Melt spinning of isotactic polypropylene: Structure development and relationship to mechanical properties

An extensive experimental study of structure development during the melt spinning of polypropylene and is as-spun polypropylene filaments is reported. Five polymers representing different molecular weights and polymerization methods were studied. WAXS, SAXS, and birefringence measurements were used to characterize the structure of the filaments. Spinning through air gives rise to monoclinic crystalline structures and spinning into cold water, the paracrystalline smectic form. Both crystalline and amorphous orientation factors were found to correlate with spinline stress for the different polymers studied. Mechanical properties of as-spun fibers such as modulus, yield strength, tensile strength, and elongation to break also correlate with spinline stress.     

Structure development in the melt spinning of nylon 66 fibers and comparison to nylon 6

The development of crystallinity and orientation during the melt spinning of nylon 66 was investigated. Nylon 66 was found to crystallize in the spinline to form the Bunn-Garner α-triclinic structure. This behavior differs from that of nylon 6. Nylon 66 was found to develop lower crystalline orientation than nylon 6 under comparable spinning conditions.     

Studies on dyeing and mechanical properties of nylon 6 filaments subjected to swelling treatments

Drawn nylon 6 filaments were subjected to swelling treatment with benzyl alcohol and aqueous solution of phenol and formic acid under slack condition and under tension. The pretreated samples were dyed with a disperse dye Foron Yellow SE-FL (C.I. Disperse Yellow 42). A considerable increase in the equilibrium dye uptake was observed as a result of swelling treatment. Studies on lateral order by X-ray methods showed that lateral order has increased considerably as a result of preswelling treatment. This apparent contradiction, viz., increase in lateral order and at the same time increase in dye upstake, is explained as due to increased void volume. Studies on mechanical properties showed that the percentage elongation is increased as a result of swelling treatment under slack condition in spite of increased lateral order. This is explained as due to the slippage of chain-folded crystallites.     

Melt spinning of high-impact polystyrene: Rubber morphology variations,orientation development,and mechanical properties

Studies of melt-spun, high-impact polystyrene filaments indicate that rubber globules are fragmented to smaller sizes with increasing drawdown ratio and spinline stress. The melt-spun fibers are highly birefringent and obey the same relationship between birefringence and stress as pure polystyrene despite the presence of the rubber globules. These results are interpreted in terms of the stress distribution across the filament cross section. Room temperature tensil force–elongation curves were obtained on the filaments, and mechanical property phenomena were interpreted in terms of the above morphology changes and orientation of polystyrene chains.     

Effect of spinning conditions on the mechanical properties of PA6/MWNTs nanofiber filaments

Carbon nanotube (CNT ) reinforced composite materials is a hot research issue now , but CNT/polymer composite nano-scale fibers still cannot be obtained readily, not mention to successfully prepare continuous CNTs/polymer composite nano-scale fiber filaments manufactured by electrospinning. In this paper, continuous filaments constructed of nano-scale PA6/MWNTs fibers in single-axis orientation were obtained by an improved wet-electrospinning technique. The effects of the concentrations of MWNTs, spinning speed and post-drawing on the mechanical properties of PA6/MWNTs nanofiber filaments were studied. The results show that when the concentrations of MWNTs is below 0.8 wt%, the increase of MWNTs content enhances the Young’s modules and breaking stress but reduces the breaking strain, while the breaking stress decreases when the MWNTs concentration exceeds 0.8 wt%. The Young’s modules and breaking stress increased as the spinning speed raised at the range of 1.8–9.0 m/min, but declined when the speed exceeded 9.0 m/min. The mechanical properties of the as-spun filaments can be improved by either dry or wet post-drawing, and the breaking stress of the wet post-drawn filaments was improved 2.64 times while that of the dry post-drawn filaments 2.28 times.     

Interaction of nylon 6-clay surface and mechanical properties of nylon 6-clay hybrid

We synthesized nylon 6-clay hybrid materials using four types of clay minerals, montmorillonite, saponite, hectrite, and synthetic mica. The mechanical properties of their injection molded specimens were measured according to ASTM. Nylon 6-clay hybrid using montmorillonite was superior to the other hybrids in mechanical properties. This might result from the difference in the interaction between nylon molecules and silicates in the hybrids. To clarify this hypothesis, we synthesized intercalated compounds of the clay minerals with glycine as the model of the hybrids, and analyzed the interaction using ¹⁵N cross polarization magic angle spinning (CP/MAS) NMR spectroscopy. The ¹⁵N-NMR result reveals that the positive charge density on the nitrogen of the intercalated compound based on montmorillonite was largest in all the intercalated compounds. It was suggested that montmorillonite interacted strongly with nylon 6 by ionic interaction. This ionic interaction was one of the reasons why these hybrid materials had superior mechanical properties. © 1995 John Wiley & Sons, Inc.     

Mechanical and structural properties of melt spun polypropylene/nylon 6 alloy filaments

Investigated in the present study are the physical properties, morphology, and structure of PP/N6 alloy filaments (10, 20 wt % N6) made with or without PP‐g‐MAH as compatibilizer. The alloy filaments produced at the take‐up speeds of 300 and 800 m/min were drawn with draw ratio of 3.5 and 2, respectively. Stress–strain curves of PP and alloy filaments show ductile and brittle behavior, respectively. It is suggested that the brittle behavior of alloy filaments is due to the presence of microvoids or micropores at the interface of PP and N6; these lead to stress concentration and thus to a decrease in tenacity, modulus, and elongation at break. Effects of the blending of N6 with PP on birefringence and crystalline and amorphous orientation factors of the composite filaments are studied. The amorphous orientation factor, f_am, of PP was found to increase with an increase in the amount of N6. The alloy filaments behaved like isostrain materials and most of the force in spinning and drawing was born by the PP phase. The presence of N6 fibrils helped to orient PP chain molecules in amorphous regions. However, the crystalline factor, f_c, of PP decreased with the increase in nylon fraction. This means the presence of the crystals of N6 caused a decrease in the orientation of the PP crystals. LSCM micrographs of the filament showed the presence of matrix–fibril morphology with the N6 fibrils oriented along the axis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 532–544, 2005     

Influence of spinning velocity on mechanical and structural behavior of PET/nylon 6 fibers

Influence of spinning velocities on the mechanical and structural properties of polyethylene terephthalate (PET)/nylon 6 blend fibers have been reported. Fibers of PET/nylon 6 containing a small percentage of nylon (5% by weight) have been melt-spun at 3 different spinning velocities (2,900; 3,200; 3,600 m/min). The fibers have been characterized by thermal, morphological, structrual, and mechanical analysis. Various techniques such as SEM, DSC, X-ray diffraction, hot water shrinkage (HWS), viscosity, and birefringence have been used. SEM analysis revealed that in the blend, nylon 6 is well-dispersed as spheres in the PET matrix. The blend shows a marked decrease in the melt-flow index, which in turn leads to a beneficial effect on the rheological properties of the PET without negatively influencing its mechanical characteristics. This finding results in a saving on energetical requirements of the processing, as both temperature and pressure of spinning can be decreased. © 1995 John Wiley & Sons, Inc.     

Effect of photodegradation on dynamic mechanical properties of nylon 6

Changes in the dynamic mechanical properties of nylon 6 (α-form) under ultraviolet light irradiation were investigated. On irradiation with spectrally dispersed ultraviolet light in the wavelength range of 219–415nm, the dynamic modulus E′ and the density of nylon 6 were increased below about 300nm. It was found that the increment in E′ and the density were the result of crosslinking. When E′ was measured with time elapsed during irradiation by light of 253.7 nm, E′ initially decreased with time, increased at a longer time, and then reached a limiting value asymptotically. From the result of the change in E′ with time, it was assumed that the scission and crosslinking reactions occur simultaneously during ultraviolet light irradiation. Thus, the change in E′ with elapsed time was exppressed by the equation E′_t = E′₀ exp (?k₁t) + E′_∞[1 ? exp (?k₂t)], where E′_t is the dynamic modulus at time t, E′₀ is the E′ at t = ₀, E′_∞ is the limiting value of E′, and k₁ and k₂ are the rate constants. The apparent activation energies for k₁ and k₂ were 3.23 and 2.50 kcal/mole, respectively, and the former value agreed with the activation energy for the scission of the amide groups. The effects of the photodegradation on the temperature dispersion of nylon 6 were also investigated. On irradiation with light at 253.7 nm, the α-relaxation which appeared at about 90°C was broadened and the intensity of the γ-relaxation at ?95°C in the tan δ-versus-temperature curve was lowered. The β-relaxation which appeared at ?45°C for the wet nylon 6 decreased its intensity.     

Structure and properties of talc-filled polyethylene and nylon 6 films

Water vapor transmission rates can be reduced by as much as 50% in polyethylene by using talc as a filler. The oxygen permeability as well as water vapor transmission rates are similarly reduced by talc in nylon 6 films. The films show low elongation at break and reduced breaking strenth in the presence of talc. The yield strength and the modulus increase with the amount of talc, whereas the elongation at yield decreases. The mechanical and the barrier properties change with the size of the filler, the smaller size being more favorable. Talc probably acts as a nucleating agent and increases the crystallinity in polyethylene and nylon. Polyethylene unit cells in talc-filled films are oriented with the (110) planes parallel to the (001) planes of talc. Nylon 6 crystals, which are in the α form in the presence of talc, are oriented with the hydrogen bonded sheets, the (002) planes, parallel to the (001) planes of talc. In both polyethylene and nylon 6, talc is oriented with the c-axis normal to the plane of the film, i.e., with the broad faces of talc flakes in the plane of the film. Lattice matching between the polymer and talc suggests epitaxy to be a contributing factor for the observed orientation of polyethylene and nylon 6 crystals.     

High‐performance filaments by melt spinning low viscosity nylon 6 using horizontal isothermal bath process

Several techniques and treatments have been developed for the production of high‐performance nylon‐6 fibers. The inherent problems of low productivity, high production cost, and high energy consumption, complexity of chemical reaction, mass transfer, and waste recovery systems make most of them inappropriate for industrial application. Horizontal isothermal bath (hIB) is an alternative ecofriendly simple treatment that can be used during melt spinning process for production of technical textile fibers. The efficacy of hIB in improving the mechanical properties of multifilament nylon‐6 yarn is studied in this research. The results showed that such treatment can increase the molecular orientation of the amorphous and crystalline functions up to 0.54 and 0.983, respectively, and raised both the amorphous isotropy and fiber birefringence by 67 and 45%, respectively. Hot drawing of the yarn at a very low draw ratio of 1.38, increased the tenacity and modulus up to 10 and 43.9 g/den, respectively, and decreased the elongation to 27%. POLYM. ENG. SCI., 55:2457–2464, 2015. © 2015 Society of Plastics Engineers     

Structure development in melt spinning filaments from polybutylene terephthalate based thermoplastic elastomers

Structure development in polybutylene terephthalate (PBT) and thermoplastic elastomers (TPEs) based on PBT during the melt spinning process was investigated. Melt spun filaments were examined using wide angle X‐ray diffraction and birefringence. Crystalline orientation was characterized in terms of Hermans‐Stein orientation factors. Crystalline orientation and birefringence were found to correlated with spinline stress better than drawdown ratio. Crystalline orientation development was strongly dependent on spinline stress. The TPEs with low PBT content had low birefringence although the crystalline orientation was often high.     

尼龙6改性研究

采用经化学改性的芳纶纤维增强尼龙6,并通过红外光谱和电镜分析其界面层,结果表明芳纶纤维经异氰酸酯化及封端稳定处理后,其表面所接技的不稳定基团-NCO转化成稳定的-NHCO-,封端结果较为明显;改性后纤维表面附有接枝物,从而使表面粗糙程度大大增加。用挤出和注塑的方法加工了PA6／Kevlar纤维（KF）复合材料,研究了它的拉伸、弯曲和冲击性能破坏形态。力学性能测试表明了改性尼龙6复合材料的拉伸和弯曲强度得到了改善,但冲击性能略为下降。     

Formation of cracks on photodegraded nylon 6 filaments

Cracks were found on the surface of drawn nylon 6 filaments irradiated with ultraviolet (UV) light from a mercury lamp under various humidities at room temperature. The cracks were formed perpendicular to the fiber axis and were of varying sizes. No cracks were observed on undrawn filaments or drawn filaments exposed to UV light in a dry atmosphere. Considerable shrinkage was found in drawn samples by thermomechanical analysis indicating the presence of residual stress in the material. The cracking is explained in terms of the residual stress and plasticization by moisture.     

Alteration of the mechanical and thermal properties of nylon 6/nylon 6,6 blends by nanoclay

Nylon 6 [N(6)], nylon 6,6 [N(6,6)], and their blends at different clay loadings were prepared. The mix was melted and injected into strip‐shaped samples. Mechanical and thermal analyses were performed to investigate the effect of blending and the incorporated clay on the mechanical and thermal properties. Enhancements in the Young's modulus and hardness were obtained for all of the nanocomposites, with a 55% increase in Young's modulus after the addition of 6 wt % nanoclay, although the improvement in tensile strength depended on the blend ratio, with greatest effects on the 50% N(6)/50% N(6,6) blend with increases of 44 and 59% for 2 and 4% clay loadings, respectively. Thermogravimetric analysis showed an enhancement in the thermal properties in the 50% N(6)/50% N(6,6) blend at 2% clay loading, and the blend exhibited ductile behavior at this loading. Increases in the crystallization peak temperatures of 10–15° in N(6,6) and the two blends 30% N(6)/70% N(6,6) and 50% N(6)/50% N(6,6) were observed after the addition of the clay. The nanoclay enhanced the γ‐/β‐form crystals in N(6) and N(6,6) neat polymers and also in the blends. Fourier transform infrared spectroscopy FT‐IR revealed the formation of hydrogen bonding and the possible formation of ionic bonds between the polymers and the nanoclay, which resulted in enhancements in the mechanical properties of the blends. The distribution of the nanoclay in the blend was well dispersed, as shown by X‐ray diffraction analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

尼龙6-聚乙烯合金/蒙脱土纳米复合材料的制备与物理机械性能

用熔融插层法制备了尼龙6-聚乙烯合金/蒙脱土纳米复合材料.X射线衍射表明,在有机蒙脱土质量分数为4%,6%时,蒙脱土被剥离成片层分散在基体中;进一步提高蒙脱土质量分数至10%,蒙脱土部分剥离,部分插层.物理机械性能测试结果表明,将有机蒙脱土加入尼龙6-聚乙烯合金中能显著提高复合材料的拉伸强度、弯曲强度、冲击强度.其中冲击强度最大可以提高100%以上.     

Effect of solvent treatments on the mechanical properties of nylon 6

The effects of absorbed solvents and chemical agents on the stress-strain and dynamic mechanical properties of nylon 6 film have been examined. The agents investigated were: water, benzyl alcohol, phenol and iodine. These materials produce changes in the crystalline structure as well as plasticization when they are absorbed. Repeated introduction and removal of phenol indicated that the change of structure takes place completely during the first absorption; after that, the effects of absorption are reversible. The pure plasticizer effect can therefore be observed by comparison of a sample containing plasticizer and a sample from which the plasticizer has been subsequently removed. The general effect of absorbed plasticizer (except for iodine) seems to depend primarily on the amount of plasticizer absorbed, and very little on its exact chemical nature. However, different agents can produce different crystalline forms. A method of analyzing the stress-strain curve is hypothesized based on the concept of a two-phase solid state structure consisting of a crystalline lattice imbedded in an amorphous matrix.     

Miscibility and mechanical properties of aryl-aliphatic polyamides/nylon 6 molecular composites

Summary A series of aryl-aliphatic polyamides, copoly(4,4-diaminobenzanilide-adipamide/2,6-naphthalamide)s, with feed mole ratios of adipic acid/2,6-naphthalene dicarboxylic acid of 1/9, 3/7, and 5/5 were synthesized. A new family of molecular composites based on the synthesized aryl-aliphatic polyamides and nylon 6 has been discovered. The molecular composites were found to have at least partial miscibility between aryl-aliphatic polyamides and nylon 6. Well-defined aryl-aliphatic polyamide microfibrils a few nanometers in diameter were observed in the molecular composites. 10 wt% aryl-aliphatic polyamide clearly promoted the toughness of nylon 6.     

The characterization of nylon 6 filaments by x-ray diffraction

A method is described for calculating crystallinity indices and crystalline orientation functions for the α and γ components of the crystalline phase of nylon 6 filaments using wide-angle x-ray diffraction (WAXS) analysis. The method is shown to be applicable to a wide range of filament samples (“conventional” as-spun, fast spun, drawn, and annealed) even when only a single broad diffraction maximum is observable from the WAXS photograph. The component indices can be used to illustrate differences present in the filament microstructure which would be unobservable if a total crystallinity index, such as that determined by density, were determined alone. For example, the initially mixed α–γ structure is retained in low-temperature drawing (75–150°C) of nylon 6 fiber, but the predominantly α form is produced at higher draw temperatures.     

聚氯乙烯纤维熔融纺丝工艺及性能研究

采用熔融纺丝技术制备聚氯乙烯(PVC)初生纤维,经过75~95℃水浴拉伸3~8倍制得PVC纤维,研究了不同增塑剂含量的PVC体系的流变性和热稳定性,通过X射线衍射和小角X射线散射分析了拉伸条件对PVC纤维结构及力学性能的影响。结果表明:PVC熔体符合切力变稀行为;增塑剂加入量越多,PVC分子间作用力越小,PVC熔体流动性越好,PVC体系热稳定性较好;PVC纤维后处理工艺拉伸倍数越大,PVC纤维结晶长周期越小,取向诱导新的结晶结构出现,分子间作用力增大,PVC纤维的强度越大;相同拉伸倍数下,后拉伸温度越高,PVC纤维强度越大;适宜PVC体系配方为PVC与邻苯二甲酸二辛酯及邻苯二甲酸二丁酯的质量比为100∶40∶20,其他添加剂若干,此配方的PVC初生纤维在95℃水浴中拉伸8倍,所得的纤维其断裂强度为1.04 c N/dtex,断裂伸长率35.78%。