Morphology of Nylon-6 blends with styrenic polymers

The morphology of blends of styrenic polymers in a matrix of 75% Nylon-6 prepared in a Brabender Plasti-Corder was examined by scanning electron microscopy. Styrene/acrylonitrile copolymers (SAN) form smaller particles as the AN level increases owing to the corresponding decrease in the SAN–polyamide interfacial tension. Various styrenic polymers containing functional groups, maleic anhydride or oxazoline type, that can react with Nylon-6 during melt processing were added to the SAN phase which also led to a decrease in the particle size owing to the graft copolymer formed in situ. The effects of functional group type, amount of functional groups per chain, amount of functional polymer added, and the miscibility of the styrene/maleic anhydride (SMA) and SAN copolymers on the morphology of the styrenic phase in the Nylon-6 matrix are described. © 1992 John Wiley & Sons, Inc.     

Thermal properties and phase transitions in blends of Nylon-6 with silk fibroin

The thermal and structural properties of binary blends of Nylon-6 (N6) and a chemically related biopolymer, Bombyx mori silk fibroin (SF), are reported in this work. Homopolymers and blends, in composition ratios of N6/SF ranging from 95/05 to 70/30, were investigated by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and wide angle X-ray scattering (WAXS). Silk fibroin typically degrades at temperatures just above 210°C, which occurs within the melting endotherm of N6. In TG studies, the measured mass remaining was slightly greater than expected, indicating the blends had improved thermal stability. No beta sheet crystals of SF were detected by FTIR analysis of the Amide I region. Strong interaction between N6 and SF chains was observed, possibly as a result of formation of hydrogen bonds between N6 and SF chains. DSC analysis showed that the addition of SF to N6 caused a decrease in the crystallization temperature, the melting temperature of the lowest melting crystals and the crystallinity of N6. Furthermore, the α-crystallographic phase dominates and the γ-crystallographic phase was not observed in N6/SF blends, in contrast to the homopolymer N6, which contains both phases. We suggest that the addition of SF might result in changes of the chain extension of N6, which lead to the appearance of α-rather than γ-phase crystals.     

Investigation of the rigid amorphous fraction in Nylon-6

A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χ _c, χ _MA, χ _RA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow the devitrification of the rigid amorphous fraction to be examined. We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief heating above this lower endotherm and immediately quenching in LN₂-cooled glass beads, the glass transition temperature and χ _RA decrease substantially, χ _MA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χ _RA to increase, and χ _MA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid amorphous fraction. Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξ_A) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of some of the RAF leads to the broadening of the glass transition region and shift of T _g.     

尼龙-6 18的晶型转变研究

以偶偶尼龙-6 18为例, 通过示差扫描量热分析(DSC), 广角X射线衍射(WAXD)与傅里叶变换红外光谱(FTIR)等方法研究了其Brill转变的过程, 探索了脂肪族聚酰胺的晶型转变的本质. X射线衍射结果表明， 随着温度的升高, 尼龙-6 18由三斜晶系转变为假六方晶型, 同时其DSC曲线上出现一个较宽的吸热峰. 红外光谱结果表明, 在其晶型转变过程中, 晶体内氢键强度逐渐减弱, 与酰胺键相连的C—C和C—N键发生扭曲. 酰胺基团之间的亚甲基链段的振动逐渐增强, 部分亚甲基单元由反式构象变成旁式构象, 最后整齐排列的亚甲基链段逐渐变得无序化.     

Hydrophilic Treatment of the Dyed Nylon-6 Fabric using High-density and Extensible Antenna-coupling Microwave Plasma System

High density and well surface-distributed oxygen microwave plasma with an extensible antenna-coupling design was utilized to modify a densely weaved and large-surface-area Nylon-6 fabric within a short treatment time. Plasma pretreatment and subsequent acrylic acid (AAc) or 2-hydroxyethyl methacrylate (HEMA) grafting process were studied and optimized at the stage after dyed and finished procedure. The monomer-grafted dyed Nylon-6 fabrics evolved lasting hydrophilic properties and thereafter created or improved surface properties such as water diffusion, drainage, moisture regain and water absorbency, in different degrees. The pHEMA-grafted sample exhibited minor effect in color perception, which was also much hydrophilic than the pAAc-grafted one. Based upon surface analyses and wetting assessment, the penetration of HEMA monomer into the plasma-treated fabric matrix contributed to the facilitation of wetting properties. This work accordingly ensures such plasma-induced system to incorporate with the pattern of hydrophilic properties on the analogous textiles without interrupting their finishing process.     

微孔尼龙-6膜的催化水解改性和DNA芯片的原位合成

基因芯片常用的载体有玻璃片、硅片、聚丙烯膜、硝酸纤维膜和尼龙膜等[1～ 4 ] .其中有机高分子膜载体由于自身荧光背景较强 ,寡核苷酸探针或 c DNA片段通常用点样法固定 ,并以同位素标记的靶基因与其杂交 ,用放射显影进行检测 ,探针密度不高且损害人体健康 .生物分子纳米标记和时间分辨荧光等检测技术可以非常有效地克服载体荧光背景[5,6 ] .因此 ,若将高分子材料进行改性 ,使其表面带有羟基、氨基和巯基等活性基团并应用于 DNA的原位合成 ,再结合新开发的生物分子标记和检测方法 ,将拓展生物芯片基材选择范围 ,并开发出新的生物芯片制…     

Novel filled polymer composites prepared from in situ polymerization via a colloidal approach: I. Kaolin/Nylon-6 in situ composites

A mineral-filled in situ composite was prepared by a colloidal approach by first suspending kaolin filler particles in aqueous caprolactam, and then polymerizing caprolactam in situ at high pressure and temperature. The purpose of this colloidal in situ polymerization is to improve particle dispersion and to enhance interaction of the filler to the polymer matrix. X-ray diffraction studies of the in situ kaolin/Nylon-6 composites revealed that the x-ray peak corresponding to the α-crystal form of Nylon-6 diminished with increasing kaolin loading, while the γ-crystal structure became more pronounced. The degree of crystallinity of Nylon-6 remained fairly unchanged with the kaolin loading level in the in situ composites. Calorimetric and dynamic mechanical studies exhibited that the glass transition temperature of the resulting composite increased significantly with increase in kaolin concentration, suggesting strong filler-matrix interaction at the kaolin/Nylon-6 interface. Scanning electron microscopic (SEM) results showed uniform filler dispersion in the in situ composites relative to the conventional melt-mixed composites. Modulus and tensile strength of these in situ composites were found to be distinctively higher than that of the conventional melt-mixed kaolin/Nylon-6 composites. However, as typical for composite materials, drawability and fracture toughness decreased with increasing kaolin loading. © 1996 John Wiley & Sons, Inc.     

醋酸乙烯酯接枝尼龙-6的研究

以ＢＰＯ为引发剂,用醋酸乙烯酯（ＶＡｃ）在尼龙 ６表面进行接枝反应。测定了反应时间、反应温度、单体浓度和引发剂浓度等对接枝率的影响。通过红外光谱、差热分析对接枝共聚物进行了表征。     

Thermal dehydration of dipotassium tetraborate tetrahydrate and crystallization of amorphous dehydration product

Summary As one of the typical examples of producing an amorphous dehydration product, the thermal dehydration process of K₂B₄O₇·4H₂O was subjected to thermoanalytical and morphological studies. An anhydrous glass was formed via three distinguished dehydration stages. The overall thermal dehydration process was characterized as a self-induced sol-gel process to form anhydrous glass. The as produced anhydrous glass exhibited glass transition at around 700 K and subsequently crystallized via two consecutive exothermic peaks at around 770 and 900 K. The final crystallization product, triclinic K₂B₄O₇, melted at 1072 K.     

Diffusion of nonionic azo dyes in nylon-6

Diffusion of 2,4-dinitroaniline and three nonionic azo dyes in Nylon-6 film was studied by analysis of the concentration-distance curves (profiles) of penetrants in the polymer. Actual diffusivities D_(c) of penetrants in polymer, diffusion coefficients as a function of the concentration C_f of penetrant in polymer, were calculated from the profile. It was found that D_(c) is almost constant or decreases gradually with decreasing C_f in the range of high-medium C_f but decreases appreciably with decreasing C_f at low C_f. The change in D_(c) with C_f was explained in terms of the dual-mode sorption-diffusion model. The penetrants diffuse in the polymer as two distinct species, i.e., a dissolved species and an adsorbed species. The former is the penetrant taken up by the polymer by a partition mechanism (dissolved species) and the latter is that taken up by Langmuir sorption (adsorbed species). The actual diffusivity D_P(c) of the dissolved species decreases with decreasing C_f. While the actual diffusivity D_L(c) of the adsorbed species normally increases gradually with decreasing C_f. D_P(c) is usually larger than D_L(c). © 1993 John Wiley & Sons, Inc.     

Interlaminar Fracture Toughness of Carbon Fiber/Epoxy Composites using Short Kevlar Fiber and/or Nylon-6 Powder Reinforcement

Mode I (G_IC) and Mode II (G_IIC) interlaminar fracture toughness of carbon-fiber/epoxy composites have been investigated as a function of the amount of short Kevlar-29 fiber (SKF) and/or Nylon-6 powder (N6P) between continuous fiber layers. G_IIC increased with increasing crack length as a consequence of the presence of SKFs bridging in the wake of propagating crack. G_IIC of SKF alone could reach the maximum at an intermediate amount of SKF. G_IIC of SKF and N6P was lower than that of SKF alone because N6P prevented the orientation of SKF to out-of-plane. The extent of SKF's bridging phenomenon may be influenced by the amount and orientation of SKF. G_IC showed no significant effect with SKF and uniform irrespective of crack length. Scanning electron microscopy after G_IIC test showed that new surfaces were created by extensive fiber bridging, pull-out and fracture of SKF in random direction without any fixed pattern. © 1997 John Wiley & Sons, Ltd.     

Thermal investigations of dehydration of lanthanide(iii) 5-nitroanthranilates

The 5-nitro-2-anthranilates of lanthanum(III), samarium(III), terbium(III), erbium(III) and lutetium(III) were obtained as hydrates having 2.5 mol of water molecules per 1 mol of compound. The compounds are isostructural. The processes of dehydration and rehydration were investigated. The first step of dehydration does not cause the change of crystal structure. The entire dehydration gives anhydrous compounds with different structure than the structure of hydrates. However, the dehydration of La, Sm, Tb and Er is reversible - the rehydration process gives the complexes having the same crystal structure as the initial compounds. Only the anhydrous lutetium complex under the influence of moisture does not give the starting compound. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal evolution of microporous nitroprussides on their dehydration process

Divalent transition metal nitroprussides form a family of microporous materials which lose their crystallization water (coordinated and zeolitic) below 100°C and then remain stable up to above 150°C. The dehydration process of representative samples in their stable phases was studied by thermo-gravimetry (TG) and differential scanning calorimetry (DSC). The copper complex dehydrates in a single step through a practically irreversible process. For cadmium and cobalt complexes the water evolution on heating takes place in two stages. The first one, where only zeolitic waters are removed, is dominated by a diffusion mechanism while, during the loss of the strongly bonded waters (second stage) the material framework effect is added. The involved activation energy and its dependence on the conversion degree were estimated evaluating the thermo-gravimetric data according to an isoconversion model.     

FTIR separation of nylon-6 chain conformations: Clarification of the mesomorphous and γ-crystalline phases

Specific infrared absorptions for each form of Nylon-6 have been indentified. Quenched films were prepared by melt casting and converted in turn to the α-crystalline and γ-crystalline structures. The films were examined using Fourier transform infrared spectroscopy (FTIR) with the attenuated total reflection configuration and by X-ray diffractometry. The FTIR spectrum of the pure mesomorphous component of the quenched film was calculated by subtracting away the contribution of α-crystalline peaks present due to incomplete quenching. A curve-fitting procedure was applied to the pure mesomorphous and gamma crystalline spectra. Several peaks in the mesomorphous spectrum are observed to develop a shoulder upon conversion to the γ-crystalline form. This is due to the extra gauche character imparted to the C? N bond between the methylene unit and the amide group. These and other band assignments were confirmed by analysis of model compounds.     

聚对苯二甲酰对苯二胺对尼龙-6共混改性的影响

<正> 聚对苯二甲酰对苯二胺(PPTA)是一种棒状的刚性高分子,由它的液晶溶液可制得高强度、高模量、耐高温纤维,这种纤维可作为增强剂以制备高性能的复合材料。若将刚性链高分子以近于分子水平分散到柔性链高分子中,可期望得到性能良好的分子复合材     

尼龙6固态后缩聚工艺研究

对尼龙6萃取切片及干燥切片的固态后缩聚工艺进行了研究。研究了聚合温度、聚合时间、氮气流速等聚合条件对固态后缩聚的影响，并测定了固态后缩聚前后切片结晶度，水分以及分子量分布的变化。实验表明：可以以尼龙6萃取切片为起始切片进行固态聚合，其聚合时间24h，聚合温度185℃。固态后缩聚后切片的分子量分布略有增加。     

Preparation of Nylon-6 Particles in Ionic Liquids

Summary: Utilizing the thermal stability of ionic liquid, micrometer-sized Nylon-6 particles were successfully prepared by hydrolytic polymerization of ε-caprolactam at high temperature with polyvinyl pyrrolidone as stabilizer in ionic liquids, 1-butyl-3-methyl imidazolium tetrafluoroborate, [Bmim][BF₄] and N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoro-methanesulfonyl)amide, [DEME][TFSA]. The obtained particles had a unique shape because Nylon-6 is a crystalline polymer. Viscosity-average molecular weights of Nylon-6 prepared in [Bmim][BF₄] and [DEME][TFSA] at 180 °C for 48 h were 4200 and 2200, respectively.     

Fermi resonance in the infrared spectra of Nylon-11

Nylon-11 is prepared by casting from the solvents trifluoroacetic acid and m-cresol and by melt-crystallization. Room-temperature infrared spectra are compared in terms of possible crystal structures. The spectra are examined for the presence of Fermi resonance which occurs between the N-H stretching fundamental mode and the overtone and combination modes of the amide I and II vibrations. An analysis of peak frequencies and intensities is used to provide support for the assignment of the amide II overtone and the amide I + II combination modes. A newly observed peak in the spectra is assigned to the amide I overtone. Symmetry considerations are discussed which predict the resonance of the overtone and combination modes with the N-H stretching fundamental. © 1992 John Wiley & Sons, Inc.     

Sorption and transport of water in nylon-6 films

Sorption and transport properties of water through films of Nylon-6 were obtained at 5, 23, and 40°C. Commercially available films were used and a Cahn electrobalance was employed for measuring the water uptake by the polymer samples. Values of the water sorption isotherms are accurately described by the Langmuir/Flory-Huggins dual-mode sorption model. At water activity values below 0.15, the volume fraction of water described by the Langmuir portion of the model was greater than the Flory-Huggins population. Solubility and diffusion coefficients of water, as well as the diffusion activation energy and enthalpy of dissolution of water for Nylon-6, were determined from the sorption experiments. Values obtained support the hypothesis of a bimodal water sorption mode, and the formation of water clusters. © 1994 John Wiley & Sons, Inc.     

The in situ reactive compatibilization of nylon-6/polystyrene blends using anhydride functionalized polystyrenes

Nylon-6/polystyrene (PS) blends were reactively compatibilized by addition of various anhydride functionalized polystyrenes. The morphology of the blends was examined using a scanning electron microscopy (SEM) technique. The particle size of the dispersed styrenic phase was about 3.2 μm for the uncompatibilized 8/2 Nylon-6/PS blend while those of the compatibilized blends were decreased by as much as two orders of magnitude depending on the amount and type of the functionalized polystyrene (FPS) added. Several low-molecular weight polystyrenes with terminal anhydride groups, prepared by two different functionalization methods, were examined. The effect of molecular weight on particle size reduction depended on the basis of comparison, mass of additive, or moles of anhydride units. A high-molecular weight random copolymer of styrene and maleic anhydride was most effective when compared on a mass basis. The increase in adhesion between the Nylon-6 and the styrenic phases caused by the in situ reaction was evaluated by a lap shear technique. The free polystyrene, Nylon-6, and Nylon-FPS copolymer formed were separated by solvent extraction technique using formic acid and toluene. The extent of coupling reaction between the functionalized polystyrenes and Nylon-6 ranged from 25 to 43%. © 1992 John Wiley & Sons, Inc.