Hydrogen bonding in polyamide 66/clay nanocomposite

Hydrogen bonding in polyamide 66/clay nanocomposite (PA66CN) was first investigated with temperature Fourier transform infrared (FTIR), the results of which were compared with that of pristine polyamide 66 (PA66) with the same thermal history. FTIR spectra at room temperature revealed that there is essentially 100% hydrogen bonding in both PA66CN and PA66, and the difference in hydrogen‐bonding status between them is tiny. Additionally, DSC showed that the crystalline degrees and melting temperatures of PA66CN and PA66 prepared by melt quenching are similar. However, the changes of hydrogen bonding with temperature in PA66CN and PA66 are different. As the temperature rose, the hydrogen bonding in PA66CN attenuated and dissociated considerably at a smaller rate than PA66. According to transmission electron microscopic morphology of PA66CN, we analyzed the effect of nanodispersion clay layers on the motion of a polymer chain and the thermal expansion of crystalline lamella for interpreting the observed phenomenon. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2313–2321, 2003     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007     

Flory-huggins interaction parameters of LCP/thermoplastic blends measured by DSC analysis

Liquid crystalline polymer/polyamide 66 (LCP/PA66) and LCP/poly(butyl terephthalate) (LCP/PBT) blends were compounded using a Brabender Plasticorder equipped with a mixing chamber. The LCP employed was a semi-flexible liquid crystalline copolyesteramide based on 30 mol% of p-amino benzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). The Flory-Huggins interaction parameters (χ12) of the LCP/ PA66 and LCP/PBT blends are estimated by melting point depression from DSC measurement. The results indicate that c12 values all are negative for LCP/PA66 and LCP/PBT blends, and when the LCP content in these blends is more than 10 mass%, the absolute value of χ₁₂ decreases. Thereby, we can conclude that LCP/PA66 and LCP/PBT blends are fully miscible in the molten state, the molecular interaction between the LCP and PA66 is stronger than that between LCP and PBT. As the LCP content in LCP/PA66 and LCP/PBT blends is more than 10 mass%, the molecular interaction between LCP and matrix polymer decreases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of morphology on ortho-positronium annihilation characteristics in polyamide 6

Samples of polyamide 6 (PA6) of different morphology were studied with use of WAXS, SAXS and PALS technique. The determined ortho-positronium characteristics reflect variations in morphology and particularly the presence of defects at the interface between the crystalline and amorphous region as well as the interaction between the crystalline and the amorphous phases existing in the polyamide samples.     

Structure development of polyamide‐66 fibers during drawing and their microstructure characterization

Structure development during drawing was studied for three sets of polyamide‐66 (PA66) fibers with density, optical microscopy, wide‐angle X‐ray diffraction, and Fourier transform infrared spectroscopy. The crystallinity, estimated by density measurements, remained virtually constant with increasing draw ratios, indicating that stress‐induced crystallization did not occur for the PA66 fibers drawn at room temperature, but there was a rapid transformation from a hedrite morphology to a fibrillar one. The absence of stress‐induced crystallization differed from the behavior of polyamide‐6, and this was attributed to the stronger hydrogen bonding between polyamide chains and the higher glass‐transition temperature of PA66. Polarized infrared spectroscopy was used to measure the transition‐moment angles of the vibrations at 936 and 906 cm^?1, which were found to be 48 and 60°, respectively. The crystalline orientation was estimated from the band at 936 cm^?1, and the increase with an increasing draw ratio was in close quantitative agreement with X‐ray diffraction data; this showed that infrared spectroscopy could be used reliably to measure the crystalline orientation of PA66 fibers. Because we were unable to obtain the transition‐moment angle of the amorphous bands, the amorphous orientation was obtained with Stein's equation. The amorphous orientation developed more slowly than the crystalline orientation, which is typical behavior for flexible‐chain polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1940–1948, 2002     

Thermal and crystallization studies of nano-hydroxyapatite reinforced polyamide 66 biocomposites

The thermal and crystalline behaviour of nano-hydroxyapatite (n-HA) reinforced polyamide 66 (PA66) biocomposites was studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). The thermal properties of PA66 and n-HA/PA66 composites were analysed by TG. The effect of hydroxyapatite on the melting and crystallization of PA66 was evaluated by DSC. DSC measurements exhibited an increase in the crystallization temperature, however, decrease in crystallinity with the addition of n-HA to the PA66 matrix, which was attributed to the hydrogen bonds between the n-HA surface and polyamide 66 molecules. With increase of n-HA content, the melting peak of the PA66 component shifted to higher temperature, suggesting constrained melting. The addition of n-HA to PA66 played the role of nucleating agent and enhanced the crystallization rate. Non-isothermal parameter a measured by Liu method varies from 1.13 to 1.18, from 1.02 to 1.07, and from 1.18 to 1.21 for PA66, 30 wt% n-HA/PA66 and 40 wt% n-HA/PA66, respectively, and the values of K_(T) systematically increase with rise in relative degree of crystallinity.     

Temperature dependent wide angle X-ray diffraction studies on the crystalline transition in water saturated and dry polyamide 6/66 copolymer

The crystalline transition in water saturated and dry polyamide 6/66 copolymer (ratio 4:1 by mol) was investigated by means of temperature dependent wide angle X-ray diffraction (WAXD). The polyamide 6/66 copolymer (PA6/66) exhibits a poorly developed α-phase at room temperature after being cooled down from the melt. Uptake of water improves the crystalline structure by mobilizing the amorphous phase, thus facilitating chain relaxation in the crystalline phase. Upon heating, the effect of the glass transition on the change of the crystal lattice constants is seen. Further heating leads to a gradual crystalline transition from the α-phase to a pseudohexagonal phase. Different from the behavior in polyamide 6, this pseudohexagonal phase does not further transform to a high temperature α′-phase before melting. The delay of the crystalline transition in the water saturated PA6/66--as compared to the dry material can be understood as a result of the better ordered crystalline structure in it.     

An Experimental and Theoretical Approach to Investigate the Effect of Chain Length on Aminothiol Adsorption and Assembly on Gold

Despite the numerous studies on the self‐assembled monolayers (SAMs) of alkylthiols on gold, the mechanisms involved, especially the nature and influence of the thiol–gold interface are still under debate. In this work the adsorption of aminothiols on Au(111) surfaces has been studied by using surface IR and X‐ray photoelectron spectroscopy (XPS) as well as by density functional theory (DFT) modeling. Two aminothiols were used, cysteamine (CEA) and mercaptoundecylamine (MUAM), which contain two and eleven carbon atoms, respectively. By combining experimental and theoretical methods, it was possible to draw a molecular picture of the thiol–gold interface. The long‐chain aminothiol produced better ordered SAMs, but, interestingly, the XPS data showed different sulfur binding environments depending on the alkyl chain length; an additional peak at low binding energy was observed upon CEA adsorption, which indicates the presence of sulfur in a different environment. DFT modeling showed that the positions of the sulfur atoms in the SAMs on gold with similar unit cells [(2√3×2√3)R30°] depended on the length of the alkyl chain. Short‐chain alkylthiol SAMs were adsorbed more strongly than long‐chain thiol SAMs and were shown to induce surface reconstruction by extracting atoms from the surface, possibly forming adatom/vacancy combinations that lead to the additional XPS peak. In the case of short alkylthiols, the thiol–gold interface governs the layer, CEA adsorbs strongly, and the mechanism is closer to single‐molecule adsorption than self‐assembly, whereas for long chains, interactions between alkyl chains drive the system to self‐assembly, leading to a higher level of SAM organization and restricting the influence of the sulfur–gold interface.     

Voltammetric Study of Methylene Blue at Thiol SAMs‐Modified Gold Electrodes

The voltammetric behavior of methylene blue (MB) at thiol self‐assembled monolayers modified gold electrodes (SAMs/Au) has been investigated. MB exhibited a redox peak at about ?0.35 V (vs.SCE) in alkaline solution at bare gold electrodes. When the gold electrodes were modified with thiol SAMs, the peak grew due to the accumulation of MB at SAMs. With the solution pH rising, more MB was accumulated, hence the peak height increased, which differed from that at bare gold electrodes. The electrode process at SAMs/Au featured the characteristics of adsorption and/or electrode reaction controlled. The enhancing action of glutathione monolayer (GSH SAM), 3‐mercaptopropionic acid monolayer (3MPA SAM) and other thiol SAMs was compared. Among these, GSH SAM made the MB peak increase more. At GSH SAM/Au, the peak height varied linearly with MB concentration over the range of 2 μM to 400 μM. So this can be developed for the determination of MB and studies concerned. The accumulation behavior caused by GSH SAM and native fish sperm dsDNA was compared. The interaction between DNA and MB was also discussed under this condition.     

Semi-crystalline poly(ε-caprolactone) brushes on gold substrate via “grafting from” method: New insights with AFM characterization

This paper is the first report about the morphology of semi-crystalline poly(ε-caprolactone) (PCL) brushes studied by Atomic Force Microscopy (AFM) in tapping mode. This represents a convenient way to observe how the growth of a polymer proceeds from a thiol monolayer on gold substrate in terms of grafting density and thiol monolayer stability. The synthesis of semi-crystalline PCL brushes was carried out by Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) from hydroxyl end-group of thiol monolayer on gold surface as catalyzed with tin octoate (Sn(Oct)₂) at 50 °C. Addition of a sacrificial initiator was also attempted in order to get a finer control over PCL crystals. For a sake of comparison, triazabicyclo[4.4.0]dec-5-ene (TBD) was also investigated as another ROP catalyst active at ambient temperature. The composition and the morphology of resulting semi-crystalline PCL brushes were characterized using X-ray Photoelectron Spectroscopy (XPS) and AFM. In the case of Sn(Oct)₂-promoted ROP of CL with or without free (sacrificial) initiator (i.e., benzyl alcohol), different types of morphologies were observed on the gold substrate, due to the thermal instability of thiol-gold bond under the experimental conditions. When TBD was used at ambient temperature, a regular and homogeneous crystalline morphology, i.e., compact PCL crystals, could be observed.     

An investigation on the structural characteristics and reinforcement of melt processed polyamide 66/multiwalled carbon nanotube composites

Properties of melt processed polyamide 66 (PA66)/multiwalled carbon nanotube composite were first characterized experimentally. The experimental results exhibited the formation of crystalline layer around the nanotubes and a considerable enhancement in mechanical properties by incorporation of multiwalled carbon nanotube up to 1 wt%. Mechanical properties were analyzed in terms of structural parameters using micromechanical models proposed in this study. It was suggested that the mechanical properties were greatly dominated by crystalline layer and nanotube length. It was also deduced that the melt mixing process caused a significant nanotube breakage restricting further enhancement of nanocomposite properties at higher nanotube contents. Surface modification of nanotube provided better polymer‐nanotube interaction; however, it increased the mechanical properties marginally. Copyright © 2014 John Wiley & Sons, Ltd.     

Crystalline structure of polyamide 12 as revealed by solid‐state 13C NMR and synchrotron WAXS and SAXS

The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state ¹³C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (l_c) and amorphous (l_a) phases, and the linear crystallinity x_cl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005     

Infrared spectroscopic characterization of oriented polyamide 66: Band assignment and crystallinity measurement

Having found much ambiguity in the infrared band assignments for polyamide 66 (PA66), we revisited some of these assignments before using infrared spectroscopy to assess microstructure changes resulting from multiple thermal treatments. We discovered that earlier assignments of the 1144 and 1180 cm⁻¹ bands to the amorphous (noncrystalline) phase were incorrect, whereas the bands at 924 and 1136 cm⁻¹ can be attributed unambiguously to the noncrystalline phase. We also confirmed that PA66 bands at 936 and 1200 cm⁻¹ are crystalline bands. The normalized absorbance of the 1224‐cm⁻¹ fold band increases in proportion to crystallinity, indicating that chain folding is the predominant mechanism of thermal crystallization in PA66. We demonstrated that infrared spectroscopy can be used to estimate the degree of crystallinity of PA66, and two methods were explored. One is a calibration method in which the band ratio of 1200 and 1630 cm⁻¹ is plotted against crystallinity measured by density. The other is an independent infrared method based on the assumption that PA66 satisfies a two‐phase structure model. The crystallinity determined by the independent infrared method showed good agreement with the crystallinity obtained from density measurements. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 516–524, 2000     

Study of nylon 66–clay nanocomposites via condensation polymerization

Nylon 66–clay (polyamide 66 (PA66)–organophilic montmorillonite (OMT)) exfoliated nanocomposites were synthesized based on nylon 66 salt and organoclay (OMT) modified by hydro-aminocaproic acid via condensation polymerization. And the nanocomposites were characterized by X-ray diffraction and transmission electronic microscopy. Exfoliated morphology with different clay content was obtained. The effects of cation exchange capacity and organic modified agent of OMT on the formation of exfoliated nanocomposites were investigated. It was shown that only suitable cation exchange capacity and organic modified agent could result in the formation of exfoliated morphology under the condition of condensation polymerization. The thermal and flammability properties of the nanocomposites were investigated through thermogravimetry and cone calorimetry experiments. Results indicate that the exfoliated nanocomposites have enhanced thermal stability and flame retardant properties compared with pure PA66.     

PA66/PA12/clay based nanocomposites: morphology and physical properties

The structure and the physical properties of several polyamide 66 (PA66)/polyamide 12 (PA12) blends containing different amounts of the two polymers and obtained by melt‐blending have been investigated. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) has also been introduced in order to further improve the physical properties and, in particular, to evaluate its effect on the blends' structure and components' miscibility. The microstructure and morphology of all the composites were analyzed by means of X‐Ray diffraction (WAXD), transmission electron microscopy (TEM), and high resolution scanning electron microscopy (SEM), while the macroscopic scale properties (mechanical behavior and water adsorption) were assessed in order to investigate and understand the materials' structure–properties relationships. The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed. The results also underlined the possibility to tailor the behavior of polymer blends in terms of mechanical water adsorption properties by varying the amount of PA12, added to PA66 with and without the addition of the OLMS. The effectiveness of the clay in modifying the components' miscibility as well as its tendency to segregate preferentially within separate PA66 domains have been assessed. WAXD results showed opposite effects of PA12 and clay on the crystallization behavior of PA66, an aspect that has also been deepened in another paper by the same authors discussing the results of the complete thermal characterization. Copyright © 2010 John Wiley & Sons, Ltd.     

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.     

HDPE solution crystallization induced by electrospun PA66 nanofiber

Nanohybrid shish?Ckebab (NHSK), induced by polyamide 66 (PA66) nanofiber, was successfully fabricated in high-density polyethylene (HDPE)/xylene solution via isothermal crystallization. The crystalline morphological features of NHSK were observed by scanning electron microscopy. In the structure of NHSK, PA66 nanofiber serves as shish and HDPE lamellae act as kebabs periodically surrounding the nanofiber. Additionally, it reveals that both HDPE solution concentration and crystallization time have significant effects on the size of HDPE kebab. That is, as the concentration and crystallization time increase, the diameter of the kebab increases. Moreover, when crystallization time further increases, the crystals decorated on PA66 nanofiber exhibit a three-dimensional growth (i.e., aggregate of crystallites) rather than a two-dimensional one (i.e., disk-like lamellae normal to the axis of nanofiber).     

Effect of benzenesulfonamide plasticizers on the glass‐transition temperature of semicrystalline polydodecamide

The effect of various benzenesulfonamide (BSA) plasticizers on the amorphous phase of semicrystalline polydodecamide (PA‐12) has been investigated. MonoBSAs appear as efficient glass‐transition temperature (T_g) depressors because of their miscibility with the host polyamide (PA), low glass transition, and small molecule size. PA‐12's T_g shifts from 50 to about 0 °C at 20 mol % of the most efficient molecules. Comparatively, the more bulky bisBSAs appear to induce less important absolute T_g decreases (30 K at 20 mol %), although these appear as more important when considering the polymer T_g to plasticizer T_g difference. This unexpected observation could be ascribed to both the amide‐sulfonamide interactions and the sterically generated disorder within the polyamide because of the plasticizer molecule's size. Phase‐separation behavior of BSA plasticizers within the host PA has also been investigated. Crystalline phenyl‐SO₂NH₂, for instance, dephased beyond 20 mol % in PA‐12, forming distinct 1–2 micrometer wide crystalline domains as a result of its high propensity to crystallize upon cooling from the melt. By contrast, slow crystallizing N,N‐dimethylBSA, which lacks any specific interaction for PA‐12, remained nevertheless dispersed at a molecular level (metastable state, no phase separation) when vitrification of the host PA‐12 amorphous phase occurred on cooling. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2208–2218, 2002     

Effect of evaporation temperature on the formation of particulate membranes from crystalline polymers by dry-cast process

The membrane formation of crystalline poly(ethylene-co-vinyl alcohol) (EVAL), poly(vinylidene fluoride) (PVDF), and polyamide (Nylon-66) membranes prepared by dry-cast process was studied. Membrane morphologies from crystalline polymers were found to be strongly dependent on the evaporation temperature. At low temperatures, all the casting solution evaporated into a particulate morphology that was governed by the polymer crystallization mechanism. The rise in the evaporation temperature changed EVAL membrane structure from a particulate to a dense morphology. However, as the temperature increased PVDF and Nylon-66 membranes still exhibited particulate morphologies. The membrane structures obtained were discussed in terms of the characteristics of polymer crystallization in the casting solution theoretically. At elevated temperatures the crystallization was restricted for the EVAL membrane because the increase rate in the polymer concentration was fast relative to the time necessary for growth of nuclei. Nonetheless, the time available for PVDF and Nylon-66 with stronger crystalline properties was large enough to form the crystallization-controlled particulate structure that differed in particle size only. In addition, particles in the PVDF membrane were driven together to disappear the boundary, but those in the Nylon-66 membrane exhibited features of linear grain boundary. The difference in particle morphology was attributed to the Nylon-66 with the most strongly crystalline property. Therefore, the kinetic difference in the crystallization rate of the polymer solution play an important role in dominating the membrane structure by dry-cast process.     

Self-assembled monolayers of alkanethiols on gold prepared in a hexagonal lyotropic liquid crystalline phase of Triton X-100/water system

In this paper, we have reported a new method of preparing self-assembled monolayers (SAMs) of decanethiol and hexadecanethiol on gold surface by using a lyotropic liquid crystalline phase as an adsorbing medium. The stability and blocking ability of these SAMs were characterized using grazing angle Fourier transform infrared (FTIR) spectroscopy and electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. The lyotropic liquid crystalline medium possesses a hexagonal structure consisting of a nonionic surfactant Triton X-100, water, and the corresponding thiol, which provides a highly hydrophobic environment to solubilize the alkanethiols and later to facilitate their delivery to the gold surface. We find that the SAMs formed from the hexagonal liquid crystalline phase are highly compact and have excellent electrochemical blocking ability towards the redox probes compared to conventional SAMs prepared from commonly used organic solvents such as ethanol. From the impedance studies, we have determined the capacitance of the monolayer-coated electrodes and the surface coverage of the SAM, which has been found to be >99.98% on gold surface. We have also estimated the extent of ionic permeability through the film and measured the rate constants for the redox reactions on the SAM-modified electrodes. Our results show that the rate constants of [Fe(CN)6](3-/4-) and [Ru(NH3)6](2+/3+) redox couples are very much lower in the case of monolayers prepared in liquid crystalline phase compared to the SAM formed in 1 mM thiol in ethanol solution, suggesting a better blocking ability of the SAMs in the former case. From the grazing angle FTIR spectroscopic studies and capacitance measurements, we have ruled out any coadsorption of surfactant molecules on the Au surface. These results suggest that SAMs of very low defect density and extremely low ionic permeability can be obtained when a hexagonal lyotropic liquid crystalline phase is used as an adsorbing medium.