High-Modulus Wholly Aromatic Fibers. I. Wholly Ordered Polyamide-Hydrazides and Poly-1,3,4-oxadiazole—Amides

Several completely ordered polyamide-hydrazide copolymers were prepared via low temperature poly condensation of aromatic diacid chlorides with symmetrical aromatic diamines containing preformed dihydrazide linkages. Highly crystalline, hot-drawn fibers of the polyamide-hydrazide containing only para-oriented phenylene units showed unusually high strength and exceptionally high initial modulus: 10.8 and 508 g/den, respectively, at 2.9% elongation-to-break. The as-spun fibers also exhibited rather high tensile strength and unusually high initial modulus: 8.2 and 291 g/den, respectively, at 9.4% elongation-to-break. The hot-drawn fiber retained considerable strength at elevated temperatures, exhibiting a tenacity of 1.4 g/den and an initial modulus of 169 g/den at 350°C. Heat-aging of the as-spun fiber at 185°C in air showed that 66% of the original tenacity, 41% of the elongation, and 86% of the modulus were retained even after 336 hr. Substitution of as little as 25 mole % meta-oriented phenylene rings for para-oriented ones resulted in loss of the ultra-high strength and modulus, giving tensile properties comparable to those of fibers from wholly aromatic polyamides of the meta-oriented type. Fibers from the polyamide-hydrazides containing 50 mole % meta-oriented rings showed similar properties. Although ordered oxadiazole-amide copolymers were obtained from diamines containing two preformed oxadiazole linkages separated by m-phenylene rings, fibers could not be spun from them. Fiber of an ordered oxadiazole-amide copolymer was obtained, however, by heat treatment of the wholly p-phenylene ordered poly amide-hydrazide copolymer precursor fiber. Such a fiber exhibited a tenacity of 15.3 g/den, 3.6% elongation-to-break, and 564 g/den initial modulus.     

On the role of friction in energy dissipation upon transverse ballistic impact on fabric

Fabrics based on high-strength nylon and aramid fibers are known to have the ability to strongly dissipate energy upon ballistic impact. This study addresses the causes of this behavior, and it is concluded that the principal contribution to energy dissipation upon transverse ballistic impact is made by friction between multifilament yarns rather than by longitudinal impact waves, as observed in the case of monofilament fibers.     

A study of yarn friction in aramid fabrics

Energy dissipation by the friction forces of yarns in aramid fabrics with different weave patterns is studied. The upper theoretical limit of the ability of fibers to absorb the energy of transverse impact is determined. The maximum pull-out force for yarns of a plain-weave fabric nonlinearly depends on the number of pulled-out yarns. In twill-weave fabrics, this dependence is linear. Changing the weave pattern is an effective way to change the pull-out forces for yarns. Owing to the slippage of the yarns, the fabric behaves as a plastic material.     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

Processing and Properties of Nanocomposite Filament Yarns with Various Filler Concentrations from Two Different Modification Methods

In this research, the possibility of producing and processing nanocomposite polypropylene filament yarns with permanent antimicrobial efficiency has been assessed by comparing two different methods. Therefore two approaches were used to mix various blending contents of antimicrobial agents based on silver/TiO₂ nano particles with PP: 1) mixing of PP powder and inorganic nanocomposite powder as an antibacterial agent with the appropriate concentration in a twin screw extruder, preparing modified granules and feeding them to the melt spinning machine, 2) producing masterbatch by a twin screw extruder and blending it with PP in the melt spinning process. In both methods, pure PP and all other combined samples had an acceptable spinnability at the spinning temperature of 240 °C and take-up speed of 2000 m/min. After producing as-spun filament yarns by a pilot plant melt spinning machine, samples were drawn, textured and finally weft knitted. Physical and structural properties of as-spun and drawn yarns with constant and variable draw ratios were investigated and compared. Moreover, the DSC, SEM and FTIR techniques have been used for samples characterization. Finally antibacterial efficiency of knitted samples was evaluated. The experimental results indicated that the maximum crystallinity reduction of modified as-spun yarns reached 5%. But by applying method 2 (masterbatch), crystallinity of modified as-spun yarns remained unchanged compared to pure yarn. However, drawing procedure has compensated this difference. By applying the second method, the drawing generally improved the increase of tenacity and modulus of modified fibers, whereas in method 1 the opposite effect was noticed in the case of constant draw ratio. Although the biostatic efficiency of nanocomposite fibers was excellent in both methods, modified fabrics obtained from method 1 showed higher bioactivity.     

BPDA/PPD/OTOL聚酰亚胺纤维的力学性能、形貌和结构

在3,3’,4,4’-联苯四酸二酐(BPDA)和对苯二胺(PPD)体系中引入3,3’-二甲基联苯胺(OTOL),显著改善了纤维的力学性能。当n(PPD)∶n(OTOL)=70∶30时,纤维的拉伸强度可达到改性前的2倍,其拉伸强度和拉伸模量分别为1.50和80 GPa。SEM照片显示了纤维的断面为圆形且没有孔穴,也没有明显的"皮芯"结构和原纤结构。WAXD和SAXS分析表明,纤维的轴向堆积和分子链取向在热牵伸过程中得到改善。     

Investigation on Physical and Mechanical Properties of WPC from Corn stalk (Lignocellulosic Fiber) and HDPE

Summary: This study has tried to use HDPE and the coupling agent consistent MAPP and cornstalk fibers, create wood plastic composite material and its physical and mechanical properties such as tensile modulus, flexural modulus and humidity absorption is measured. After determining the percentage of 20, 30 and 40% of corn stalk fibers in the product and the use of two longitudinal mesh levels of 40 and 80 of them and using the 5% MAPP coupling agent testing was done and it was shown that increasing fiber length and percent increase in product humidity is absorbed. This is while the declines by increasing the fiber length changes of samples were during the tensile tests. In the bending test also increased fiber length and flexural modulus was increased.     

聚对苯二甲酰对苯二胺纤维的热老化行为与机理研究

在250～400℃空气中对自由状态下对位芳纶进行等温热老化处理,采用万能材料试验机、红外光谱法、广角X射线衍射法、声速法和特性黏数法表征了老化过程中力学性能和结构的变化.结果表明,在老化初期,由于分子链的解取向,强度随时间快速下降;随后的热分解使强度随老化时间继续降低,符合二级反应动力学模型,其热老化表观活化能为32.4kJ/mol.老化样品的强度随温度升高显著下降,但高于350℃时热交联反应变得明显,同时结晶度增大和结晶结构完善,使强度的损失速率减小.老化样品的模量随老化温度的升高而增大,低于350℃时,非晶态分子链的解取向占优,模量较未热老化样品低;升高至350℃时,结晶结构完善占优,表现在第二类晶格畸变参数降低、表观微晶尺寸增大,特别是微晶横向融合使a,b轴方向尺寸显著增大,模量明显高于未老化样品.     

Tensile properties and structure of polypropylene fibres spun from a blend of different polymer grades

 The tensile behavior of fibres, spun from a blend of small percentage of plastic grade poly-propylene with fibre grade poly-propylene, was studied in relation to their structure. The spinning and drawing process was optimized in order to increase the elastic moduli of produced filament yarns. By such optimization of the process a tenacity of 0.7 GPa, an elastic modulus of 14.8 GPa and a dynamic modulus of 19 GPa were attained. From diffuse small-angle X-ray scattering the presence of voids, up to 11.5%, was established. Voidness of the fibrillar structure was confirmed with electron micrographs. In spite of the rather drastic changes in morphology the mechanical properties of high void fibrillar structures are good, indicating that the load bearing units of the filament have maintained their integrity. The improved mechanical behavior of highly drawn fibres spun from 10/90 plastic/fibre grade polymer blend is related to higher crystalline and above all to higher amorphous orientation. Received: 12 December 1996 Accepted: 28 February 1997     

Impact fracture behavior of nylon-6/ABS blends

Tensile and impact properties of uncompatibilized nylon-6/ABS blends have been studied over the entire range of compositions. The blends were prepared by extrusion and, subsequently, injection molded into tensile specimens and rectangular plaques. The impact fracture performance was characterized using recently proposed models based on fracture mechanics, for various fracture behaviors. The results showed that nylon-6 breaks in a brittle manner. With the addition of ABS, the blend exhibits the same behavior with a slightly lower impact resistance up to about 60 wt %. A sudden jump in the value of impact fracture energy is observed around 70 wt % ABS with a brittle—ductile transition in the mechanism of fracture. The transition in fracture mechanisms is confirmed through observation of the fracture surfaces by scanning electron microscopy (SEM). Tensile tests showed that the elongation at break increases only slightly between 0 and 50% ABS content, but a significant jump occurs around 70% ABS, reaching a 6-fold increase in comparison to that of the pure components. SEM observation of etched samples shows that a cocontinuous morphology occurs around 70 wt % ABS. The peak observed for the elongation at break and the jump in impact performance, as well as the onset of brittle–ductile transition, are attributed to this morphological effect. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2583–2592, 1997     

The temperature‐dependent ballistic performance and the ductile‐to‐brittle transition in polymer networks

The temperature dependence of the ballistic impact performance of a series of transparent polymer networks is evaluated. A systematic series of homogeneous epoxy/propylene‐oxide‐based thermosets, a nanoscale phase‐separated epoxy/dual amine thermoset, and two homogeneous, completely aliphatic materials synthesized via ring‐opening metathesis polymerization are examined. The Vogel temperature (T_o) and the Kauzmann temperature (T_K) are critical parameters for scaling the temperature‐dependent ballistic impact performance of each class of materials. The ductile‐to‐brittle transition temperature in a series of propylene‐oxide amine‐cured epoxies occurs at the material T_K, corresponding to a sharp drop in fracture toughness and ballistic impact performance. Two aliphatic, ring‐opening metathesis polymerized materials are found to exhibit no clear transition from purely ductile to purely brittle behavior, but the temperature dependence is still scaled to a single curve when normalized by T_o. The cooperatively rearranging region (CRR) or the volume of this region is related to the breadth of temperatures over which these materials exhibit purely ductile deformation both quasi‐statically and at higher rates. The temperature‐dependent performance is discussed in the context of the configurational entropy. The breadth of the ductility window is related to the size of the CRR, calculated from calorimetric measurements at the resin T_g. Published 2019. This article is a U.S. Government work and is in the public domainin the USA. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 511–523     

Nanostructural evidence of mechanical aging and performance loss in ballistic fibers

It is understood that the ballistic resistance of aromatic polyamide fibers is related to the fiber's ultimate tensile strength, strain‐to‐failure, and Young's modulus. Ideal high‐performance ballistic materials maximize these properties while minimizing material density. Equally important is long‐term mechanical and chemical stability: the fibers should not exhibit performance loss over their lifetime. However, less is known quantitatively about their modes of degradation, and experimental methods to quantify the aging and degradation in these fibers are critical. Multiple variations of next generation high‐performance fibers have been investigated under chemical and mechanical accelerated aging conditions. Performance losses have been empirically correlated to chemical degradation of the polymer chain and nanostructural changes in the fiber morphology through X‐ray photoelectron spectroscopy (XPS). Here, we introduce positron annihilation lifetime spectroscopy measurements as a sensitive method to quantify the early onset of damage in the flexed fibers as quantified through changes in the nanoscale void structure in the material. Published 2017.^? J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1711–1717     

The Mechanical Deformation Process of Electrospun Polymer Nanocomposite Fibers

Summary: The mechanical deformation processes of poly(methyl methacrylate)/ montmorillonite nanocomposites and their electrospun fibers were investigated by in situ tensile tests under a transmission electron microscope depending on their morphology. While the polymer nanocomposites deformed in a brittle manner, i.e., crazing, the electrospun polymer nanocomposite fibers deformed through a shear flow process leading to “nanonecking” due to the strong overlap of stress fields caused by nanopores within the fiber under a uniaxial tensile load. This unique change in deformation behavior provides the possibility that the intrinsic brittle material could be manipulated to be ductile without sacrificing its other attractive properties through a well‐controlled electrospinning process.

TEM micrograph of a low temperature fractured fiber showing the nanoporous surface structure.     

High-Modulus Wholly Aromatic Fibers. II. Partially Ordered Polyamide-Hydrazides

Partially ordered polyarnide-hydrazides were produced by the poly condensation of diacid chlorides with aminobenz-hydrazides, the order that results being a consequence of the considerably more rapid reaction of a diacid chloride with the hydrazide group in competition with the aromatic amine group of the aminobenzhydrazide. Fibers were produced from a series of such polymers containing from 50 mole % meta-oriented phenylene rings to 100 mole % para-oriented ones. Fiber from the wholly para-oriented type of polymer exhibited very high strength and modulus: 12.5 and 468 g/den, respectively, at 4.3% elongation-to-break. Although the crystallinity and density observed for hot-drawn fibers of partially ordered completely para-oriented polyarnide-hydrazides were comparable to the crystallinity and density of fibers of the isomeric wholly ordered polymer, the partially ordered polymers were more readily spun to the ultra-high strength and high modulus type fibers, probably because their greater solubility made them easier to spin.     

Effect of fiber length and composition on mechanical properties of carbon fiber‐reinforced polybenzoxazine

The mechanical strength and modulus of chopped carbon fiber (CF)‐reinforced polybenzoxazine composites were investigated by changing the length of CFs. Tensile, compressive, and flexural properties were investigated. The void content was found to be higher for the short fiber composites. With increase in fiber length, tensile strength increased and optimized at around 17 mm fiber length whereas compressive strength exhibited a continuous diminution. The flexural strength too increased with fiber length and optimized at around 17 mm fiber length. The increase in strength of composites with fiber length is attributed to the enhancement in effective contact area of fibers with the matrix. The experimental results showed that there was about 350% increase in flexural strength and 470% increase in tensile strength of the composites with respect to the neat polybenzoxazine, while, compressive properties were adversely affected. The composites exhibited an optimum increase of about 800% in flexural modulus and 200% in tensile modulus. Enhancing the fiber length, leads to fiber entanglement in the composites, resulted in increased plastic deformation at higher strain. Multiple branch matrix shear, debonded fibers and voids were the failures visualized in the microscopic analyses. Defibrillation has been exhibited by all composites irrespective of fiber length. Fiber debonding and breaking were associated with short fibers whereas clustering and defibrillation were the major failure modes in long fiber composites. Increasing fiber loading improved the tensile and flexural properties until 50–60 wt% of fiber whereas the compressive property consistently decreased on fiber loading. Copyright © 2008 John Wiley & Sons, Ltd.     

Degradation of ROMP-based bio-renewable polymers by UV radiation

The degradation of a bio-renewable polymer under UV exposure was studied using various methods. Degradation of the bio-renewable polymer increased with increasing exposure time. Enhanced cross-link density in the early stage of degradation was confirmed by Soxhlet extraction. Tensile testing showed a transition from ductile failure to brittle fracture. Surface cracks and embrittlement were primary reasons for most reductions in mechanical properties, such as tensile strength and breaking strain. The effects of degradation were confined to the surface of thick bio-based polymer specimens, confirmed by both SEM and PAS-FTIR. Depth profile studies of degraded samples showed that the concentration of oxidation products, such as hydroxyl and carbonyl groups, varied with depth depending on the diffusion of oxygen.     

聚苯硫醚纤维的抗张强度与工艺和结构的关系

以熔融纺丝法制备出不同结晶度的各向同性聚苯硫醚纤维作为样品,根据密度和声速测定值确定出PPS晶相和无定形相的本征横向声模量E0⊥,c(4.40 GPa)和E0⊥,am(1.99 GPa).利用密度梯度法测定出的结晶度Xc和X-衍射法测定的晶区取向因子fc,按照Samules模型计算出不同牵伸和定型工艺下制备的PPS纤维样品的非晶区取向因子(fam),在此基础上分析PPS纤维抗张强度与牵伸定型工艺参数、结构之间的关系.结果表明,PPS纤维的最佳牵伸温度及紧张热定型温度分别在90℃和190℃附近;提高PPS纤维的牵伸温度及紧张热定型温度可以增加纤维的结晶度,在一定范围内对纤维抗张强度的增加有促进作用;但较高的牵伸温度及紧张热定型温度不利于纤维非晶区取向的提高,造成PPS纤维抗张强度降低.牵伸倍数的增加可以有效提高PPS纤维的非晶区取向程度,抗张强度也随着增加.     

Epoxy resin toughened with thermoplastic

Highly crosslinked, brittle epoxy resin based on tètraglycidyl-4,4′-diaminodiphenyl methane (TGDDM) cured with 4,4′-diaminodiphenyl sulphone (DDS) is widely used as a matrix material for aerospace composite applications. This work describes how inclusion of a polyetherimide (PEI) thermoplastic rich phase can significantly toughen the resin without a fall in apparent stiffness, which accompanies the more traditional method of rubber toughening. Dynamic mechanical analysis and scanning electron microscopy are used to characterize morphology, while fracture toughness and flexural modulus measurements are also performed on the cured resins. The extent of toughening is found to be dependent upon PEI concentration and test temperature. It is observed that the PEI rich phase toughens through ductile drawing across the faces of the advancing crack tip, and that this is the dominant toughening mechanism in the material.     

Study of the thermomechanical behavior of UHMWPE yarns under different loading paths

UHMWPE viscoelastic fibers show great interest as reinforcement within composites and especially when used in SRPs (Self-Reinforced Polymers). They provide ductility, lightness and recyclability, benefits that glass or carbon fibers cannot provide. It is, therefore, necessary to increase knowledge about the behavior of UHMWPE fibers. Before the thermomechanical characterization of these yarns, an experimental protocol is proposed, validated and it supplements the existing standard. Monotonous, load-unload and creep tensile tests were carried out on Doyentrontex® yarns. Temperature and strain rate dependencies were observed. A time-temperature superposition is used to reconstruct the evolutions of modulus at 0.5%, maximum strength, and strain at break at 23 °C over a wide range of strain rates. The behavior of the yarns studied appears to be complex. Indeed, at low temperatures, a hyperelastic type of behavior, combined with plasticity, predominates whereas a more elasto-viscoplastic one emerges at 100 °C. From creep tests, a time-temperature-stress level superposition leads to the reconstruction of the yarns creep behavior over a long period at the reference temperature 23 °C and the reference stress level, which is 40% of the stress at break in tensile tests at any given test temperature.