Morphology and structure of nylon‐2,14 single crystals from dilute solution

A perfect single crystal of nylon‐2,14 was prepared from 0.02% (w/v) 1,4‐butanediol solution by a “self‐seeding” technique and isothermal crystallization at 120 and 145 °C. The morphology and structure features were examined by transmission electron microscopy with both image and diffraction modes, atomic force microscopy, and wide‐angle X‐ray diffraction (WAXD). The nylon‐2,14 single crystal grown from 1,4‐butanediol at 145 °C inhabited a lathlike shape with a lamellar thickness of about 9 nm. Electron diffraction and WAXD data indicated that nylon‐2,14 crystallized in a triclinic system with lattice dimensions a = 0.49 nm, b = 0.51 nm, c = 2.23 nm, α = 60.4°, β = 77°, and γ = 59°. The crystal structure is different from that of nylon‐6,6 but similar to that of other members of nylon‐2Y. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1913–1918, 2002     

Water‐assisted melt compounding of nylon‐6/pristine montmorillonite nanocomposites

An exploratory pioneering study on the fabrication of nylon‐6/montmorillonite (MMT) nanocomposites with the aid of water as an intercalating/exfoliating agent via melt compounding in a twin‐screw extruder was conducted. Commercial nylon‐6 pellets and pristine MMT powder were directly fed into the hopper of the extruder. Water was then injected into the extruder downstream. After interactions with the nylon‐6 melt/pristine MMT system, water was removed from the extruder further downstream via a venting gate. As such, no third‐component residual was left within the extrudates. Transmission electron microscopy micrographs showed that pristine MMT was uniformly dispersed in the nylon‐6 matrix. The contact time between water and the nylon‐6/pristine MMT system inside the extruder was so short that nylon‐6 was subjected to very little hydrolysis, if any. The resultant nanocomposites showed higher stiffness, superior tensile strength, and improved thermal stability in comparison with their counterparts obtained without water assistance and the nylon‐6/organic MMT nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1100–1112, 2005     

Fracture toughness of nylon‐6 blends with maleated rubbers

The fracture toughness of blends of nylon‐6 with maleated ethylene–propylene rubber and maleated styrene/hydrogenated butadiene/styrene triblock copolymer was investigated with a single‐edge‐notched three‐point‐bending instrumented Dynatup test. The blends for which the rubber particle size was less than 0.7 μm fractured in a ductile manner over the whole range of ligament lengths, whereas the blends with particles larger than 0.7 μm showed a ductile‐to‐brittle transition with the ligament length. In this regime, ductile fracture was observed for specimens with short ligaments, whereas brittle fracture was seen for those with long ligaments. The ductile fracture behavior was analyzed with the essential‐work‐of‐fracture model, whereas linear elastic fracture mechanics techniques were used to analyze the brittle fracture behavior. The fact that the ductile fracture energy was larger for the blends with the styrene/hydrogenated butadiene/styrene triblock copolymer than for those with ethylene–propylene rubber was due to the larger dissipative energy density of the blends based on the styrene/hydrogenated butadiene/styrene triblock copolymer. Both the critical strain energy release rate (G_IC) and the plane‐strain critical stress intensity factor (K_IC) increased as the rubber particle size decreased for both blend systems. The G_IC and K_IC parameters had similar values, regardless of the rubber type, when the rubber particle size was fixed. The transition ligament length was near the size criterion for plane‐strain conditions for both blend systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1739–1758, 2004     

Ferroelectric behavior and polarization mechanism in odd‐odd polyamide 11,11

Ferroelectric and piezoelectric behavior in odd‐odd polyamide 11,11 are successfully detected for the first time. The maximum coercive field (E_c) of 90 MV/m, and a remnant polarization (P_r) of 40 mC/m² are obtained at room temperature. A piezoelectric strain coefficient (d₃₃) value as high as ?3.9 pC/N has been found in stretched polyamide 11,11 film. The structural change of samples before and after poling is investigated by wide‐angle X‐ray diffraction patterns, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The results indicate that the nature of the ferroelectricity originates from amide group dipoles in the γ‐form crystal regions. Hysteresis behavior appears to result from the crystallites reversal mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1094–1099     

Polymorphism of nylon‐6 in multiwalled carbon nanotubes/nylon‐6 composites

The effects of pristine and amino‐functionalized multiwalled carbon nanotubes (MWNTs) on the crystallization behaviors of nylon‐6 were investigated by differential scanning calorimetry and X‐ray diffraction. The results indicate the presence of polymorphism in nylon‐6 and its composites, which is dependent on the MWNTs concentration and the cooling rate. More MWNTs and slow cooling from the melt favors the formation of α crystalline form. With the increase in cooling rates, the crystallinity of neat nylon‐6 decreases, and that of the composites decreases initially but increases afterward. Moreover, the degree of crystallinity of the composites is higher than neat nylon‐6 under high cooling rates, counter to what is observed under low cooling rates. The heterogeneous nucleation induced by MWNTs and the restricted mobility of polymer chains are considered as the main factors. Furthermore, addition of MWNTs increases the crystallization rate of α crystalline form but amino‐functionalization of MWNTs weakens this effect. The influence of thermal treatment on the crystalline structure of MWNTs/nylon‐6 composites is also discussed. A γ–α phase transition takes place at lower temperature for MWNTs/nylon‐6 composites than for nylon‐6. The annealing peaks of the composites annealed at 160 °C are higher than that of neat nylon‐6, and the highest annealing peak is obtained for amino‐functionalized MWNTs/nylon‐6 composites. This phenomenon is closely related to the different nucleation and recrystallization behaviors produced by various MWNTs in confined space. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1499–1512, 2006     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

Structural characteristics and moisture sorption behavior of nylon‐6/clay hybrid films

The structure of nylon‐6 hybrids with synthetic or natural clays was investigated for melt‐pressed films with Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry in comparison with the nylon‐6 homopolymer. In contrast to the development of familiar α‐form crystals in plain nylon‐6 film, the hybrid films produced γ‐form crystals when nylon‐6 was conjugated with synthetic mica, whereas the hybridization with natural montmorillonite gave rise to both α‐ and γ‐crystalline modifications. The degree of crystallinity of the nylon‐6 hybrid with synthetic mica was the highest of the three series. Moisture sorption isotherms obtained for these nylon‐6‐based films were all typically sigmoid‐shaped, although the prevalence of a higher crystallinity in the hybrid samples lowered the degree of moisture regain. The sorption behavior was analyzed well in terms of the parameters of a Brunauer–Emmett–Teller multiplayer adsorption model and a Flory–Huggins treatment. It was also observed that the cluster formation of the water adsorbed into the nylon‐6 matrix tended to be restricted by the hybridization with clay. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 479–487, 2002; DOI 10.1002/polb.10106     

Morphological characterization of nylon‐6 nanocomposite following a large‐scale simple shear process

A commercial grade nylon‐6/clay nanocomposite (from Ube industries) is subjected to a large‐scale simple shear orientation process and the resulting morphology is investigated. Both the orientation and aspect ratio of nanoclays, which can be altered by the simple shear process, are studied. The incorporation of well‐dispersed nanoclays into the nylon matrix greatly reduces the nylon chain mobility as well as the percent crystallinity. Two types of lamellar orientation have been found, as revealed by small‐angle X‐ray scattering. One type of lamellae is oriented ～41° away from the clay surface, whereas the simple shear process induces another weakly preferred lamellar orientation nearly perpendicular to the clay surface. The formation of the above lamellar orientations appears to be related to both orientation of the clay in the nanocomposite and the simple shear process. The possible molecular mechanisms leading to the final morphology of the nylon‐6/clay nanocomposite is discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3555–3566, 2005     

Effect of silver nanoparticles on the dynamic crystallization behavior of nylon‐6

The effect of introducing silver nanoparticles on the rheological properties and dynamic crystallization behavior of nylon‐6 was investigated. The nanocomposites showed slightly higher viscosity than pure nylon‐6 in the low‐frequency range even at an extremely low loading level of the silver particles (0.5–1.0 wt %). The nanoparticles had a more noticeable effect on the storage modulus than on the loss modulus of a nylon‐6 melt and reduced its loss tangent. They increased the crystallization temperature of nylon‐6 by about 14 °C and produced a sharper crystalline peak. The silver nanoparticles promoted the crystallization of nylon‐6, and their effect on the dynamic crystallization of nylon‐6 at 200 °C was more notable at a lower shear rate and at 190 °C at a higher frequency. Nylon‐6 produced large spherulitic crystals, but the nanocomposites showed a grainy structure. In addition, the silver nanoparticles reduced the fraction of the α‐form crystal but increased that of the γ‐form crystal. The nanocomposites crystallized at 190 °C showed a lower melting temperature than nylon‐6 by about 3 °C, whereas the nanocomposites crystallized at 200 °C showed almost the same melting temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 790–799, 2004     

Effect of EVM/EVA‐g‐MAH ratio on the structure and properties of nylon 1010 blends

The nylon 1010/ethylene‐vinyl acetate rubber (EVM)/maleated ethylene‐vinyl acetate copolymers (EVA‐g‐MAH) ternary blends were prepared. The effect of EVM/EVA‐g‐MAH ratio on the toughness of blends was examined. A super tough nylon 1010 blends were obtained by the incorporation of both EVM and EVA‐g‐MAH. Impact essential work of fracture (EWF) model was used to characterize the fracture behavior of the blends. The nylon/EVM/EVA‐g‐MAH (80/15/5) blend had the highest total fracture energy at a given ligament length (5 mm) and the highest dissipative energy density among all the studied blends. Scanning electron microscopy images showed the EVM and EVA‐g‐MAH existed as spherical particles in nylon 1010 matrix and their size decreased gradually with increasing EVA‐g‐MAH content. Large plastic deformation was observed on the impact fracture surface of the nylon/EVM/EVA‐g‐MAH (80/15/5) blend and related to its high impact strength. Then with increasing EVA‐g‐MAH proportion, the matrix shear yielding of nylon/EVM/EVA‐g‐MAH blends became less obvious. EVM and EVA‐g‐MAH greatly increased the apparent viscosity of nylon 1010, especially at low shear rates. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 877–887, 2009     

Blends of nylon‐6 with phenol‐containing polymers

The miscibility of nylon‐6 with poly(4‐vinylphenol) (PVPh) or poly(1‐hydroxy‐2,6‐methylphenylene) (p‐Cl‐novolac) was studied with differential scanning calorimetry and small‐angle X‐ray scattering techniques. Both PVPh and p‐Cl‐novolac are miscible with nylon‐6 at the molecular level. The presence of the phenolic polymers affects the crystallization of nylon‐6 and suppresses its melting point. PVPh increases the long space order in crystalline nylon‐6 because it increases the thickness of the amorphous layers. In contrast, a small quantity of p‐Cl‐novolac tends to decrease the long space order. It seems that p‐Cl‐novolac distributed in the amorphous regions introduces more order in these regions and makes the amorphous layers thinner. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 841–850, 2001     

Polymer crystalline structure and morphology changes in nylon‐6/ZnO nanocomposites

The influence of ZnO nanoparticles on the crystalline structures of nylon‐6 under different crystallization conditions (annealing at different temperatures from the amorphous solid, isothermal crystallization from the melt at different temperatures, and crystallization from the solution) has been examined with differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared. ZnO nanoparticles can induce the γ‐crystalline form in nylon‐6 when it is cooled from the melted state and annealed from the amorphous solid. This effect of ZnO nanoparticles increases with decreasing particle size and changes under different crystallization conditions. The effects of ZnO nanoparticles on the crystallization kinetics of nylon‐6 have also been studied with DSC. The results show that ZnO nanoparticles have two competing effects on the crystallization of nylon‐6: inducing the nucleation but retarding the mobility of polymer chains. Finally, the melting behavior of the composites has been investigated with DSC, and the multiple melting peaks of composites containing ZnO nanoparticles and pure nylon‐6 are ascribed to the reorganization of imperfect crystals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1033–1050, 2003     

Simulation of solid‐state polycondensation of nylon‐66

A new model of solid‐state polymerization of nylon‐6,6 has been developed. The polymer crystalline fraction is assumed to consist of only repeat units, leaving end‐groups and condensate in the amorphous fraction. Many effects neglected by previous models are considered, such as variable crystallinity, initial moisture and starting molecular weight. This model is compared to experimental data with good agreements. Differential scanning calorimetry graphs show that the crystalline structure phase tends to be increasingly perfect during heat treatment, indicative of the premelting temperature drawing near the melting point up to 14 °C after solid‐state polycondensation with little change of melting point. Copyright © 2000 John Wiley & Sons, Ltd.     

Molecular transport of aromatic hydrocarbons through nylon‐6/ethylene propylene rubber blends: Relationship between phase morphology and transport characteristics

Molecular transport of aromatic hydrocarbons through nylon/ethylene propylene rubber (EPR) blend has been investigated in the temperature range of 25 to 65 °C. The effect of blend ratio on the transport behavior was studied in detail. Nylon/EPR‐50/50 blend shows the lowest uptake among all the systems studied. This behavior is related to blend morphology, density, and crystallinity of the blend composition. The transport property was correlated with the extent of interfacial adhesion in the blends. The effects of temperature and penetrant size on the sorption behavior were examined. Thermodynamic and Arrhenius parameters were evaluated from the diffusion data. Theoretical and experimental diffusion results were compared. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2136–2153, 2000     

Multiple melting and crystallization of nylon‐66/montmorillonite nanocomposites

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with organically modified montmorillonite (MMT). The organic MMT layers were exfoliated in a nylon‐66 matrix as confirmed by wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy. The presence of MMT layers increased the crystallization temperature of nylon‐66 because of the heterogeneous nucleation of MMT. Multiple melting behavior was observed in the nylon‐66/MMT nanocomposites, and the MMT layers induced the formation of form II spherulites of nylon‐66. The crystallite sizes L₁₀₀ and L₀₁₀ of nylon‐66, determined by WAXD, decreased with an increasing MMT content. High‐temperature WAXD was performed to determine the Brill transition in the nylon‐66/MMT nanocomposites. Polarized optical microscopy demonstrated that the dimension of nylon‐66 spherulites decreased because of the effect of the MMT layers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2861–2869, 2003     

Relaxation peak broadening and polymer chain dynamics in aramid‐fiber‐reinforced nylon‐66 microcomposites

The relationship between the parameter of symmetric broadening of the glass‐transition relaxation process and the structure of aramid‐fiber‐reinforced nylon‐66 microcomposites is investigated in this article. The approach is based on a previously derived model that sets a quantitative interrelation between the Cole–Cole parameter α, the relaxation time, and the fractal dimension of a mobile polymer segment. The microcomposite, the dielectric response of which reflects the transcrystallinity effects, indeed exhibits significantly different values, such as higher Kirkwood correlation factor and α exponent values, in comparison with the control materials, and this indicates its different crystalline morphology and perhaps lower order in the amorphous phase. However, at this stage, it is still difficult to establish a quantitative relationship with the polymer chain dynamics. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 217–223, 2003     

Synthesis and characterization of polyurethane–urea nanoparticles containing methylenedi‐p‐phenyl diisocyanate and isophorone diisocyanate

Water‐based polyurethane–urea (WPUU) nanoparticles containing 4,4′‐methylenedi‐p‐phenyl diisocyanate (MDI) and isophorone diisocyanate (IPDI) were synthesized by a stepwise prepolymer mixing process, that is, the consecutive formation of hydroxyl‐terminated and isocyanate‐terminated polyurethane prepolymers. The reaction behavior, chemical structure, and consequent morphology of the polyurethane prepolymers and WPUU were investigated with Fourier transform infrared (FTIR), gel permeation chromatography, and NMR techniques with MDI concentrations ranging from 0 (pure IPDI) to 50% with respect to the total moles of isocyanate. Wide‐angle X‐ray diffraction and differential scanning calorimetry patterns showed that the crystallinity of WPUU, which mostly originated from crystallizable poly(tetramethylene adipate) polyol, was significantly affected by the MDI content. Both the crystallinity and melting temperature of WPUU decreased as the MDI content increased. Deconvoluted relative peak areas of the carbonyl region in the FTIR spectrum revealed that the effect of hydrogen bonding among the hard segments became favorable as the MDI content increased, whereas the hydrogen bonding of the soft segments significantly decreased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4353–4369, 2004     

Tensile deformation of electrospun nylon‐6,6 nanofibers

Nylon‐6,6 nanofibers were electrospun at an elongation rate of the order of 1000 s^?1 and a cross‐sectional area reduction of the order of 0.33 × 10⁵. The influence of these process peculiarities on the intrinsic structure and mechanical properties of the electrospun nanofibers is studied in the present work. Individual electrospun nanofibers with an average diameter of 550 nm were collected at take‐up velocities of 5 and 20 m/s and subsequently tested to assess their overall stress–strain characteristics; the testing included an evaluation of Young's modulus and the nanofibers' mechanical strength. The results for the as‐spun nanofibers were compared to the stress–strain characteristics of the melt‐extruded microfibers, which underwent postprocessing. For the nanofibers that were collected at 5 m/s the average elongation‐at‐break was 66%, the mechanical strength was 110 MPa, and Young's modulus was 453 MPa, for take‐up velocity of 20 m/s—61%, 150 and 950 MPa, respectively. The nanofibers displayed α‐crystalline phase (with triclinic cell structure). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1482–1489, 2006     

Polymorphism in nylon‐11/montmorillonite nanocomposite

The polymorphism behavior in nylon‐11/montmorillonite (MMT) nanocomposite was investigated by wide‐angle X‐ray diffraction (WAXD) and variable‐temperature infrared spectroscopy. The results of WAXD and IR confirmed the presence of the γ‐crystalline form of nylon‐11, which is induced and stabilized by MMT. However, the hydrogen bond in the nanocomposite and its temperature dependence also exhibited some differences from neat nylon‐11. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 253–259, 2004