Kinetics of the solid‐state polymerization of nylon‐6

The kinetics of the thermally induced solid‐state polymerization (SSP) of nylon‐6 were examined in both a fixed‐bed reactor and a rotary reactor. Factors such as the regulator content, the reaction temperature and time, the particle size, the type and geometry of the nylon‐6 prepolymer, the nitrogen gas flow rate, the water content of the nitrogen gas flow, and the polymerization process were studied. The results showed that the regulator content, the reaction temperature and time, and the particle size were the primary factors, and that the others were negligible. Moreover, the SSP rate and number‐average molecular weight (M_n) increased with increasing reaction temperature and time and decreasing particle size. The SSP rate and M_n had maximum values with increasing regulator content in an experimental range of 0.03–0.07 wt %. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 616–621, 2002; DOI 10.1002/app.10341     

Preparation of conductive polyaniline/nylon‐6 composite films by polymerization of aniline in nylon‐6 matrix

Polyaniline (PANI)/Nylon‐6 composite films were prepared by oxidative polymerization of aniline (ANI) inside host Nylon‐6 film. Such a composite has the desired electro‐active and mechanical properties to serve as a self‐standing functional unit. Comparative studies on sorption of ANI by Nylon‐6 matrix from various ANI containing media were conducted revealing superior ANI uptake from neutral ANI solution in water. ANI content was measured to be as high as 12%. Spectroscopic measurements showed that hydrogen bonding seemed to play important role in ANI sorption by Nylon‐6 matrix. Polymerization was monitored using atomic force microscopy and conductivity measurements. The morphology studies showed the appearance of PANI nanodomains on Nylon‐6 surface in the early stages of the polymerization. Eventually the domains coalesced during polymerization forming a continuous PANI layer. The conductivity measurements confirmed the change of the morphology from isolated islands to continuous conducting surface by drastic increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry     

Structure and property study of nylon‐6/clay nanocomposite fiber

The crystal structures of nylon‐6 and nylon‐6/clay fibers were investigated on annealing and drawing. Annealing increased the γ‐crystalline form of both fibers, as indicated by the DSC curves, and its effect was dominant in nylon‐6/clay fiber. On drawing, the γ‐crystalline form was easily converted into the α form in nylon‐6, whereas it was still observed at a relatively high spin‐draw ratio in nylon‐6/clay fiber. However, although the α‐crystal form was dominant in nylon‐6, the γ‐crystal form was dominant in nylon‐6/clay with annealing and drawing, on the basis of the XRD data. The fast crystallization rate of nylon‐6/clay compared with pure nylon‐6 was confirmed, on the basis of the Avrami exponent. The initial modulus of nylon‐6/clay fiber was 30 % higher than the neat nylon‐6 fiber. The reinforcing effect of clay on the dynamic storage modulus was observed. Copyright © 2004 Society of Chemical Industry     

Influence of grafting on structural and optical properties of nylon‐6 fibers

This study throws light on the change of the optical properties and some structural properties due to graft copolymerization of polydiallyldimethyl ammonium chloride (PDADMAC) and polyacrylamide (PAA) of nylon‐6 fibers. Multiple‐beam interferometric technique in transmission was used to study the change of the diameter, refractive indices, and birefringence of nylon‐6 fibers at different graft yields. The results were utilized to investigate the isotropic refractive index, the mean polarizabilities per unit volume, dielectric constant, dielectric susceptibility, and surface reflectivity for nylon‐6 and grafted nylon‐6 fiber. The effect of grafted PAA onto modified nylon‐6 fibers containing PDADMAC on the crystallinity was studied by X‐ray diffraction. These results reflect good effect of grafting on the optical and structural properties of nylon‐6 fibers. The opto‐thermal properties of grafted PAA with different graft yields have been studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Shielding‐effectiveness modeling of carbon‐fiber/nylon‐6,6 composites

We have formulated a linear theory for the shielding effectiveness of composite matrix materials and have tested the theory for various amounts of ThermalGraph DKD X carbon fiber within nylon 6,6. The theory predicts that the most important parameters for the shielding effectiveness of a sample are the carbon‐fiber volume percentage and the frequency of the wave to be shielded. Although we expected the model to be valid at low filler‐loading levels, it actually performs remarkably, covering an electrical‐resistivity range of 10¹⁶ (at low filler‐loading levels) to 10¹ Ω cm (at high filler‐loading levels), well above the percolation threshold of electrical‐resistivity theory. The model performs much better than those reported in the literature and can be used to determine filler loadings needed to provide a certain level of shielding of electromagnetic waves. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 62–69, 2005     

Mechanical properties and morphology of nylon‐6 hybrid composites

In this investigation, the influence of filler type and filler content on the mechanical properties of nylon‐6 is investigated. The mineral fillers were selected on the basis of their shape and size: flake‐like kaolin and talc, spherical glass beads or fibrous wollastonite. These fillers were added to nylon‐6 individually or in mixed combinations. They were added at different percentages varying between 10 and 30% w/w. Samples of the composites were prepared by the injection moulding process. Uniaxial tensile, Izod impact and flexural tests were carried out. Tensile strength, elongation at break, modulus of elasticity and impact energy were obtained and compared. In case of single fillers the results showed that the tensile strength, modulus of elasticity and their flexural values for nylon‐6 composite improve with the increase in filler content while mixed compounds showed no significant changes above 15% + 15% w/w filler. However, for single and mixed filler up to 10% w/w, the impact strength and maximum elongation at break showed significant decrease. In general, the maximum improvement in mechanical the addition of 10–15% w/w filler. Copyright © 2003 Society of Chemical Industry     

Preparation of conducting nylon‐6 electrospun fiber webs by the in situ polymerization of polyaniline

For the preparation of conducting polyaniline (PANI)/nylon composites with high electrical conductivity as well as superior mechanical properties such as flexibility and lightness, PANI/nylon‐6 composite nanofiber webs were prepared via the electrospinning process with a nylon‐6/formic acid polymer solution, and then PANI on the surface of the nylon‐6 electrospun nanofiber webs was chemically polymerized. The electrical conductivity measurements showed that the conductivity of the PANI/nylon‐6 composite electrospun fiber webs was superior to that of PANI/nylon‐6 plain‐weave fabrics because of the high surface‐area/volume ratios. On the other hand, the volume conductivities of the PANI/nylon‐6 composite electrospun fiber webs increased from 0.5 to 1.5 S/cm as the diffusion time increased from 10 min to 4 h because of the even distribution of PANI in the electrospun fiber webs. However, the surface conductivities of the PANI/nylon‐6 composite electrospun fiber webs somewhat decreased from 0.22 to 0.14 S/cm as the diffusion time increased because of PANI contaminated with aniline monomers, aniline oligomers, and some alkyl chains, which served as electrical resistants. These results were confirmed with Fourier transform infrared, electron spectroscopy for chemical analysis, and morphology analysis. It was concluded that the diffusion time for the in situ polymerization of PANI in electrospun fiber webs was optimized at approximately 3 h. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 983–991, 2005     

Effects of diffusional water removal and heat transfer in nylon 6 reactors

The effects of diffusional water removal and heat transfer on the polymerization of ε-caprolactam were investigated by solving the systems of differential mass and energy balance equations using a finite difference method. Two types of contacting scheme between inert gas and reaction mass have been chosen for study. One is a hollow sphere system and the other is a wetted-wall type hollow cylinder system. The reaction system was designed to be in equilibrium with respect to monomer conversion. The interfacial area per unit volume and the diffusional depth have profound effects on the water content and the temperature of the reaction mass, and consequently on the molecular weight of the polymer produced. Larger interfacial area per unit volume and smaller diffusional depth lead to a higher rate of water removal and heat transfer. In case of larger interfacial area per unit volume, the higher interfacial temperature gives rise to higher molecular weight polymer. For the interfacial area per unit volume of 26.67 m²/m³, the number average chain length reaches as high as 277 and the polydispersity as high as 2.06 when the interfacial temperature is 270°C. The heat transfer greatly affects the content of cyclic dimer in the product so that the hollow cylinder type reactor is preferred, because it is easier to control the temperature of the later portion of the reactor.     

Physical–mechanical properties and morphological study on nylon‐6 recycling by injection molding

The effect of the multiple recycling of nylon‐6 by injection molding on its physical–mechanical properties and morphology was studied after each cycle of injection. These studies were made in order to know how many times it is possible to recycle the nylon‐6 without significant loss of the physical–mechanical properties. Optical and electronic microscopy were used to evaluated the morphology. Molecular weight changes were determinated by gel permeation chromatography (GPC). The nylon‐6 was recycled 10 times, until the eighth cycle the properties of the material did not suffered any change. Changes of 10–15% in the properties between nylon‐6 with 10 cycles of injection and virgin material were observed. An exception was the percentage of elongation that decreased 70% gradually until in the tenth cycle of injection. The results from GPC show that the molecular weight of nylon‐6 increased with recycling (M_w = 17% and M_n = 14%). With the reprocess was also observed the presence of gels. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 851–858, 2000     

Crystallization and melting behavior of multi‐walled carbon nanotube‐reinforced nylon‐6 composites

The crystallization and melting behavior of neat nylon‐6 (PA6) and multi‐walled carbon nanotubes (MWNTs)/PA6 composites prepared by simple melt‐compounding was comparatively studied. Differential scanning calorimetry (DSC) results show two crystallization exotherms (T_{CC, 1} and T_{CC, 2}) for PA6/MWNTs composites instead of a single exotherm (T_{CC, 1}) for the neat matrix. The formation of the higher‐temperature exotherm T_{CC, 2} is closely related to the addition of MWNTs. X‐ray diffraction (XRD) results indicate that only the α‐phase crystalline structure is formed upon incorporating MWNTs into PA6 matrix, independently of the cooling rate and annealing conditions. These observations are significantly different from those for PA6 matrix, where the increase in cooling rate or decrease in annealing temperature results in the crystal transformation from α‐phase to γ‐phase. The crystallization behavior of PA6/MWNTs composites is also significantly different from those reported in PA6/nanoclay systems, probably due to the difference in nanofiller geometry between one‐dimensional MWNTs and two‐dimensional nanoclay platelets. The nucleation sites provided by carbon nanotubes seem to be favorable to the formation of thermodynamically stable α‐phase crystals of PA6. The dominant α‐phase crystals in PA6/MWNTs composites may play an important role in the remarkable enhancement of mechanical properties. Copyright © 2005 Society of Chemical Industry     

Friction and wear studies on nylon‐6/SiO2 nanocomposites

Composites of nanometer‐sized silica (SiO₂) filler incorporated in nylon‐6 polymer were prepared by compression molding. Their friction and wear properties were investigated on a pin on disk tribometer by running a flat pin of steel against a composite disc. The morphologies of the composites as well as of the wear track were observed by scanning electron microscopy (SEM). The addition of 2 wt % SiO₂ resulted in a friction reduction (μ) from 0.5 to 0.18 when compared with neat nylon‐6. This low silica loading led to a reduction in wear rate by a factor of 140, whereas the influence of higher silica loadings was less pronounced. The smooth morphology obtained after the wear test indicated the negligible contribution to friction of the pin to the nanocomposite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1855–1862, 2004     

Effect of diacid stabilizers on kinetics of hydrolytic polymerization of ϵ‐caprolactam in industrial reactors

The rate constants in hydrolytic polymerization of ε‐caprolactam are dependent on the concentration of carboxylic acid groups in the reaction medium. Therefore, the use of diacid stabilizers for regulating molecular weight are likely to have favorable effect on the kinetics of polymerization compared to monoacid stabilizers, which are traditionally used in such polymerizations. To understand the kinetics of polymerization in the presence of diacid stabilizer compared to monoacid stabilizer, mathematical kinetic models were developed using the end group approach. These models were used to quantify the effect of both stabilizers on nylon‐6 synthesis in a closed isothermal batch reactor at different temperatures in the range of 245–265°C. The kinetic model for the diacid‐stabilized system was then extended to an industrial VK tube reactor using the process model developed earlier for the monoacid stabilized system. Both the mathematical modeling and experimental results showed that the presence of diacid stabilizer could significantly enhance the overall kinetics of the reaction compared to the monoacid stabilized system and in turn, resulted in reduction of the polymerization time by about 20–25%. The study suggests that diacid stabilizers may be used preferably over monoacid stabilizers in synthesis of nylon‐6 to reduce the cost of polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ternary reactive blends of nylon‐6 matrix with dispersed rigid brittle polymer and elastomer

Except by elastomers, the toughness of nylon‐6 (N‐6) can be improved by the addition of rigid poly(styrene‐co‐maleic anhydride) (SMA). In this case, strength and stiffness are also enhanced. Combination of SMA with maleated ethylene‐propylene rubber or styrene‐ethene/butene‐styrene with a total content below 15% gives a ternary blend having a toughness level close to elastomer toughening, whereas the strength and stiffness reached at least the Nylon‐6 values. An explanation is a synergistic combination of both elastomer and rigid polymer toughening mechanisms. An opposite effect on mechanical behavior was found with high contents of both additives. Except for worsened strength and stiffness, in some cases, a higher elastomer content even did not enhance the toughness. This effect can be explained by too fine phase structure found, causing the matrix ligament dimension to be below its minimum critical value. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1404–1411, 1999     

Structure and thermal behavior of nylon‐6/polytetrahydrofuran triblock copolymers obtained via anionic polymerization

The structure, crystallization, and phase behavior of nylon6‐b‐polytetrahydrofuran‐b‐nylon6 triblock copolymers synthesized via activated anionic polymerization have been studied. The composition, molecular weight of polytetrahydrofuran (PTHF) soft block, and type of polymeric activators (PACs) have been varied. Differential Scanning Calorimetry (DSC), Wide‐Angle X‐ray Diffraction (WAXD), Transmission Electron Microscopy (TEM), and Polarized Light Microscopy (PLM) experiments have revealed that in triblock copolymers only the nylon‐6 component crystallizes while PTHF segments are amorphous. The soft blocks do not alter the spherulitic crystalline structure of nylon‐6 and hard blocks crystallize in the α‐modification. The degree of crystallinity decreases with increasing PTHF concentration. The phase behavior has been investigated by Dynamic Mechanical Thermal Analysis (DMTA). Two different glass transition temperatures (T_g) for all samples have been observed. This indicates that nylon‐6 and PTHF segments are not molecularly miscible and the copolymers are microphase separated. The mechanical properties of the copolymers synthesized have been evaluated. Nylon‐6 copolymers with soft block concentrations up to 10 w/w %, exhibit improved notched impact strength in comparison to the nylon‐6 homopolymer, retaining relatively high hardness and tensile strength. All copolymers possess low water absorption and good thermal stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1448–1456, 2002; DOI 10.1002/app.10448     

Interior synthesizing of ZnO nanoflakes inside nylon‐6 electrospun nanofibers

Doping of the polymeric electrospun nanofibers by metal oxides nanoparticles is usually performed by electrospinning of a colloidal solution containing the metal oxide nanoparticles. Besides the economical aspects, electrospinning of colloids is not efficient compared with spinning of sol–gels, moreover well attachment of the solid nanoparticles is not guaranteed. In this study, reduction of zinc acetate could be performed inside the nylon‐6 electrospun nanofibers; so polymeric nanofibers embedding ZnO nanoflakes were obtained. Typically, zinc acetate/nylon‐6 electrospun nanofibers were treated hydrothermally at 150°C for 1 h. Besides the utilized characterization techniques, PL study affirmed formation of ZnO. The produced nanofibers showed a good antibacterial activity which improves with increasing ZnO content. Overall, the present study opens new avenue to synthesize hybrid nanofibers by a facile procedure. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optimal operation of ethylene polymerization reactors for tailored molecular weight distribution

This work presents a comprehensive steady‐state model of the high‐pressure ethylene polymerization in a tubular reactor able to calculate the complete molecular weight distribution (MWD). For this purpose, the probability generating function technique is employed. The model is included in an optimization framework, which is used to determine optimal reactor designs and operating conditions for producing a polymer with tailored MWD. Two application examples are presented. The first one involves maximization of conversion to obtain a given MWD, typical of industrial operation. Excellent agreement between the resulting MWD and the target one is achieved with a conversion about 5% higher than the ones commonly reported for this type of reactor. The second example consists in finding the design and operating conditions necessary to produce a polymer with a bimodal MWD. The optimal design for this case involves a split of the initiator, monomer, and modifier feeds between the main stream and two lateral injections. To the best of our knowledge, this is the first work dealing with the optimization of this process in which a tailored shape for the MWD is included. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Mica reinforced nylon‐6: Effect of coupling agents on mechanical,thermal, and dielectric properties

The effects of applying titanate (TYZOR® TPT) and silane (DYNASYLAN VTMO) coupling agents to wet ground muscovite mica in nylon‐6 composites are described. Nylon‐6 composites of 5–40 wt % filler loadings were compounded using an APV Baker twin‐screw extruder. Mica (25 wt %) brought about an increase in the Young's modulus, flexural strength, and flexural modulus but did not produce significant variations in tensile and impact strength. Hence different coupling agents were employed. It was observed that titanate coupling agent improved the tensile strength and the Young's modulus of the composites much while the impact properties were enhanced by the silane coupling agent. An attempt was made to use ?‐caprolactum in improving the interfacial adhesion of the filler and the matrix. It was observed that ?‐caprolactum improved the flexural modulus of the composites most. The effect of coupling agents on the dielectric strength, heat distortion temperature, and morphology were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4074–4081, 2006     

Natural abundance 15n solid‐state nmr study of nylon‐6 in blends

Natural abundance solid‐state nuclear magnetic resonance spectroscopy (NMR) of nitrogen‐15 (¹⁵N) was applied to investigate the films of nylon‐6 and their blends with poly(propylene oxide) (PPO). The NMR ¹⁵N results allowed us to identify the crystalline forms present in these blends and also confirmed the previous NMR results obtained by ¹³C‐NMR study. From all NMR data the antiplasticization phenomena and plasticization effects caused by PPO content, in the blends were characterized. The polyoxide action is a function of its proportion. However, because the samples were prepared by solution casting, the residual solvent action cannot be ignored. The ¹⁵N chemical shift changes were influenced by both PPO and residual solvent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3872–3875, 2003