尼龙6超韧化研究进展

介绍了超韧尼龙6的最新研究进展.主要介绍了几种超韧尼龙6的制备方法,其中马来酸酐接枝聚烯烃弹性体与尼龙6-无机纳米复合材料共混,能得到刚性、强度和韧性综合性能较好的超韧尼龙.     

尼龙6超韧化

介绍了国外在尼龙６超韧化改性研究领域中的最新进展。主要介绍几经龙６共混物及其增韧的机理。     

分子复合型尼龙—6合金材料的研究进展

本文概述了分子复合型尼龙－６合金材料的发展及最新研究动态，介绍了近十几年来国内外和种典型尼龙－６分子复合的制备、结构与性能、增强机理，预示了分子复合型尼龙－６合金材料的开发前景。     

MC尼龙/纳米碳酸钙复合材料最优制备工艺的研究

用均匀设计法和人工神经网络法等技术对MC尼龙／纳米碳酸钙复合材料的制备工艺条件进行了深入的探讨，确定了最优工艺条件，并验证了最优工艺条件。MC尼龙／纳米碳酸钙复合材料的最优制备工艺条件为：纳米碳酸钙的质量分数为1．0％，催化剂的质量分数为0．15％，活化剂的质量分数0．36％，模具温度为160℃。     

尼龙-6的拉伸多次屈服行为及球晶形态的研究

研究了不同拉伸速度下尼龙-6的多次屈服成颈行为,并采用生物显微镜研究了尼龙-6的球晶形貌。结果表明：在拉伸速率低于50m／min的条件下,可观察到尼龙-6明显的多次屈服成颈行为,这应与拉伸条件下球晶演变形成的微纤维的缺陷有关：采用生物显微镜,可观察到尼龙-6球晶中的发射状微纤、球晶形貌和晶界。     

The Influence of Interfacial Adhesion on the Predicted Young's Modulus of Mica-Reinforced Nylon-6

Particle-filled polymer composites have become attractive because of their wide applications and low cost. Various factors influence the mechanical properties of thermoplastic composites. Of these, the aspect ratio of the reinforcement, interfacial adhesion, and binder content are the most important. Other than these, the particle size and particle size distribution of the reinforcement also influence the mechanical properties. In this paper, injection molded mica composites were investigated, using nylon-6 as a binder. Many models are available to predict the Young's modulus of the composites. A theoretical model for Young's modulus by Lewis and Nielsen was used to predict the Young's modulus of the composites. Tetra isopropyl titanate (TYZOR® TPT) was used to modify the adhesion between the reinforcement and the binder by mixing it with the reinforcement prior to compounding. It was found that Young's modulus was greater than the predicted values.     

季鏻盐改性黏土及其对尼龙6性能的影响

首先采用季鏻盐作为插层剂对钠基黏土进行插层改性,制备有机黏土,再与尼龙6熔融共混,成功制备尼龙6/有机黏土纳米复合材料。XRD测试结果表明:季鏻盐改性黏土可以与尼龙6形成纳米复合材料。转矩流变仪的测试结果显示:有机黏土能够略微改善尼龙6树脂的加工性能。力学性能的测试结果显示:有机黏土的含量在3%~5%范围内其,纳米复合材料的力学性能最佳。     

In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers

Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC₆H₄-NH₂) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.     

Rheology of Short Nylon-6 Fiber Reinforced Styrene-Butadiene Rubber

ABSTRACT

The rheological characteristics of short Nylon-6 fiber reinforced styrene butadiene rubber (SBR) were studied using a capillary rheometer. The study was done with respect to the effect of shear rate, fiber concentration, and temperature on shear viscosity and die swell. All the melts showed pseudoplastic nature, which decreased with increasing temperature. Shear viscosity increased in the presence of fibers. Introduction of fiber reduces the temperature sensitivity of the rubber matrix. A reduction in die swell was found in presence of fibers.     

Toughenability of Nylon-6 with CaCO3 filler particles: new findings and general principles

The mechanical behavior of Nylon-6 blends modified by two types of CaCO₃ particles of 0.7 and 3.5 μm diameter with particle volume fractions ranging from 0.05 to 0.28 was studied between −30 and 60°C in slow tension, and at 20°C in bending impact. Additional experiments were also carried out at 20°C to determine the plane stress fracture toughness of the blends in Single-Edge-Cracked-Plate configurations; all fracture behavior was followed extensively by SEM fractography.

Experiments demonstrated that the particles are attached to the matrix only through a differential thermal–contraction–pressure and particle separation preceded plastic response in all instances. As a consequence of the above ease in debonding, the yield strengths of the blends drop systematically with increasing particle concentration.

In slow tension all blends showed a well defined plastic stretching response following necking, but the stable post-necking stretch was severely limited by an overabundance of large particle clusters which acted as super-critical flaws to initiate premature termination of stretching. The present findings show that in these blends with their high plastic resistances, critical flaw sizes that trigger brittle response are in the range of 8–12 μm, well under the sizes of many of the particle clusters encountered in the blends.

In contrast with the attractively tough response of the rubber modified Nylon-6 blends of Murato lu et al. [Polymer 36 (1995) 921; Polymer 36 (1995) 4771] all present blends showed only disappointing brittle behavior under Izod impact conditions. This was traced to the development of substantial levels of triaxial tensile stresses arising from only partial separation of rigid particles from the matrix in the early phases of impact response.

Based on the new findings a number of general principles on toughenability with both compliant and rigid particle modification are presented and supported by simple micro mechanical models.     

Effects of processing history and annealing on polymorphic structure of nylon-6/montmorillonite nanocomposites

The effects of processing history and annealing treatment on the thermal property and polymorphic structure of nylon-6/clay nanocomposites (NCNs) have been investigated. The nanocomposites, including intercalated and exfoliated ones, were prepared by extruding nylon-6 (N6) with sodium montmorillonite (Na-MMT) or organo-montmorillonite (OMMT), respectively. DSC analysis revealed multiple melting endotherms in either the extruded or the injection-molded N6 and NCNs samples. It has been observed that a small exothermic peak around 195 °C just before the lower melting peak in the skin regions. We demonstrated that this sub-T_m transition was directly related to the processing-induced shear stresses. WAXD analysis was further performed to characterize the polymorphic structure of injection-molded N6 and NCNs before and after annealing. Annealing at a temperature (80 °C) above the T_g of N6 resulted in increase of the absolute content of γ-form in the skin regions and of the relative content of γ-form in the core regions of NCNs. In particular, annealing only leaded to increase the fraction of γ-form in the exfoliated N6/OMMT nanocomposites, which might be related to a confining effect of MMT platelet on the polymer chains mobility.     

Rheological Characteristics of Short Nylon-6 Fiber Reinforced Styrene Butadiene Rubber Containing Epoxy Resin as Bonding Agent

ABSTRACT

The rheological characteristics of short Nylon-6 fiber–reinforced Styrene Butadiene rubber (SBR) in the presence of epoxy resin–based bonding agent were studied with respect to the effect of shear rate, fiber concentration, and temperature on shear viscosity and die swell using a capillary rheometer. All the composites containing bonding agent showed a pseudoplastic nature, which decreased with increasing temperature. Shear viscosity was increased in the presence of fibers. The temperature sensitivity of the SBR matrices was reduced on introduction of fibers. The temperature sensitivity of the melts was found to be lower at higher shear rates. Die swell was reduced in the presence of fibers. Relative viscosity of the composites increased with shear rate. In the presence of epoxy resin bonding agent the temperature sensitivity of the mixes increased. Die swell was larger in the presence of bonding agent.     

Crystal structure and thermodynamic parameters of Nylon-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density ρ_c, amorphous density p_a equilibrium heat of fusion δH°_m and equilibrium melting temperature T°_m. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity. ρ_c and ρ_a were estimated to be 1.098 and 1.003 g/cm³ respectively. The ρ_c obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 Å, b = 5.4 Å, c = 27.8 Å, α = 49°, β = 77°, γ = 63.5°. The unit cell contained one monomeric unit, the space group was P1 , and the correct value of ρ_c was 1.135 g/cm³. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. δ H°_m was estimated to be 244.0 J/g by extrapolation of δH°_m in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V = 1/ρ_c). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T_m-T_c method failed in determining T°_m and a Kamide double extrapolation method was adopted. The T°_m value so obtained was 487 K.     

High-modulus fibres of nylon-6 prepared by a dry-spinning method

Nylon-6 filaments with tensile strengths at break up to 1 GPa and initial moduli in the range of 16 to 19 GPa have been produced by dry-spinning of solutions of nylon-6 in cosolvent mixtures of formic acid and chloroform followed by hot-drawing at 200°C–240°C. Tensile strengths and elastic moduli of the nylon-6 fibres were strongly dependent on the draw ratio, on the molecular weight of the polymer, on the polymer concentration in the spinning solution and on concentration of nonsolvent in the spinning solution. At high concentrations of nonsolvent in the spinning solution, the as-spun fibres of nylon-6 were composed of ball-like structural units, formed possibly due to the liquid-liquid phase separation in the polymer/solvent/nonsolvent ternary system. Formation of ball-like structures reduced the ultimate mechanical properties of hot-drawn fibres of nylon-6.     

Nanoindentation and morphological studies on injection-molded nylon-6 nanocomposites

The nanoindentation behavior and morphology of the injection-molded specimens of nylon-6 (PA6)/clay nanocomposites prepared by melt-compounding have been studied in present study. The elastic and plastic properties as well as creep behavior of PA6 and its nanocomposites are comparatively evaluated as the function of clay loading by using nanoindentation technique. The anisotropic characteristics in mechanical properties are studied by indenting the injection-molded specimens in two different directions (i.e. parallel and perpendicular to the injection direction). The uneven distribution of both the clay nanofiller and the crystallinity of the polymeric matrix induced by melt-processing leads to the variation of the mechanical property of the nanocomposites in certain directions and locations within the molded specimens. The microstructural and morphological changes of PA6 upon incorporating with clay nanofiller are evidenced by transmission electron microscopy and small-angle X-ray scattering, which are closely correlated with the anisotropy of the mechanical properties observed by nanoindentation.     

Relation between ductility and segmental mobility of nylon-6

High-resolution solid-state ¹⁵N and ¹³C NMR and dynamic mechanical measurements were carried out for solution grown crystals of the α- and γ-forms of nylon-6 to understand the relation between segmental mobility including interchain interactions and ductility of polyamides. The ductility, in the temperature range of 100-180 °C, was lower for the α-crystals than for γ-crystals. ¹⁵N chemical shift revealed that the hydrogen bonding was stronger for the γ-crystals than for α-crystals. In addition, lower mobility of NH group in the γ-crystals than in α-crystals was shown by results. The results suggest that the ductility of nylon-6 could not be simply related to the strength of hydrogen bonding. Highly crystalline films of aggregates of solution grown α-crystals and γ-crystals showed no crystalline relaxation in the temperature dependence of dynamic mechanical loss factor, suggesting an existence of strong intermolecular interactions in the crystalline regions although data indicated that the mobility of methylene units was higher in the γ-crystals than in α-crystals. Information on the large-scale chain dynamics in the crystalline regions might be necessary to understand the low ductility of polyamides.     

Effect of lactic acid on polymer crystallization chain conformation and fiber morphology in an electrospun nylon-6 mat

The role of lactic acid (LA) on the polymer crystallization chain conformation and the surface modification of the electrospun nylon-6 fibers were examined. The effect of different amounts of LA on the polymer crystallization chain conformation of nylon-6 mat was evaluated using XRD, FT-IR and Raman spectroscopy whereas the surface modification of the electrospun mats was examined by FE-SEM, contact angle and mechanical properties measurement. It was found that the transition of meta-stable γ-form into the thermodynamically stable α-form was achieved by increasing the amounts of LA in the blend mixture. The adhesive property of LA was found to be responsible for the transformation from non-bonded to the point-bonded structure of nanofibers in the electrospun nylon-6 mat. The resultant LA/nylon-6 hybrid mat with improved hydrophilicity and mechanical properties may be a potential candidate for tissue scaffold.     

尼龙6/纳米钛合金复合材料的制备及结构

将经过有机化处理的纳米钛合金粉体与尼龙6通过熔融共混制备成了尼龙6/纳米钛合金复合材料。X-射线衍射和透射电镜显示,在钛合金粉体含量低时,钛合金粉体在尼龙6基体中实现了纳米尺度的分散,但随钛合金粉体含量增加,团聚现象明显增加;红外光谱(IR)分析和Molau试验表明,复合材料中钛合金粉体与周围尼龙6分子间存在某种键合;实验结果还表明,钛合金粉体对尼龙6基体的化学结构和结晶形态没有产生明显的影响。     

Fibrillation of thermotropic liquid crystalline polymer enhanced by nano-clay in nylon-6 matrix

The influence of well-dispersed nano-clay filler on the morphology of thermotropic liquid crystalline polymer (TLCP) in nylon-6 matrix was investigated by melt extrusion process. The good dispersion of clay in the hybrid blends was confirmed by X-ray diffraction, transmission electron microscopy and rheological measurement. Morphological observation showed that the clay platelets had dramatic influences on the dispersion and deformation of TLCP phase. The TLCP droplets got smaller at the clay content ≤3 wt%, and deformed into fibrils at the clay content up to 5 and 7 wt%. The morphology evolution of TLCP in the hybrid blends, especially at 7 wt% of clay loading, was consistent well with the prediction based on the micro-rheology parameters such as the viscosity ratio of the dispersed phase to the matrix (η_d/η_m) and the ratio of capillary number to the critical capillary number (Ca/Ca_crit). This enhanced fibrillation of TLCP droplets was attributed to the role of nano-clay particles as a compatibilizer to improve the interfacial adhesion and to suppress the interfacial slip between TLCP and nylon phases in the melt, so that the shear stress was effectively transferred to the dispersed TLCP phase.     

Properties of nylon-6-based composite reinforced with coconut shell particles and empty fruit bunch fibres

Novel natural fibre composites of nylon-6 reinforced with coconut shell (CS) particles and empty fruit bunch (EFB) fibres have been investigated. Fillers were alkali treated before melt compounding with nylon-6. Mechanical, thermal and rheological properties of composites were measured. Tensile modulus was found to improve with both fillers up to 16% for nylon-6/CS composite and 10% for nylon-6/EFB composite, whereas a moderate increase in tensile strength was observed only with CS composites. Differences in the strengthening mechanisms were explained by the morphology of the two fillers, empty fruit bunch fibres having a weaker cellular internal structure. Observation of composite morphology using SEM showed that both fillers were highly compatible with nylon-6 due to its hydrophilic nature. Both fillers were found to cause a slight drop in crystallinity of the nylon matrix and to lower melt viscosity at typical injection moulding strain rates. Moisture absorption increased with addition of both fillers.