒/100毫升。
本发明还涉及包括折叠芯结构的复合材料面板。
附图简述
图1是折叠芯结构的例证。
发明详述
本发明涉及具有高压缩模量的折叠芯结构。折叠芯是由比较薄的平面薄片材料折叠而成的折叠几何图案的三维结构。图1中示出了折叠结构的实例。在美国专利6,935,997 B2和6,800,351 B1中论述了此类折叠或者棋盘格状的片材结构。山形是三维折叠棋盘格状芯结构的普通图案。
折叠的棋盘格状芯结构包含非织造纤维片材,已用热固性树脂对所述非织造纤维片材进行了涂覆或浸渍。
本发明的折叠芯包含按片材材料加上树脂涂层的总重量计的至少50重量%含量的树脂。非织造片材在用树脂浸渍前的表现密度由以下公式限定:
Dp=K×((dr×(100-%r)/%r)/(1+dr/ds×(100-%r)/%r)其中Dp是浸渍前非织造纸片材的表现密度,dr是固化树脂的密度,ds是浸渍前非织造片材中固体材料的密度,%r是固化树脂在最终芯结构中的重量百分比含量,并且K是值为1至1.5的数字。
所述非织造片材在用树脂浸渍前具有不超过30秒/100毫升的Gurley空气阻力。
薄片材料的高渗透性使得树脂可在树脂浸渍过程期间良好地渗透到片材材料中,使得片材的厚度在涂覆之后与未经涂覆的非织造片材的厚度没有显著的差异。
非织造片材折叠芯的自由体积/空隙含量可基于非织造片材的表观密度和非织造片材中固体材料的密度或者通过片材横截面的图像分析来测量。
用于本发明的非织造片材的厚度取决于折叠芯的最终用途或所需特性,在一些实施方案中,片材的厚度通常为3至20密耳(75至500微米)。在一些实施方案中,非织造片材的基重为0.5至6盎司/平方码(15至200克/平方米)。
用于本发明的折叠芯的非织造片材包含70至100重量份的高模量高强度纤维和不超过30重量%的粘合剂,所述纤维具有至少200克/旦尼尔(180克/分特)的初始杨氏模量、至少10克/旦尼尔(9克/分特)的韧度。
根据最终的用途,可将不同的材料用作非织造片材粘合剂。优选的粘合剂包括聚间苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺、聚磺酰胺(PSA)、聚苯硫醚(PPS)和聚酰亚胺。可将不同的高模量高强度纤维以连续纤维、短纤维(絮凝物)、纸浆或者它们的组合的形式用于本发明的折叠芯的高模量高强度纤维非织造片材。优选的纤维种类包括对位芳族聚酰胺、液晶聚酯、聚苯并唑、聚吡啶并唑、聚磺酰胺、聚苯硫醚、聚烯烃、碳、玻璃和其它无机纤维、或它们的混合物。
本文所用术语“芳族聚酰胺”是指这样的聚酰胺,其中至少85%的酰胺(-CONH-)连接基直接连接到两个芳族环。添加剂可与所述芳族聚酰胺一起使用。实际上已发现,可将多达10重量%的其他聚合材料与芳族聚酰胺共混,或者可使用共聚物,所述共聚物具有多达10%的替代芳族聚酰胺的二胺的其他二胺,或多达10%的替代芳族聚酰胺的二酰氯的其他二酰氯。对位芳族聚酰胺纤维和这些纤维的各种形式可以商标Kevlar得自E.I.du Pont de Nemours and Company(Wilmington,Delaware),并且可以商标Twaron得自Teijin,Ltd.。可商购获得的用于本发明的聚苯并唑纤维包括ZylonPBO-AS(聚(对亚苯基-2,6-苯并双唑))纤维、ZylonPBO-HM(聚(对亚苯基-2,6-苯并双唑))纤维,这二者均得自Toyobo Co.Inc,Osaka,Japan。可用于本发明的可商购获得的碳纤维包括得自Toho Tenax America,Inc,Rockwood,TN的Tenax纤维。可用于本发明的可商购获得的液晶聚酯纤维包括得自Kuraray America Inc.,(New York,NY)的VectranHS纤维。
本发明的折叠芯结构的非织造片材也可包含与较高模量的纤维共混的较低长度和模量的纤维。在共混物中较低长度纤维的量将基于具体的折叠芯结构所期望的长度而变化。低强度纤维的量越高,折叠芯结构的强度将会越低。在一个优选的实施方案中,较低强度纤维的量应当不超过30%。此类较低强度纤维的实例是间位芳族聚酰胺纤维和聚对苯二甲酰乙二胺纤维。
本发明的折叠芯的非织造片材可包含少量的无机颗粒并且代表性的颗粒包括云母、蛭石等。这些性能增强添加剂的加入旨在向非织造片材和最终的芯结构赋予特性,诸如改善的耐火性、热导率、尺寸稳定性等。
优选的用于本发明的折叠芯的非织造片材的种类是纸材或者湿法成网的非织造材料。但是,也可使用通过其它技术制备的非织造材料,所述技术包括针刺法、粘合剂粘结、热粘结和水刺法。
用来制造本发明的折叠芯的纸材(湿法成网的非织造纸材)可在实验室用筛分仪至商业规模造纸机器范围内的任何规模的设备上形成,包括诸如长网造纸机或斜网造纸机之类的常用机器。典型方法涉及:在含水液体中制造纤维材料和粘合剂的分散体,所述纤维材料例如絮状物和/或纸浆,从分散体中排出液体以获得湿组合物并干燥湿纸组合物。可通过如下方式来制备分散体:分散纤维,然后添加粘合剂;或者分散粘合剂,然后添加纤维。还可通过将纤维分散体与粘合剂分散体合并来制备最终分散体;分散体可任选地包含其他添加剂,例如无机材料。分散体中的纤维浓度按分散体的总重量计可在0.01至1.0重量%的范围内。粘合剂在所述分散体中的浓度按固体的总重量计为最多30重量%。在典型方法中,分散体的含水液体通常为水,但是可包含各种其他物质,例如pH值调节剂、成型助剂、表面活性剂、消泡剂等。含水液体通常以如下方式从分散体中排出:将分散体引导至筛网或其他有孔支撑件上,保留分散的固体,然后使液体流过,从而得到湿纸组合物。湿组合物在支撑件上形成之后,通常通过真空或其他压力进一步脱水,并且通过蒸发剩余液体进一步干燥。
在一个优选实施方案中,可将纤维和聚合物粘合剂一起制浆以形成混合物,该混合物在网筛或网带上转化成纸材。现将参考授予Tokarsky的美国专利4,698,267和4,729,921、授予Hesler等的美国专利5,026,456、授予Kirayoglu的美国专利5,223,094和5,314,742中由各种类型的纤维材料和聚合物粘合剂形成纸材的例证性的方法。
只要形成了纸材,就根据目标的最终密度将其压延至期望的密度或者不将其压延。
在后一种情况下,在成形期间可通过如下方式对密度执行某些调整:最优化网案上的真空和湿压机中的压力。
一般通过将连续的卷绕丝切割成特定长度的段来制备絮状物。如果絮状物的长度小于2毫米,则一般来讲太短而不能形成具有足够强度的纸材;如果絮状物的长度大于25毫米,则非常难以形成均匀的湿法纤网。难以制备具有足够横截面均匀度和可重复生产性的直径小于5微米的絮状物,尤其是直径小于3微米的絮状物。如果絮状物的直径大于20微米,则非常难以形成轻至中等基重的均匀纸材。
如本文所用,术语“纸浆”是指具有杆和一般从其中延伸的纤丝的纤维材料的颗粒,其中杆一般为柱形并且直径为约10至50微米,并且纤丝为一般连接到杆上的细小的、毛发样的构件,所述构件测量的直径仅为一微米的若干分之几或者几微米并且长度为约10至100微米。在美国专利5,084,136中一般性地描述了一种用于制备芳族聚酰胺纸浆的可能的例证性方法。
一种优选的用于本发明的湿法成网的非织造材料的粘合剂类型是纤条体。
如本文所用,术语“纤条体”是指小的薄膜状的基本上为二维颗粒的细分聚合物产品,其具有约100至1000微米的宽度和约0.1至1微米的厚度。通常通过使聚合物溶液流动至与该溶液的溶剂不混容的液体的凝固浴中来制备纤条体。聚合物溶液流在聚合物凝固时经受剧烈剪切力和紊流。
优选的用于本发明纤条体的聚合物包括芳族聚酰胺(聚间苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺)。
美国专利6,913,570 B2和7,115,089 B2以及美国专利申请2007/0141376中描述了用于将纤网坯转换加工为折叠芯结构的方法。
制备折叠芯的方法通常包括以下步骤:a)在未加工的材料纤维网中形成重复的折线图案;b)开始形成折叠;c)进一步形成折叠;d)稳定化处理三维折叠构型。
可在形成折叠芯形态之前或者在芯的折叠完成后在非织造片材上施用树脂浸渍。也可使用两段式浸渍方法,其中在形态形成之前将部分树脂浸渍入非织造片材中并且在形态形成后将余量浸渍。当在形态形成前进行非织造片材的树脂浸渍时,优选树脂是部分固化的。这种部分固化方法(称为B-分段)在复合材料工业中是熟知的。通过B-阶段我们表示在聚合反应中的中间阶段,其中树脂遇热软化并且是塑性的和可溶的,但是其没有完全地溶解或者熔化。B-分段的底物仍能够进行进一步的加工成期望的折叠芯形态。
当在芯为折叠的之后进行树脂浸渍时,通常顺序地进行以下重复的步骤:浸渍、然后移除溶剂并使树脂固化。此类浸渍方法与用于制备蜂窝芯结构的那些相似。优选的最终的芯密度(非织造片材加上树脂)在20至150kg/m3的范围内。在树脂浸渍加工期间,将树脂吸收到非织造片材之中并且涂覆于其上。
根据本发明的折叠芯的最终应用,可使用不同的树脂来涂覆和浸渍非织造片材。此类树脂包括酚醛树脂、环氧树脂、聚酯树脂、聚酰胺树脂、和聚酰亚胺树脂。优选酚醛树脂和聚酰亚胺树脂。酚醛树脂通常符合美国军用规格MIL-R-9299C。也可利用这些树脂的组合。合适的树脂可得自公司诸如Hexion Specialty Chemicals(Columbus,OH)或者Durez Corporation(Detroit,MI)。
以上发明的折叠芯可用于制备复合材料面板,所述面板具有结合到所述折叠芯结构的至少一个外表面上的表面板。所述表面板材料可为塑料片材或板材、纤维增强的塑料(预浸料坯)或金属。在压力并且通常用粘性薄膜加热或者来自预浸料坯中树脂的热将所述表面板连结到芯结构。在压力下、烤箱或者高压釜中进行固化。此类技术为本领域的技术人员所熟知。
测试方法
使用非织造片材的厚度来计算非织造片材的表观密度,所述片材的厚度使用ASTM D645-97在约50kPa的压力下测量并且使用ASTM D646-96测量纸张重量。使用ASTM D1907-07测量纤维的纤度。
非织造片材的Gurley空气阻力(孔隙率)的测定方法为:根据TAPPIT460,使用1.22kPa的差压来测量约6.4平方厘米圆形面积纸材的空气阻力,以秒/100毫升圆柱体位移为单位。
根据ASTM C271-61来确定折叠芯的密度。
根据ASTM C365-57来确定芯的压缩强度和压缩模量。
所述芯的比压缩强度和比压缩模量通过压缩强度和压缩模量的值除以芯的密度来计算。
实施例
实施例1
在常规的纸材成型设备上形成包含81重量%的对位芳族聚酰胺絮凝物和19重量%的间位芳族聚酰胺纤条体的高模量高强度纤维的非织造片材。所述对位芳族聚酰胺为Kevlar49,其具有1.5旦尼尔/长丝(1.7分特/长丝)的标称长丝线密度、6.4mm的切割长度、24克/旦尼尔的韧度和960克/旦尼尔的模量。此类纤维可得自E.I.DuPont de Nemours and Company(Wilmington,DE)。如授予Gross的美国专利3,756,908所述来制备所述间位芳族聚酰胺纤条体。
然后将非织造片材压延从而制备最终片材,所述最终片材具有0.50g/cm3的表观密度、2.5盎司/平方码(85克/平方米)的纸张重量和2秒/100毫升的Gurley孔隙率。所述非织造片材的0.50g/cm3的表观密度定向于在最终的芯中约65重量%的树脂含量,其基于以下公式:
Dp=K×((dr×(100-%r)/%r)/(1+dr/ds×(100-%r)/%r)其中Dp是浸渍前非织造纸片材的表现密度,dr是固化树脂的密度(1.25g/cm3),ds是浸渍前非织造片材中固体材料的密度(1.4g/cm3),%r是基体树脂在最终芯中的重量百分比含量,并且K是值为1.0至1.5的数字。
经压延的非织造片材用甲阶酚醛树脂类的酚醛树脂浸渍,所述酚醛树脂具有35重量%的固体含量和70mPa×秒的粘度,蒸发溶剂(甲醇/Dowanol PM)然后所述树脂部分固化为B-阶段从而制备树脂浸渍的非织造片材(预浸料坯)。然后根据授予Kehrle的美国专利6,913,570,由预浸渍的B-阶段的材料形成折叠芯。制备出了如图1所示的Z字形曲折折叠的图案。所述芯的几何参数为:I1=15.00mm,I3=5.00mm,psi=18度,S=4.20mm,L=10.42mm,高度=29.95mm。通过在180℃下热处理最终的芯1.5小时来将树脂完全地固化。最终的折叠芯结构具有47.9kg/m3的密度和总芯重量68%的树脂含量。比压缩强度为0.0189(N/mm2)/(kg/m3)并且比压缩模量为1.14(N/mm2)/(kg/m3)。主要数据总结于表1中。
比较实施例1
如实施例1形成高模量高强度纤维的非织造片材,但是将其压延至0.85g/cm3的表观密度和2.5盎司/平方码(85克/平方米)的纸张重量。片材的Gurley孔隙率为约5秒。
然后如实施例1将非织造片材转化为折叠芯结构。除了高度为30.13mm之外,该芯的几何参数与实施例1中完全相同。
最终的折叠芯结构具有50.9kg/m3的密度和总芯重量70%的树脂含量。比压缩强度为0.0197(N/mm2)/(kg/m3)并且比压缩模量为0.58(N/mm2)/(kg/m3)。主要数据总结于表1中。
表1
从表1中的总结可以看出,实施例1的折叠芯结构具有根据本发明的表观密度和树脂向非织造片材渗透最优化的非织造片材,其与比较实施例1中由现有技术中有代表性的较高密度的非织造片材制成的折叠芯结构相比,提供了双倍的压缩模量(硬度)。两种芯的压缩强度相似。这证实了对于用于制备折叠芯结构的非织造片材的密度和浸渍入非织造片材的树脂含量两者的优化使得压缩模量显著地改善。
Claims (7)
1.包括多个折叠的棋盘格状构型的芯结构,所述折叠的棋盘格状构型还包含:
(a)非织造片材,所述非织造片材包含具有至少200克/旦尼尔(180克/分特)的模量和至少10克/旦尼尔(9克/分特)的韧度的纤维,其中在用树脂浸渍之前:
(1)所述非织造片材具有由以下公式计算出的表观密度:Dp=K×((dr×(100-%r)/%r)/(1+dr/ds×(100-%r)/%r),其中Dp是所述非织造片材在浸渍前的表观密度,dr是固化树脂的密度,ds是在浸渍前所述非织造片材中固体材料的密度,%r是在最终的芯结构中固化树脂的重量百分比含量,K是值为1.0至1.5的数字;
(2)所述非织造片材具有不大于30秒/100毫升的Gurley孔隙率;和
(b)固化树脂,所述固化树脂的量使得固化树脂的重量百分比为固化树脂和非织造片材的合并重量的至少50%。
2.权利要求1的芯结构,其中所述非织造片材包含70-100重量%的纤维和0-30重量%的粘合剂。
3.权利要求2的芯结构,其中所述非织造片材为湿法成网的非织造片材。
4.权利要求2的芯结构,其中所述粘合剂包含间位芳族聚酰胺纤条体。
5.权利要求2的芯结构,其中所述纤维包含对位芳族聚酰胺纤维。
6.复合材料面板,所述复合材料面板包括根据前述任一项权利要求所述的芯结构和至少一个连接到所述芯结构的至少一个外表面的表面板。
7.根据权利要求6的结构面板,其中所述表面板由树脂浸渍的纤维、塑料或金属制成。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18962008P | 2008-08-21 | 2008-08-21 | |
US61/189620 | 2008-08-21 | ||
PCT/US2009/054581 WO2010022311A1 (en) | 2008-08-21 | 2009-08-21 | Folded core having a high compression modulus and articles made from the same |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102131636A true CN102131636A (zh) | 2011-07-20 |
Family
ID=41217776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2009801326655A Pending CN102131636A (zh) | 2008-08-21 | 2009-08-21 | 具有高压缩模量的折叠芯和由其制成的制品 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20100048078A1 (zh) |
EP (1) | EP2318204B1 (zh) |
JP (1) | JP2012500864A (zh) |
KR (1) | KR20110044915A (zh) |
CN (1) | CN102131636A (zh) |
CA (1) | CA2730906C (zh) |
MX (1) | MX2011001843A (zh) |
WO (1) | WO2010022311A1 (zh) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130157001A1 (en) | 2011-12-19 | 2013-06-20 | E I Du Pont De Nemours And Company | Structural core |
US20130183484A1 (en) | 2012-01-12 | 2013-07-18 | E I Du Pont De Nemours And Company | Core structures comprising tannin resin |
US9434142B2 (en) | 2012-01-26 | 2016-09-06 | E I Du Pont De Nemours And Company | Method of making a sandwich panel |
US20140113104A1 (en) | 2012-02-23 | 2014-04-24 | E I Du Pont De Nemours And Company | Fiber-resin composite sheet and article comprising the same |
US20150190981A1 (en) | 2014-01-08 | 2015-07-09 | E I Du Pont De Nemours And Company | Metallic core having a high compression strength and articles made from same |
EP3546210A1 (en) * | 2018-03-27 | 2019-10-02 | COGEBI société anonyme | Mica based three dimensional structures |
JPWO2021106650A1 (zh) | 2019-11-29 | 2021-06-03 | ||
US11926088B2 (en) | 2019-11-29 | 2024-03-12 | Toray Industries, Inc. | Prepreg, preform, fiber-reinforced composite material, and method for producing said prepreg, said preform or said fiber-reinforced composite material |
EP4067034A4 (en) | 2019-11-29 | 2023-12-27 | Toray Industries, Inc. | FIBER REINFORCED COMPOSITE MATERIAL AND SANDWICH STRUCTURE |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5137768A (en) * | 1990-07-16 | 1992-08-11 | E. I. Du Pont De Nemours And Company | High shear modulus aramid honeycomb |
CN1436121A (zh) * | 2000-06-16 | 2003-08-13 | 纳幕尔杜邦公司 | 蜂窝结构 |
US20080145601A1 (en) * | 2006-12-15 | 2008-06-19 | Levit Mikhail R | Honeycomb from controlled porosity paper |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5026456A (en) * | 1990-06-14 | 1991-06-25 | E. I. Du Pont De Nemours And Company | Aramid papers containing aramid paper pulp |
DE19913830A1 (de) * | 1999-03-26 | 2000-09-28 | Jochen Pflug | Faltwabe aus Wellpappe, Verfahren und Vorrichtung zu deren Herstellung |
JP3321141B2 (ja) * | 2000-04-03 | 2002-09-03 | 昭和飛行機工業株式会社 | アラミドハニカムおよびその製造方法 |
JP2004123983A (ja) * | 2002-10-04 | 2004-04-22 | Toyobo Co Ltd | 成形材料ならび成形物とその製法 |
DE10252941B4 (de) * | 2002-11-14 | 2009-09-10 | Airbus Deutschland Gmbh | Verfahren zur Herstellung einer Kernstruktur für einen Kernverbund |
EP1963567B1 (en) * | 2005-12-21 | 2010-10-27 | E.I. Du Pont De Nemours And Company | Pipd paper and components made therefrom |
US8025949B2 (en) * | 2006-12-15 | 2011-09-27 | E.I. Du Pont De Nemours And Company | Honeycomb containing poly(paraphenylene terephthalamide) paper with aliphatic polyamide binder and articles made therefrom |
US20080286522A1 (en) * | 2006-12-15 | 2008-11-20 | Subhotosh Khan | Honeycomb having a low coefficient of thermal expansion and articles made from same |
US20100047515A1 (en) * | 2008-08-21 | 2010-02-25 | E. I. Du Pont De Nemours And Company | Honeycomb Core Having a High Compression Strength and Articles Made from the Same |
-
2009
- 2009-08-18 US US12/542,766 patent/US20100048078A1/en not_active Abandoned
- 2009-08-21 MX MX2011001843A patent/MX2011001843A/es active IP Right Grant
- 2009-08-21 WO PCT/US2009/054581 patent/WO2010022311A1/en active Application Filing
- 2009-08-21 CA CA2730906A patent/CA2730906C/en active Active
- 2009-08-21 JP JP2011524021A patent/JP2012500864A/ja active Pending
- 2009-08-21 EP EP20090791775 patent/EP2318204B1/en active Active
- 2009-08-21 CN CN2009801326655A patent/CN102131636A/zh active Pending
- 2009-08-21 KR KR1020117006254A patent/KR20110044915A/ko not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5137768A (en) * | 1990-07-16 | 1992-08-11 | E. I. Du Pont De Nemours And Company | High shear modulus aramid honeycomb |
CN1436121A (zh) * | 2000-06-16 | 2003-08-13 | 纳幕尔杜邦公司 | 蜂窝结构 |
US20080145601A1 (en) * | 2006-12-15 | 2008-06-19 | Levit Mikhail R | Honeycomb from controlled porosity paper |
Also Published As
Publication number | Publication date |
---|---|
JP2012500864A (ja) | 2012-01-12 |
CA2730906C (en) | 2016-07-12 |
MX2011001843A (es) | 2011-03-29 |
US20100048078A1 (en) | 2010-02-25 |
EP2318204B1 (en) | 2013-10-02 |
KR20110044915A (ko) | 2011-05-02 |
EP2318204A1 (en) | 2011-05-11 |
WO2010022311A1 (en) | 2010-02-25 |
CA2730906A1 (en) | 2010-02-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102131636A (zh) | 具有高压缩模量的折叠芯和由其制成的制品 | |
CA2561329C (en) | Aramid paper blend | |
CN101965425A (zh) | 具有高剪切强度的芯及由其制成的制品 | |
CN102123855A (zh) | 具有高压缩强度的蜂窝芯和由其制成的制品 | |
CN102666084A (zh) | 基于碳纤维纸的蜂窝芯以及由蜂窝芯制成的制品 | |
JP6120415B2 (ja) | 構造コア | |
EP2501856B1 (en) | Folded core based on carbon fiber paper and articles made from same | |
CA2669979C (en) | Honeycomb containing poly(paraphenylene terephthalamide) paper with aliphatic polyamide binder and articles made therefrom | |
EP2802710B1 (en) | Core structures comprising tannin resin | |
CN106794653B (zh) | 具有高压缩强度的蜂窝结构芯 | |
EP1963567B1 (en) | Pipd paper and components made therefrom | |
US20110244175A1 (en) | Honeycomb Core Having a High Compression Strength and Articles Made from the Same | |
US20110244193A1 (en) | Folded Core Having a High Compression Modulus and Articles Made from the Same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110720 |