CN113366165B - 氧化石墨烯接枝的pbo纤维及其生产方法，和在飞艇艇身和轻于空气的航空器中的应用 - Google Patents
氧化石墨烯接枝的pbo纤维及其生产方法，和在飞艇艇身和轻于空气的航空器中的应用 Download PDFInfo
- Publication number
- CN113366165B CN113366165B CN201980077682.7A CN201980077682A CN113366165B CN 113366165 B CN113366165 B CN 113366165B CN 201980077682 A CN201980077682 A CN 201980077682A CN 113366165 B CN113366165 B CN 113366165B
- Authority
- CN
- China
- Prior art keywords
- pbo
- graphene oxide
- glutaraldehyde
- resorcinol
- coating
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000000576 coating method Methods 0.000 claims abstract description 46
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012783 reinforcing fiber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 7
- 239000005437 stratosphere Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001782 photodegradation Methods 0.000 description 5
- 230000006750 UV protection Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64B—LIGHTER-THAN AIR AIRCRAFT
- B64B1/00—Lighter-than-air aircraft
- B64B1/58—Arrangements or construction of gas-bags; Filling arrangements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Aviation & Aerospace Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
在对紫外线引起的降解具有增强抗性的PBO纤维的生产方法中，在PBO纤维上提供涂层，其中该涂层包括通过与戊二醛和间苯二酚聚合而交联的氧化石墨烯。该纤维对轻于空气的航空器有用。
Description
技术领域
本发明涉及PBO
纤维上的氧化石墨烯涂层；生产这种涂覆的纤维的方法，具有这种涂层的PBO纤维，具有这种纤维的飞艇艇身以及具有包含这种纤维的机身的轻于空气的航空器。
背景技术
这种材料相对于重量具有优异的强度，已经提议将其作为飞艇材料，例如，Maekawa和 Yoshino在2008年9-10月刊发的《Journal of Aircraft》第45卷第5期上发表的文章《高性能飞艇蒙皮材料的撕裂扩展》中。如本文所报导，PBO用于以PBO为底布的层压板中。
与其他市售高性能纤维相比，PBO除了具有较高的比强度外，还具有较高的抗蠕变性，因此特别适用于飞艇轻质高强度层压板材料中的纤维增强。Zhai和Euler在美国航空航天学会于2005年9月26日至28日在弗吉尼亚州阿灵顿召开的AIAA第五届航空、技术、集成和运营会议(ATIO)上发表的文章《高空应用中的轻于空气航空系统的材料挑战》一文中对此进行了讨论。
然而，还已知PBO非常容易受到原子氧的降解，因此当用作平流层中高空飞艇的材料，必须暴露于原子氧中时，要对其加以保护。Chen等人于2015年1月16日发表在《复合材料科学与技术》的第106卷第32-38页的文章《硅烷和氧化石墨烯在PBO纤维上的接枝：同时具有改善的界面和耐原子氧性能的纤维/聚合物基复合材料的多功能界面》中对此进行了讨论，这可在以下网页http://www.sciencedirect.com/science/article/pii/S0266353814003832上找到。在本文中，在PBO纤维和包含GO和硅烷的涂层之间使用APTMS进行桥接。其记载有“PBO– APTMS–GO同时显示出界面剪切强度(IFSS)和AO耐腐蚀性显着增强。”这些作者还提交了中国专利申请CN103820996，公开了使用氢化铝锂-乙醚处理PBO纤维对PBO纤维进行羟基官能化处理。CN105908489中还公开了在PBO上的石墨烯纳米带涂层。
PBO的另一个缺点是快速光降解，不仅受紫外线降解，而且受可见光降解。已经发现水分和氧气的存在会加速光降解。在日本东洋纺公司的技术信息手册(于2005年6月修订)中，被称为“专业纤维
”，可以从因特网上获得，网址为：http://www.toyobo- global.com/seihin/kc/pbo/zylon-p/bussei-p/technical.pdf，记载有耐光性是用氙灯耐气候欧姆计评估的。在暴露的初始阶段，材料强度急剧下降，并且比对照研究中的聚芳酰胺纤维的下降幅度更大。实验结果表明，暴露于日光下6个月后的残余强度约为35％，因此得出结论，户外使用PBO必须用覆盖材料保护。
由于这些原因，尽管在高强度和低蠕变方面具有明显的优势，但是当这种纤维材料用于处于光强度高且化学反应性高的环境中的平流层飞艇时面临着其他挑战。期望提供一种使 PBO更能抵抗平流层中的光降解和反应性气体的方法，以便将其用于高空飞艇的艇身。
对于飞艇，在US9598165中提出了氟化氧化石墨烯用于提高气密性，这是飞艇的另一重要方面。在EP2719219中，也关注了各种热塑性纤维的石墨烯涂层的气密性。然而，尽管在气密性和抗原子氧性方面具有优势，但是在CN102173145B中报道了氧化石墨烯具有良好的透明性，这使其不能成为保护PBO免受光降解的良好候选者。因此，为了对纤维进行紫外防护，CN105088793提出了将氧化锌与氧化的石墨烯混合。CN106087396提出了将氧化石墨烯浆料烘烤到聚磺酰胺纤维上，以具有良好的机械性能和良好的抗紫外线性能。对于聚芳酰胺纤维，通过对纤维进行多巴胺改性并结合石墨烯涂层获得了抗紫外线性。
发明内容
因此，本发明的目的是提供本领域的改进。特别地，目的是提高PBO纤维的耐光性。更具体地说，目的是提供一种用于高空飞艇的艇身材料。该目的通过以下提出的方法和产品来实现。
发明人已经发现，PBO上简单涂一层氧化石墨烯GO不能充分或令人满意地保护PBO免受光、紫外线以及臭氧的降解。更近的研究表明，不仅表面涂层不均匀，而且涂层中有开口都会使光穿透到纤维中并使之降解。此外，似乎仅具有GO的涂层不能提供足够的光防护。考虑到上述CN102173145B中关于尽管具有GO涂层却具有良好的透明性，这就不足为奇了。然而，发明人发现，在PBO的涂覆之前或期间，GO与复杂分子的明显的交联增加了对光和紫外降解的保护。
令人惊讶的是，为GO的3D结构研发的方法似乎非常适合于这种交联以及涂覆过程。 Sudeep(发明人之一)等人2013年发表在《ACS Nano》第7卷第8期7034-7040页的文章《共价互连的三维氧化石墨烯固体》中公开了一种GO的3D涂覆方法，其通过引用并入本文。该文章可在因特网上找到，网址为http://pubs.acs.org/doi/ipdf/10.1021/nn402272u。
通过使氧化石墨烯GO与戊二醛GAD簇和间苯二酚Res簇交联，在PBO表面上形成了三维结构。所得的涂层适当地附着在其他惰性的PBO表面上，并且具有均匀的厚度，该厚度足够厚以保护PBO免于降解。
需要指出的是，使用戊二醛代替甲醛具有更好的性能。此外，甲醛的毒性使该物质没有吸引力，因为通常的生产设施不可使用这种有毒物质。
已经发现，涂层的干燥环境导致更好的附着性和稳定性。据信GO具有将水分掺入涂层或纤维表面中的趋势，这导致涂层质量较低。这是一个令人惊讶的发现，因为水分倾向于改善GO的稳定性。干燥的生产环境对PBO材料本身也有益，因为它对水分敏感。水分对PBO的影响不仅是生产设备需要注意的一个因素，还是涂层材料应用于飞艇时需要注意的一个因素，因为只要飞艇不在平流层中，就会暴露于大气中的湿气中。例如，在涂覆期间，环境中的湿度为1kg空气中小于2g水蒸气，例如小于1g/kg或者甚至小于0.5g/kg。它与平流层形成对比，在平流层中，空气通常是每千克空气包含0.3克水蒸气。
通过以下阐述的方法和产品实现了上述目的。
一种对紫外线和臭氧引起的降解具有增强抗性的PBO纤维的生产方法，该方法包括在 PBO纤维上提供涂层，该涂层包括通过与戊二醛和间苯二酚聚合而交联的氧化石墨烯。
一种用于减少PBO纤维的光降解的方法，其中在所述PBO纤维上施加涂层，所述涂层包括通过与戊二醛和间苯二酚聚合而交联的氧化石墨烯。
一种涂覆有与戊二醛和间苯二酚交联的氧化石墨烯的PBO纤维。
一种包括增强纤维层的层压材料，该增强纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
一种飞艇艇身，包括纤维层，所述纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
一种轻于空气的航空器，包括机身，该机身包括作为气体屏障和承重结构的层压材料，该层压材料包括增强纤维层，该增强纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
涂覆有与戊二醛和间苯二酚交联的氧化石墨烯的PBO纤维的应用，用于减少由暴露于光、紫外线或臭氧辐射或化学反应引起的PBO纤维降解。
附图说明
将参考附图更详细地解释本发明，其中
图1示出了GO的间苯二酚和戊二醛(Res-GAD)交联和PBO纤维的改性；
图2示出了各种PBO纤维涂层的
单丝的强度测量值与紫外线暴露时间的关系；
图3示出了各种PBO纤维涂层的
单丝的以百分率计算的强度保持率与紫外线暴露时间的关系；
图4示出了所测量的PBO
单丝的阻力实验值与紫外线暴露时间的关系，以牛顿为单位；
图5示出了图4的实验值，其中高强度暴露时间已换算为平流层中紫外线暴露的估计时间；
图6说明了PBO
单丝的强度与臭氧暴露时间的关系；
图7示出了PBO
单丝的以百分率计算的强度保持率与臭氧暴露时间的关系。
具体实施方式
图1示出了氧化石墨烯GO与戊二醛GAD簇和间苯二酚Res簇的交联。在PBO纤维上进行涂覆处理的涂覆过程之前或期间，交联产生三维结构。
GO和交联GO的合成也按照发明人之一Sudeep等人2013年发表在ACS Nano第7卷第8期7034-7040页上的文章《共价互连的三维氧化石墨烯固体》中所述的进行，这可在因特网上找到，网址为http://pubs.acs.org/doi/ipdf/10.1021/nn402272u。
GO的合成。氧化石墨烯的合成如下。将浓H2SO4/H3PO4的9∶1混合物(360∶40mL) 加入到石墨薄片(3.0g，1wt当量)和KMnO4(18.0g，6wt当量)的混合物中。然后将反应物加热至50℃并搅拌12h。将反应冷却至室温，并倾倒在含30％H2O2(3mL)的冰上。然后将材料依次用200mL水、200mL 30％HCl和200mL乙醇(2次)洗涤。用200mL乙醚使该多次洗涤处理后残留的材料凝结，将所得的悬浮液在0.22μm孔径的PTFE膜上过滤。
GO的交联。将干燥的GO分散在去离子水(5mg/mL)中，并用间苯二酚(11mM)和戊二醛溶液(22mM)处理。将所得的粘性液体状材料和溶液超声处理3小时。
对于实验中使用的PBO纤维，购买了
复丝，并从中取出单丝用于涂层。这些细丝的直径为12μm。
在第一个实验中，通过将细丝浸入溶液中，然后干燥细丝，将材料涂覆到PBO单丝中。对于大规模生产，喷涂似乎是一种更可行的方法。
对于紫外线辐射，使用了Dinies公司的设备，请参阅 http://shop.dinies.com/product_info.php？info＝p96_uv-chamber-m1.html，即装有长波紫外线辐射源的紫外线室M1，提供365nm的长波紫外线光，辐射面积为195x190mm。纤维所在位置的 365nm长波紫外线辐射强度为1900W/m2。
图2示出了各种PBO涂层的强度测量值与紫外线暴露时间的关系。
实验使用了四种状态的PBO单丝。四个曲线中的最低曲线与原始(未涂覆的)PBO纤维有关。将测得的数据与日本东洋纺公司的类似数据进行了比较，并发现数据之间具有一致性，这证明了结果是可靠的。
具有交联的GO的涂层显着改善了PBO纤维的抗紫外线性。通过重复涂覆5到30次，可以实现进一步的改进。重复涂覆实现的改进不仅是由于涂层较厚，而且还由于后续层覆盖了一层中的缺陷，从而使涂层更均匀，并由此获得了更好的保护。
在与原始PBO纤维达到相同的强度降低时，涂覆的PBO纤维的暴露时间要长约100倍。暴露300小时后，涂覆的PBO纤维的强度约为原始纤维强度的两倍。
图3示出了各种纤维状态以百分率计算的强度保持率与紫外线暴露时间的关系。观察到涂覆有交联的GO的PBO单丝的强度保持率最高。多层涂层比单一涂层具有更显着的效果。
图4示出了直到断裂所必须施加的力，以牛顿为单位。对于涂覆有交联GO的PBO单丝，该力是原始的2到3倍高，这取决于涂层的数量。
图5示出了时间线上的实验值，其中以小时计的暴露时间被转换为平流层中预期的估计暴露时间。在很大程度上，用灯暴露10小时相当于在平流层中暴露一周。观察到，对于单丝， 30层的涂层在33周后保持稳定，使得其可以承受相对于其出厂状态大约三分之一的力，并且优于原始的PBO三倍以上。
图6示出了各种PBO涂层的强度测量值与臭氧暴露时间的关系。暴露期间的臭氧浓度为 18ppm。这项研究表明，臭氧暴露对PBO单丝的强度降低具有显着影响。涂覆有交联GO的改性单丝具有增强的屏蔽效果，使得在臭氧暴露100小时后，其强度高于原始PBO单丝的三倍。
图7示出了当暴露于18ppm的臭氧时，原始的单丝和涂覆有交联的GO的单丝的强度保持率，以百分率计算。它表明，在暴露于臭氧100小时后，涂覆有交联GO的PBO单丝的强度保持率是原始单丝的三倍。
进行单丝实验是为了具有明确光滑的表面。但是，据信涂覆的PBO复丝，例如
复丝纤维的结果会更好，因为涂层会更好地粘附在表面上，而该表面较不光滑。此外，一个位置上的一根细丝的潜在弱点可以通过在该位置上其他细丝的强度来补偿，这样一束细丝中变弱的细丝的断裂风险就比实验中的单丝断裂的风险更低。
Claims (8)
1.一种对紫外线引起的降解具有增强抗性的PBO纤维的生产方法，所述方法包括在所述PBO纤维上提供涂层，所述涂层包括通过与戊二醛和间苯二酚聚合而交联的氧化石墨烯。
2.根据权利要求1所述的方法，其中所述涂层包括分散在去离子水中且用mM比为1：2的间苯二酚和戊二醛进行处理的GO。
3.根据权利要求2所述的方法，其中所述涂层包括分散在去离子水中且用包含11mM的间苯二酚和22mM的戊二醛的溶液进行处理的GO。
4.一种涂覆有与戊二醛和间苯二酚交联的氧化石墨烯的PBO纤维。
5.一种层压材料，包括增强纤维层，所述增强纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
6.一种飞艇艇身，包括纤维层，所述纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
7.一种轻于空气的航空器，包括机身，所述机身包括作为气体屏障和承重结构的层压材料，所述层压材料包括增强纤维层，所述增强纤维层包括PBO纤维，所述PBO纤维涂覆有与戊二醛和间苯二酚交联的氧化石墨烯。
8.涂覆有与戊二醛和间苯二酚交联的氧化石墨烯的PBO纤维的应用，用于减少由暴露于光、紫外线辐射或化学反应引起的PBO纤维降解。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201862771224P | 2018-11-26 | 2018-11-26 | |
| US62/771,224 | 2018-11-26 | ||
| PCT/EP2019/082458 WO2020109247A1 (en) | 2018-11-26 | 2019-11-25 | Graphene-oxide grafted pbo (zylon®) fibers; method for production and applications to airship hulls and lighter than air vehicles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113366165A CN113366165A (zh) | 2021-09-07 |
| CN113366165B true CN113366165B (zh) | 2022-12-30 |
Family
ID=68731967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980077682.7A Active CN113366165B (zh) | 2018-11-26 | 2019-11-25 | 氧化石墨烯接枝的pbo纤维及其生产方法，和在飞艇艇身和轻于空气的航空器中的应用 |
Country Status (29)
| Country | Link |
|---|---|
| US (1) | US11958584B2 (zh) |
| EP (1) | EP3887594B1 (zh) |
| JP (1) | JP7371095B2 (zh) |
| KR (1) | KR102740797B1 (zh) |
| CN (1) | CN113366165B (zh) |
| AU (1) | AU2019387317B2 (zh) |
| CA (1) | CA3120921C (zh) |
| CL (1) | CL2021001376A1 (zh) |
| DK (1) | DK3887594T3 (zh) |
| EA (1) | EA202191344A1 (zh) |
| ES (1) | ES2941649T3 (zh) |
| FI (1) | FI3887594T3 (zh) |
| HR (1) | HRP20230316T1 (zh) |
| HU (1) | HUE061397T2 (zh) |
| IL (1) | IL283370B2 (zh) |
| LT (1) | LT3887594T (zh) |
| MA (1) | MA54280B1 (zh) |
| MD (1) | MD3887594T2 (zh) |
| MX (1) | MX2021006143A (zh) |
| PE (1) | PE20212255A1 (zh) |
| PH (1) | PH12021551209B1 (zh) |
| PL (1) | PL3887594T3 (zh) |
| PT (1) | PT3887594T (zh) |
| RS (1) | RS64092B1 (zh) |
| SG (1) | SG11202105450UA (zh) |
| SI (1) | SI3887594T1 (zh) |
| UA (1) | UA128735C2 (zh) |
| WO (1) | WO2020109247A1 (zh) |
| ZA (1) | ZA202104084B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (zh) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | 石墨烯/pbo复合纤维的制备方法 |
| KR20150049403A (ko) * | 2013-10-30 | 2015-05-08 | 금오공과대학교 산학협력단 | Pbo섬유의 uv저항성 향상을 위한 표면처리방법 |
| CN105908489A (zh) * | 2016-05-12 | 2016-08-31 | 哈尔滨工业大学 | 一种石墨烯纳米带界面改性pbo纤维及其制备方法 |
| CN106012492A (zh) * | 2016-05-30 | 2016-10-12 | 哈尔滨工业大学 | 一种双官能超支化硅氧烷改善pbo纤维抗紫外性能的方法 |
| KR101734895B1 (ko) * | 2015-12-11 | 2017-05-12 | 금오공과대학교 산학협력단 | 개질된 폴리헤드랄 올리고머릭 실세스퀴옥산(poss)를 이용한 자외선 저항성 및 압축강도가 향상된 폴리파라페닐렌벤조비스옥사졸 나노복합체섬유 및 이의 제조방법 |
| CN108486861A (zh) * | 2018-04-25 | 2018-09-04 | 浙江梵彼斯特轻纺发展有限公司 | 一种抗紫外老化pbo纤维的制备工艺 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120097194A1 (en) * | 2002-09-09 | 2012-04-26 | Reactive Surfaces, Ltd. | Polymeric Coatings Incorporating Bioactive Enzymes for Catalytic Function |
| CN102173145B (zh) | 2011-01-06 | 2013-03-13 | 西安理工大学 | 一种氧化石墨烯涂覆膜的制备方法 |
| US8867467B2 (en) | 2011-06-08 | 2014-10-21 | Marvell World Trade Ltd | Efficient transmission for low data rate WLAN |
| US9598165B2 (en) | 2012-10-08 | 2017-03-21 | Lockheed Martin Corporation | Gas barrier material with atomic sheet |
| CN103820996B (zh) | 2014-03-04 | 2016-02-17 | 哈尔滨工业大学 | 一种二元接枝改性pbo纤维的制备方法 |
| CN105088793A (zh) | 2015-08-25 | 2015-11-25 | 无锡市长安曙光手套厂 | 一种无纺布、其制备方法及其应用 |
| CN106087396B (zh) | 2016-06-07 | 2018-11-23 | 上海工程技术大学 | 一种石墨烯/聚砜酰胺复合织物及其制备方法 |
| UA124471C2 (uk) | 2016-10-24 | 2021-09-22 | Сей Са | Літальний апарат з корпусом, шаруватий матеріал для такого корпусу і спосіб виробництва такого шаруватого матеріалу |
| WO2018111568A2 (en) | 2016-12-14 | 2018-06-21 | Board Of Regents, The University Of Texas System | Maleated polymer-graphene oxide composite elastomer and article containing a composite elastomer |
| CN107794749B (zh) | 2017-10-27 | 2020-05-12 | 杭州高烯科技有限公司 | 一种石墨烯增强的对位芳香族聚酰胺纤维束及其制备方法 |
| EP4086225A1 (en) * | 2021-05-04 | 2022-11-09 | Consejo Superior de Investigaciones Científicas (CSIC) | 3d graphene aerogels |
| CN113293614B (zh) * | 2021-05-28 | 2023-01-24 | 成都新晨新材科技有限公司 | 一种耐紫外老化性能的pbo纤维上浆剂、pbo纤维及其制备方法 |
-
2019
- 2019-11-25 MD MDE20210947T patent/MD3887594T2/ro unknown
- 2019-11-25 SG SG11202105450UA patent/SG11202105450UA/en unknown
- 2019-11-25 RS RS20230249A patent/RS64092B1/sr unknown
- 2019-11-25 JP JP2021529458A patent/JP7371095B2/ja active Active
- 2019-11-25 PE PE2021000767A patent/PE20212255A1/es unknown
- 2019-11-25 ES ES19812733T patent/ES2941649T3/es active Active
- 2019-11-25 MX MX2021006143A patent/MX2021006143A/es unknown
- 2019-11-25 EP EP19812733.4A patent/EP3887594B1/en active Active
- 2019-11-25 CN CN201980077682.7A patent/CN113366165B/zh active Active
- 2019-11-25 HU HUE19812733A patent/HUE061397T2/hu unknown
- 2019-11-25 DK DK19812733.4T patent/DK3887594T3/da active
- 2019-11-25 LT LTEPPCT/EP2019/082458T patent/LT3887594T/lt unknown
- 2019-11-25 FI FIEP19812733.4T patent/FI3887594T3/fi active
- 2019-11-25 PH PH1/2021/551209A patent/PH12021551209B1/en unknown
- 2019-11-25 PT PT198127334T patent/PT3887594T/pt unknown
- 2019-11-25 WO PCT/EP2019/082458 patent/WO2020109247A1/en unknown
- 2019-11-25 PL PL19812733.4T patent/PL3887594T3/pl unknown
- 2019-11-25 KR KR1020217019771A patent/KR102740797B1/ko active Active
- 2019-11-25 UA UAA202103231A patent/UA128735C2/uk unknown
- 2019-11-25 AU AU2019387317A patent/AU2019387317B2/en active Active
- 2019-11-25 CA CA3120921A patent/CA3120921C/en active Active
- 2019-11-25 HR HRP20230316TT patent/HRP20230316T1/hr unknown
- 2019-11-25 MA MA54280A patent/MA54280B1/fr unknown
- 2019-11-25 SI SI201930483T patent/SI3887594T1/sl unknown
- 2019-11-25 US US17/297,023 patent/US11958584B2/en active Active
- 2019-11-25 EA EA202191344A patent/EA202191344A1/ru unknown
-
2021
- 2021-05-23 IL IL283370A patent/IL283370B2/en unknown
- 2021-05-26 CL CL2021001376A patent/CL2021001376A1/es unknown
- 2021-06-14 ZA ZA2021/04084A patent/ZA202104084B/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (zh) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | 石墨烯/pbo复合纤维的制备方法 |
| KR20150049403A (ko) * | 2013-10-30 | 2015-05-08 | 금오공과대학교 산학협력단 | Pbo섬유의 uv저항성 향상을 위한 표면처리방법 |
| KR101734895B1 (ko) * | 2015-12-11 | 2017-05-12 | 금오공과대학교 산학협력단 | 개질된 폴리헤드랄 올리고머릭 실세스퀴옥산(poss)를 이용한 자외선 저항성 및 압축강도가 향상된 폴리파라페닐렌벤조비스옥사졸 나노복합체섬유 및 이의 제조방법 |
| CN105908489A (zh) * | 2016-05-12 | 2016-08-31 | 哈尔滨工业大学 | 一种石墨烯纳米带界面改性pbo纤维及其制备方法 |
| CN106012492A (zh) * | 2016-05-30 | 2016-10-12 | 哈尔滨工业大学 | 一种双官能超支化硅氧烷改善pbo纤维抗紫外性能的方法 |
| CN108486861A (zh) * | 2018-04-25 | 2018-09-04 | 浙江梵彼斯特轻纺发展有限公司 | 一种抗紫外老化pbo纤维的制备工艺 |
Non-Patent Citations (1)
| Title |
|---|
| "Covalently Interconnected Three-Dimensional Graphene Oxide Solids";Parambath M. Sudeep等;《ACS NANO》;20130827;第7卷(第8期);第7034-7040页 * |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Titanium dioxide nanoparticles-coated aramid fiber showing enhanced interfacial strength and UV resistance properties | |
| Venkataraman et al. | Aerogels for thermal insulation in high-performance textiles | |
| Zhang et al. | Facile preparation of hyperbranched polysiloxane-grafted aramid fibers with simultaneously improved UV resistance, surface activity, and thermal and mechanical properties | |
| CN107901539B (zh) | 复合体 | |
| Seghini et al. | Effects of oxygen and tetravinylsilane plasma treatments on mechanical and interfacial properties of flax yarns in thermoset matrix composites | |
| US3853657A (en) | Bonding of poly(ethylene terephthalate) induced by low-temperature plasmas | |
| CN113366165B (zh) | 氧化石墨烯接枝的pbo纤维及其生产方法，和在飞艇艇身和轻于空气的航空器中的应用 | |
| Hemvichian et al. | Enhancing compatibility between poly (lactic acid) and thermoplastic starch using admicellar polymerization | |
| KR101429802B1 (ko) | 통기성 복합 시트의 제조 방법 | |
| Hettiarachchi et al. | Synthesis of calcium carbonate microcapsules as self-healing containers | |
| DK180274B1 (en) | Graphene oxide-coated PBO fibers (Zylon®) fibers; method of production and use on airship hooks and lighter-than-air vessels. | |
| EA041395B1 (ru) | Привитые оксидом графена волокна пбо (zylon®), способ производства и применения для корпусов летательных аппаратов и транспортных средств легче воздуха | |
| CN105239400A (zh) | 一种玄武岩纤维内墙保温网格布 | |
| US10479726B2 (en) | Fibersizing with small amounts of nanomaterials | |
| BR112021010103B1 (pt) | Método para produzir uma fibra de pbo, fibra de pbo, material laminado, casco de dirigível, veículo mais leve que o ar, e, uso de fibras de pbo | |
| JPH11315470A (ja) | 炭素繊維織物の製造法 | |
| JP6442268B2 (ja) | 透明不燃性シートとその製造方法 | |
| CN111519465A (zh) | 一种抗静电防油耐高温的特殊离型纸及其制备方法 | |
| JP2019502033A (ja) | 積層された金属化テキスタイル層を含む物品、特に太陽光防護用物品、および前記物品を得るために金属層をグラフトする方法 | |
| Diblíková et al. | Properties of functional epoxy coatings modified by carbon nanoparticles | |
| EP0860405B1 (de) | Wetterfester, nicht brennbarer Stoff und Verfahren zu dessen Herstellung | |
| JPS6030336A (ja) | 複合材料 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Hurenburg, Zug, Switzerland Applicant after: Sceye AG Address before: Lausanne Applicant before: Sceye AG |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Swiss Chu Gezhou Applicant after: Sceye AG Address before: Hurenburg, Zug, Switzerland Applicant before: Sceye AG |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |