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Keywords = poly(p-phenylene terephthalamide)

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15 pages, 6972 KiB  
Article
Preparation of Mechanically Strong Aramid Nanofiber Gel Film with Surprising Entanglements and Orientation Structure Through Aprotic Donor Solvent Exchange
by Zeyu Chen, Chuying Yu and Wenbin Zhong
Materials 2025, 18(5), 1142; https://doi.org/10.3390/ma18051142 - 4 Mar 2025
Viewed by 907
Abstract
Aramid nanofiber (ANF), a nanoscale building block with a prominently complex structure, can be prepared by splitting poly(p-phenylene terephthalamide) (PPTA) fibers into negatively charged ANFs in a deprotonating manner in a DMSO/KOH solvent system, followed by a subsequent re-protonation process using a proton-donor [...] Read more.
Aramid nanofiber (ANF), a nanoscale building block with a prominently complex structure, can be prepared by splitting poly(p-phenylene terephthalamide) (PPTA) fibers into negatively charged ANFs in a deprotonating manner in a DMSO/KOH solvent system, followed by a subsequent re-protonation process using a proton-donor reagent. There are rare reports regarding the utilization of an aprotic donor reagent to convert deprotonated ANF dispersion into film or gel with a controllable structure and high mechanical properties. In this work, dichloromethane, as an anhydrous aprotic donor solvent, has been introduced into the deprotonated ANF dispersion to replace DMSO, containing PPTA molecules and hydroxyl ions, leading to the gelation of deprotonated ANF dispersions, forming a film (ANFDCM) possessing a surprisingly highly entangled and oriented structure, as proven by SEM results. Due to the attenuation of electrostatic repulsion in the dispersion, partially deprotonated ANFs intertwined and cross-linked through π–π conjugation among a large number of benzene rings in PPTA molecules. After treating ANFDCM with water for re-protonation, the as-prepared film (ANFDCM-W) exhibited high tensile strength (307.7 MPa) and toughness (74.7 MJ m−3). Full article
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11 pages, 3194 KiB  
Article
Creation of Polymer Hydrogelator/Poly(Vinyl Alcohol) Composite Molecular Hydrogel Materials
by Yutaka Ohsedo and Wakana Ueno
Gels 2023, 9(9), 679; https://doi.org/10.3390/gels9090679 - 23 Aug 2023
Cited by 5 | Viewed by 1750
Abstract
Polymer hydrogels, including molecular hydrogels, are expected to become materials for healthcare and medical applications, but there is a need to create new functional molecular gels that can meet the required performance. In this paper, for creating new molecular hydrogel materials, the gel [...] Read more.
Polymer hydrogels, including molecular hydrogels, are expected to become materials for healthcare and medical applications, but there is a need to create new functional molecular gels that can meet the required performance. In this paper, for creating new molecular hydrogel materials, the gel formation behavior and its rheological properties for the molecular gels composed of a polymer hydrogelator, poly(3-sodium sulfo-p-phenylene-terephthalamide) polymer (NaPPDT), and water-soluble polymer with the polar group, poly(vinyl alcohol) (PVA) in various concentrations were examined. Molecular hydrogel composites formed from simple mixtures of NaPPDT aqueous solutions (0.1 wt.%~1.0 wt.%) and PVA aqueous solutions exhibited thixotropic behavior in the relatively low concentration region (0.1 wt.%~1.0 wt.%) and spinnable gel formation in the dense concentration region (4.0 wt.%~8.0 wt.%) with 1.0 wt.% NaPPDT aq., showing a characteristic concentration dependence of mechanical behavior. In contrast, each single-component aqueous solution showed no such gel formation in the concentration range in the present experiments. No gel formation behavior was also observed when mixed with common anionic polymers other than NaPPDT. This improvement in gel-forming ability due to mixing may be due to the increased density of the gel’s network structure composed of hydrogelator and PVA and rigidity owing to NaPPDT. Full article
(This article belongs to the Special Issue Advances in Smart and Tough Hydrogels)
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16 pages, 6402 KiB  
Article
Anti-Ballistic Performance of PPTA/UHMWPE Laminates
by Long Zhu, Weixiao Gao, Dmitriy A. Dikin, Simona Percec and Fei Ren
Polymers 2023, 15(10), 2281; https://doi.org/10.3390/polym15102281 - 12 May 2023
Cited by 6 | Viewed by 4000
Abstract
Poly(p-phenylene terephthalamide) (PPTA) and ultra-high-molecular-weight polyethylene (UHMWPE) are high-performance polymer materials largely used for body armor applications. Although composite structures from a combination of PPTA and UHMWPE have been created and described in the literature, the manufacture of layered composites from [...] Read more.
Poly(p-phenylene terephthalamide) (PPTA) and ultra-high-molecular-weight polyethylene (UHMWPE) are high-performance polymer materials largely used for body armor applications. Although composite structures from a combination of PPTA and UHMWPE have been created and described in the literature, the manufacture of layered composites from PPTA fabrics and UHMWPE films with UHMWPE film as an adhesive layer has not been reported. Such a new design can provide the obvious advantage of simple manufacturing technology. In this study, for the first time, we prepared PPTA fabrics/UHMWPE films laminate panels using plasma treatment and hot-pressing and examined their ballistic performance. Ballistic testing results indicated that samples with moderate interlayer adhesion between PPTA and UHMWPE layers exhibited enhanced performance. A further increase in interlayer adhesion showed a reverse effect. This finding implies that optimization of interface adhesion is essential to achieve maximum impact energy absorption through the delamination process. In addition, it was found that the stacking sequence of the PPTA and UHMWPE layers affected ballistic performance. Samples with PPTA as the outermost layer performed better than those with UHMWPE as the outermost layer. Furthermore, microscopy of the tested laminate samples showed that PPTA fibers exhibited shear cutting failure on the entrance side and tensile failure on the exit side of the panel. UHMWPE films exhibited brittle failure and thermal damage at high compression strain rate on the entrance side and tensile fracture on the exit side. For the first time, findings from this study reported in-field bullet testing results of PPTA/UHMWPE composite panels, which can provide important insights for designing, fabricating, and failure analysis of such composite structures for body armors. Full article
(This article belongs to the Special Issue Development in Fiber-Reinforced Polymer Composites)
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18 pages, 5530 KiB  
Article
Implication of Freeze–Thaw Erosion and Mechanism Analysis of High-Performance Aromatic Liquid Crystal Fibers
by Hai Wan, Yanping Wang, Wenbin Jin, Shuohan Huang, Yimin Wang, Yong He, Peng Wei, Yuwei Chen and Yumin Xia
Polymers 2023, 15(9), 2001; https://doi.org/10.3390/polym15092001 - 23 Apr 2023
Viewed by 2066
Abstract
According to the demand for high-performance fibers for high-latitude ocean exploration and development, this paper selects representative products of high-performance liquid crystal fibers: thermotropic liquid crystal polymer fibers (TLCP) and poly p-phenylene terephthalamide (PPTA) fibers. Through a series of freeze–thaw (F–T) experiments for [...] Read more.
According to the demand for high-performance fibers for high-latitude ocean exploration and development, this paper selects representative products of high-performance liquid crystal fibers: thermotropic liquid crystal polymer fibers (TLCP) and poly p-phenylene terephthalamide (PPTA) fibers. Through a series of freeze–thaw (F–T) experiments for simulating a real, cold marine environment, we then measure the retention of mechanical properties of these two kinds of fibers. Before that, due to the difference in their chemical structures, we tested their Yang–Laplace contact angle (YLCA) and water absorption; the results suggested that PPTA fibers would absorb more moisture. Surprisingly, then, compared with thermotropic liquid crystal polymer (TLCP) fibers, the retention of the mechanical properties of poly p-phenylene terephthalamide (PPTA) fibers decreased by around 25% after the F–T experiments. The Fourier-transformed infrared (FT-IR) analysis, the attenuated total reflection (ATR) accessory analysis and the degree of crystal orientation measured by two-dimensional wide-angle X-ray diffraction (2D-WAXD) confirm that no changes in the chemical and the orientation structure of the crystal region of the fibers occurred after they underwent the F–T cycles. However, as observed by scanning electron microscopy (SEM), there are microcracks of various extents on the surface of the PPTA fibers, but they do not appear on the surface of TLCP fibers. It is obvious that these microcracks will lead to the loss of mechanical properties; we infer that the moisture absorbed by the PPTA fibers freezes below the freezing point, and the volume expansion of the ice causes the collapse of the microfibrillar structure. The two sorts of fibers subjected to the F–T experiments are immersed in a sodium chloride solution, and the amount of water infiltrated into the PPTA microfibrillar structure is evaluated according to the content of sodium ions in the fiber surface and subsurface layers through X-ray spectroscopy (EDS) elemental analysis. From the above analysis, we found that TLCP fibers can more effectively meet the operating standards of the severe and cold marine environment. Full article
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19 pages, 7119 KiB  
Article
Improved Strength and Heat Distortion Temperature of Emi-Aromatic Polyamide 10T-co-1012 (PA10T/1012)/GO Composites via In Situ Polymerization
by Yanchao Dong, Pingli Wang, Zhonglai Ren, Tianyuan Liu, Zhichao Zhen, Bo Lu, Fei Li and Junhui Ji
Molecules 2023, 28(4), 1960; https://doi.org/10.3390/molecules28041960 - 18 Feb 2023
Cited by 7 | Viewed by 2527
Abstract
In this paper, an effective method for preparing poly (p-phenylene terephthalamide) -co- poly (dodecanedioyl) decylamine (PA10T/1012)/graphene oxide (GO) composites by pre-dispersion and one-step in situ polymerization was proposed for the first time. During the process of polycondensation, the condensation between the terminal amino [...] Read more.
In this paper, an effective method for preparing poly (p-phenylene terephthalamide) -co- poly (dodecanedioyl) decylamine (PA10T/1012)/graphene oxide (GO) composites by pre-dispersion and one-step in situ polymerization was proposed for the first time. During the process of polycondensation, the condensation between the terminal amino groups of PA10T/1012 chains and the oxygen-containing functional groups of GO allowed nylon to be grafted onto graphene sheets. The effects of polymer grafting on the thermal and mechanical properties of (PA10T/1012)/GO composites were studied in detail. Due to the interaction between PA10T/1012 grafted graphene sheets and its matrix, GO is well dispersed in the PA10T/1012 matrix and physically entangled with it, forming a cross-linked network structure of polymer bridged graphene, thus obtaining enhanced tensile strength, tensile modulus and impact strength. More importantly, benefiting from the cross-linked network structure, the heat distortion temperature (HDT) of the composite is greatly increased from 77.3 °C to 144.2 °C. This in situ polycondensation method opens a new avenue to prepare polycondensate graphene-based composites with high strength and high heat distortion temperatures. Full article
(This article belongs to the Special Issue Fullerenes, Graphenes and Carbon Nanotubes Nanocomposites)
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10 pages, 1546 KiB  
Article
New Insights in the Synthesis of High-Molecular-Weight Aromatic Polyamides-Improved Synthesis of Rod-like PPTA
by Guiomar Hernández, Sergio Ferrero, Helmut Reinecke, Camino Bartolomé, Jesús M. Martinez-Ilarduya, Cristina Álvarez and Ángel E. Lozano
Int. J. Mol. Sci. 2023, 24(3), 2734; https://doi.org/10.3390/ijms24032734 - 1 Feb 2023
Cited by 2 | Viewed by 3421
Abstract
By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it was possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high-value-added material Kevlar), with a molecular weight much higher [...] Read more.
By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it was possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high-value-added material Kevlar), with a molecular weight much higher than that obtained with the classical and industrial polyamidation method. The optimization of the method has consisted of using, together with the silylating agent, a mixture of pyridine and a high-pKa tertiary amine. The research was complemented by a combination of nuclear magnetic resonance and molecular simulation studies, which determined that the improvements in molecular weight derive mainly from the formation of silylamide groups in the growing polymer. Full article
(This article belongs to the Collection State-of-the-Art Macromolecules in Spain)
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17 pages, 14047 KiB  
Review
Recent Advances in Self-Assembly and Application of Para-Aramids
by Chunjie Xie, Shixuan Yang, Ran He, Jianning Liu, Yuexi Chen, Yongyi Guo, Zhaoxia Guo, Teng Qiu and Xinlin Tuo
Molecules 2022, 27(14), 4413; https://doi.org/10.3390/molecules27144413 - 9 Jul 2022
Cited by 18 | Viewed by 4695
Abstract
Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the “infusible and insoluble” characteristic [...] Read more.
Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the “infusible and insoluble” characteristic of PPTA gives rise to its poor processability, which limits its scope of application. The strong interactions and orientation characteristic of aromatic amide segments make PPTA attractive in the field of self-assembly. Chemical derivation has proved an effective way to modify the molecular structure of PPTA to improve its solubility and amphiphilicity, which resulted in different liquid crystal behaviors or supramolecular aggregates, but the modification of PPTA is usually complex and difficult. Alternatively, higher-order all-PPTA structures have also been realized through the controllable hierarchical self-assembly of PPTA from the polymerization process to the formation of macroscopic products. This review briefly summarizes the self-assembly methods of PPTA-based materials in recent years, and focuses on the polymerization-induced PPTA nanofibers which can be further fabricated into different macroscopic architectures when other self-assembly methods are combined. This monomer-started hierarchical self-assembly strategy evokes the feasible processing of PPTA, and enriches the diversity of product, which is expected to be expanded to other liquid crystal polymers. Full article
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15 pages, 11123 KiB  
Article
Improving Interlayer Adhesion of Poly(p-phenylene terephthalamide) (PPTA)/Ultra-high-molecular-weight Polyethylene (UHMWPE) Laminates Prepared by Plasma Treatment and Hot Pressing Technique
by Long Zhu, Dmitriy A. Dikin, Simona Percec and Fei Ren
Polymers 2021, 13(16), 2600; https://doi.org/10.3390/polym13162600 - 5 Aug 2021
Cited by 10 | Viewed by 3825
Abstract
Poly(p-phenylene terephthalamide) (PPTA) is a high-performance polymer that has been utilized in a range of applications. Although PPTA fibers are widely used in various composite materials, laminar structures consisting of PPTA and ultra-high-molecular-weight polyethylene (UHMWPE), are less reported. The difficulty in making such [...] Read more.
Poly(p-phenylene terephthalamide) (PPTA) is a high-performance polymer that has been utilized in a range of applications. Although PPTA fibers are widely used in various composite materials, laminar structures consisting of PPTA and ultra-high-molecular-weight polyethylene (UHMWPE), are less reported. The difficulty in making such composite structures is in part due to the weakness of the interface formed between these two polymers. In this study, a layered structure was produced from PPTA fabrics and UHMWPE films via hot pressing. To improve the interlayer adhesion, oxygen plasma was used to treat the PPTA and the UHMWPE surfaces prior to lamination. It has been found that while plasma treatment on the UHMWPE surface brought about a moderate increase in interlayer adhesion (up to 14%), significant enhancement was achieved on the samples fabricated with plasma treated PPTA (up to 91%). It has been assumed that both surface roughening and the introduction of functional groups contributed to this improvement. Full article
(This article belongs to the Special Issue Adhesive Properties of Polymeric Composites)
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13 pages, 3125 KiB  
Article
Effect of High Molecular Weight PPTA on Liquid Crystalline Phase and Spinning Process of Aramid Fibers
by Cuiqing Teng, Hui Li, Jing Liu, Hao Gu, Haijuan Kong and Muhuo Yu
Polymers 2020, 12(5), 1206; https://doi.org/10.3390/polym12051206 - 25 May 2020
Cited by 28 | Viewed by 7489
Abstract
High molecular weight poly (p-phenylene-terephthalamide) (h-PPTA) was blended with the commercial PPTA in concentrated sulfuric acid to improve the spinnability of the polymer solutions and the mechanical properties of the as-spun fibers. h-PPTA in the solution has an influence on the [...] Read more.
High molecular weight poly (p-phenylene-terephthalamide) (h-PPTA) was blended with the commercial PPTA in concentrated sulfuric acid to improve the spinnability of the polymer solutions and the mechanical properties of the as-spun fibers. h-PPTA in the solution has an influence on the temperature of the formation of liquid crystalline phenomenon. The temperature range with the existence of the liquid crystalline phase increases upon the contents of h-PPTA in the solution, and the extended temperature window is helpful for the preparation of PPTA fibers by the dry-jet wet-spinning technology. The long-chains of h-PPTA enhance the inter-macromolecular interactions and induce the orientation of short-chains for PPTA along the fiber axis under the shear stress in the spinneret and the stretching stress at the air gap. These effects also increase the maximum drawing ratio in the spinning process and improve the mechanical properties of the obtained fibers. The crystallinity and crystal orientation of the fibers are investigated by X-ray diffraction, and results from sonic velocity test further confirm ordering state of the macromolecular chains. The fibril morphologies of the fibers are also studied by a scanning electric microscope. Full article
(This article belongs to the Section Polymer Processing and Engineering)
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13 pages, 8398 KiB  
Article
Enhancing the Interfacial Adhesion with Rubber Matrix by Grafting Polydopamine-Carbon Nanotubes onto Poly(p-phenylene terephthalamide) Fibers
by Xuan Yang, Qunzhang Tu, Xinmin Shen, Qin Yin, Ming Pan, Chengming Jiang and Caibing Hu
Polymers 2019, 11(8), 1231; https://doi.org/10.3390/polym11081231 - 24 Jul 2019
Cited by 20 | Viewed by 3467
Abstract
To enhance the interfacial adhesion between poly(p-phenylene terephthalamide) (PPTA) fibers and a rubber matrix without damaging the fiber structures, aminated carbon nanotubes (NH2-CNTs) were mildly deposited onto the fiber surface by combining the biomimetic modification of dopamine via the Michael addition [...] Read more.
To enhance the interfacial adhesion between poly(p-phenylene terephthalamide) (PPTA) fibers and a rubber matrix without damaging the fiber structures, aminated carbon nanotubes (NH2-CNTs) were mildly deposited onto the fiber surface by combining the biomimetic modification of dopamine via the Michael addition reaction. Furthermore, differences between the “one-step” method and the “two-step” method were researched through adjusting the addition sequence of NH2-CNTs. The surface morphologies and chemical structures of PPTA fibers before and after modification were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The mechanical properties of fibers and the adhesive properties with rubber were tested using an electronic tensile tester of single-filament and universal testing machine, respectively. After modification by the “one-step” method for 24 h, the single-filament tensile strength of the modified fibers increased by 16.5%, meanwhile, the pull-out force of the modified fibers to rubber increased by approximately 59.7%. Compared with the “two-step” method, the “one-step” method had superiority due to the short reaction time and the large deposition rate of CNTs. Full article
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16 pages, 4439 KiB  
Article
A Novel Method for Deposition of Multi-Walled Carbon Nanotubes onto Poly(p-Phenylene Terephthalamide) Fibers to Enhance Interfacial Adhesion with Rubber Matrix
by Xuan Yang, Qunzhang Tu, Xinmin Shen, Pengxiao Zhu, Yi Li and Shuai Zhang
Polymers 2019, 11(2), 374; https://doi.org/10.3390/polym11020374 - 20 Feb 2019
Cited by 26 | Viewed by 4521
Abstract
In order to enhance the interfacial adhesion of poly(p-phenylene terephthalamide) (PPTA) fibers to the rubber composites, a novel method to deposit multi-walled carbon nanotubes (MWCNTs) onto the surface of PPTA fibers has been proposed in this study. This chemical modification was performed through [...] Read more.
In order to enhance the interfacial adhesion of poly(p-phenylene terephthalamide) (PPTA) fibers to the rubber composites, a novel method to deposit multi-walled carbon nanotubes (MWCNTs) onto the surface of PPTA fibers has been proposed in this study. This chemical modification was performed through the introduction of epoxy groups by Friedel–Crafts alkylation on the PPTA fibers, the carboxylation of MWCNTs, and the ring-opening reaction between the epoxy groups and the carboxyl groups. The morphologies, chemical structures, and compositions of the surface of PPTA fibers were characterized by scanning electron microscope, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results showed that MWCNTs were uniformly deposited onto the surface of PPTA fibers with the covalent bonds. The measurement of contact angles of the fibers with polar solvent and non-polar solvent indicated that the surface energy of deposited fibers significantly increased by 41.9% compared with the untreated fibers. An electronic tensile tester of single-filament and a universal testing machine were utilized to measure the strength change of the fibers after modification and the interfacial adhesion between the fibers and the rubber matrix, respectively. The results showed that the tensile strength had not been obviously reduced, and the pull-out force and peeling strength of the fibers to the rubber increased by 46.3% and 56.5%, respectively. Full article
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14 pages, 10300 KiB  
Article
Effects of (Oxy-)Fluorination on Various High-Performance Yarns
by Iris Kruppke, Matthias Bartusch, Rico Hickmann, Rolf-Dieter Hund and Chokri Cherif
Molecules 2016, 21(9), 1127; https://doi.org/10.3390/molecules21091127 - 26 Aug 2016
Cited by 8 | Viewed by 5999
Abstract
In this work, typical high-performance yarns are oxy-fluorinated, such as carbon fibers, ultra-high-molecular-weight polyethylene, poly(p-phenylene sulfide) and poly(p-phenylene terephthalamide). The focus is on the property changes of the fiber surface, especially the wetting behavior, structure and chemical composition. Therefore, [...] Read more.
In this work, typical high-performance yarns are oxy-fluorinated, such as carbon fibers, ultra-high-molecular-weight polyethylene, poly(p-phenylene sulfide) and poly(p-phenylene terephthalamide). The focus is on the property changes of the fiber surface, especially the wetting behavior, structure and chemical composition. Therefore, contact angle, XPS and tensile strength measurements are performed on treated and untreated fibers, while SEM is utilized to evaluate the surface structure. Different results for the fiber materials are observed. While polyethylene exhibits a relevant impact on both surface and bulk properties, polyphenylene terephthalamide and polyphenylene sulfide are only affected slightly by (oxy-)fluorination. The wetting of carbon fiber needs higher treatment intensities, but in contrast to the organic fibers, even its textile-physical properties are enhanced by the treatment. Based on these findings, the capability of (oxy-)fluorination to improve the adhesion of textiles in fiber-reinforced composite materials can be derived. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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