Mechanical properties of PA6/PA12 blend specimens prepared by selective laser sintering

The use of polymeric blends can increase the range of structures and properties of selective laser sintering (SLS) parts. This study investigates the processing of a binary polar system using polyamide 6 (PA6) and polyamide 12 (PA12) by SLS. The mixture composition and processing conditions, and their influence on the dynamic mechanical properties of the specimens manufactured were evaluated. The maximum tan δ values suggest that PA6 and PA12 have similar visco-dissipative behavior. The PA6/PA12 blends behavior varied according to the relaxation phenomena of the pure components, proportionally to the blend composition. The creep test showed that blends with a higher amount of PA6 had greater plastic deformation and less elastic recovery. In the fatigue test the 20/80 and 50/50 blends presented good fatigue resistance under the test conditions.     

The microstructural characterization of PA6/PA12 blend specimens fabricated by selective laser sintering

This study investigates the processing of blends of polyamide 6 (PA6) and polyamide 12 (PA12) by selective laser sintering (SLS) using a CO₂ laser. Powder properties of undiluted polymers, mixture composition, and processing parameters, as well as their influence on the microstructure of the specimens manufactured, were evaluated. Polyamides showed higher absorption of laser energy during the sintering of blend specimens, with subsequent thermal energy transfer to the melting of the polymeric phases. The structure of parts obtained by SLS is dependent on the process parameters and the characteristics of the powder material to be processed. The microstructures of PA6/PA12 blend specimens were heterogeneous, with co-continuous and disperse phases depending on the quantity of PA12. The porosity and crystallinity also changed as a function of the component proportions. The use of polymeric blends can increase the range of structures and properties of SLS parts.     

Adsorption of copper(II) ions by keratin/PA6 blend nanofibres

Mats of randomly oriented nanosized filaments, prepared by electrospinning wool keratin/polyamide 6 blends in formic acid, were evaluated as adsorbents of Cu²⁺ ions. The adsorption capacity was evaluated as a function of the nanofibre composition, specific surface area, initial metal ion concentration, contact time and pH of the solution. The adsorption tests revealed that keratin-based nanofibres highly adsorb Cu²⁺ ions and the adsorption capacity increases with increasing the specific surface area of the nanofibre mats. The maximum adsorption capacities for nanofibre mats containing 50%, 70% and 90% (wt.%) of keratin were found to be 61.7 (mg/g), 90 (mg/g) and 103.5 (mg/g), respectively. The Cu²⁺adsorption onto the keratin rich nanofibres is highly pH-dependent and the optimum pH was found above the isoelectric point of keratin. The experimental data fit the pseudo second-order kinetic model. Infrared analysis demonstrated the formation of complexes between Cu²⁺ ions and keratin that involve terminal free carboxyl groups of the protein.     

Morphology of a phase-separated and a molecular composite PBT/ABPBI polymer blend

The structure and morphology of homopolymers and blends of rigid-rod poly(p-phenylene benzobisthiazole) (PBT) and semiflexible coil poly[2,5(6)benzimidazole] (ABPBI) were examined by wide-angle x-ray diffraction and scanning and transmission electron microscopy. When samples were processed from a solution where the total polymer concentration of 30% PBT/70% ABPBI blend was greater than a critical concentration, large-scale phase separation occurred and 0.1–4 μm ellipsoidal particles were present in a ductile matrix. The ellipsoids were chiefly composed of aggregates of well-oriented 10-nm PBT crystallites, while the matrix material was chiefly ABPBI. When the concentration was less than a critical concentration, the solution was optically homogeneous. In processing of fiber and film samples from the homogeneous solution, large-scale phase separation was inhibited by rapid coagulation in a water bath. After heat treatment, these samples were found to contain crystallites of both PBT and ABPBI with lateral dimensions of ordered regions no larger than 3 nm. The PBT homopolymer was dispersed in the matrix at the molecular level in ordered regions at a scale no larger than 3 nm, resulting in a rigid-rod molecular composite. In the rigid-rod molecular composite fiber both the molecular-level dispersion and high orientation contributed to higher values of strength and modulus compared to the properties of a phase-separated fiber. The strength and modulus of highly oriented fiber were only 25% higher than those of planar isotropically oriented film, suggesting that the level of dispersion of rod molecules is more important than orientation of the reinforcing phase in rigid-rod molecular composites.     

Morphology and permeability of cellulose/chitin blend membranes

A series of biodegradable cellulose/chitin blend membranes were successfully prepared from blend solution of cellulose and chitin in 9.5 wt% NaOH/4.5 wt% thiourea aqueous solution coagulating with 5.0 wt% (NH₄)₂SO₄. The influence of chitin content on the morphology and structure of the membranes was studied by scanning electron microscopy, environmental scanning electron microscopy and wide-angle X-ray diffractometry, as well as Fourier transform infrared spectroscopy. Using double-cell method and solution depletion method, the permeability and partition coefficients of three model drugs (ceftazidine, cefazolin sodium, and thiourea) were determined in phosphate buffer solution to clarify the diffusion mechanism governing transport of solutes in these membranes. Diffusion coefficients were calculated from the permeability and partition coefficients in terms of Fick's law. The effects of the chitin content, pH, ionic strength, molecular size and temperature on the drug diffusion were also studied. Our results revealed that all of the membranes had a porous-like structure. The introduction of chitin exhibited great influence on the morphology and crystal structure of the blend membranes, resulting in a significant different permeability. For the first time, a dual diffusion mechanism with some hindrance of molecular diffusion via polymer obstruction was employed to explain the transport of drugs in the membranes.     

Interfacial electron transfer energetics studied by high spatial resolution tip-enhanced Raman spectroscopic imaging

Interfacial electron transfer (ET) in TiO?-based systems is important in artificial solar energy harvesting systems, catalysis, and in advanced oxidative waste water treatment. The fundamental importance of ET processes and impending applications make the study of interfacial ET a promising research area. Photoexcitation of dye molecules adsorbed on the surface of wide band gap semiconductors, such as TiO?, results in the injection of electrons from the dye molecules to the conduction band of the semiconductor or energetically accessible surface electronic states. Using Raman spectroscopy and ensemble-averaging approaches,t he chemical bonding and vibrational relaxation of the ET processes have been extensively studied. However, due to the complexity of the interfacial ET energetics and dynamics, significant questions remain on characterizing the source of the observed complexities. To address these important issues, we have applied advanced spectroscopic and imaging techniques such as confocal and tip-enhanced near-field Raman as well as photoluminescence spectroscopic and topographic imaging. Here we explore single surface states on TiO? as well as the interfacial electronic coupling of alizarin to TiO? single crystalline surfaces.     

Morphology of ABC triblock copolymer/homopolymer blend systems

Morphological variations of ABC triblock copolymers through the blending of B or A/C homopolymers, all with short chain lengths, were studied experimentally. The samples were symmetric ISP triblock copolymers, where I, S, and P denote polyisoprene, polystyrene, and poly(2‐vinylpyridine), and component homopolymers. Microphase‐separated structures of the solvent‐cast films were observed with transmission electron microscopy and small‐angle X‐ray scattering. For an ISP/S system, the lattice constant of the tricontinuous gyroid structure (G‐structure) increased with an increase in the volume fraction of S (?_s) if the amount of added homopolymer was small, but it reached a certain limit, reflecting the fact that the midblock chain had a limit for chain stretching. For I/ISP/P blends, on the contrary, the lattice constant of the G‐structure continued increasing with decreasing ?_s. This result shows that the I and P domains did not have a limit for chain stretching because the two end blocks had free ends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1135–1141, 2002     

Morphology and thermal properties of a PC/PE blend with reactive compatibilization

Reactive compatibilization of immiscible polymers is becoming increasingly important and hence a representative study of a polycarbonate/high density polyethylene (PC/HDPE) system is the focus of this paper. A grafted copolymer PC‐graft‐ethylene‐co‐acrylic acid (PC‐graft‐EAA) was generated as a compatibilizer in situ during processing operation by ester and acid reaction between PC and ethylene‐acrylic acid (EAA) in the presence of the catalyst dibutyl tin oxide (DBTO). As the polyethylene (PE) matrix does not play any part during the synthesis of the copolymer and since PC and EAA are also immiscible, to simplify the system, the influence of this copolymer formation at the interface between PC and EAA on rheological properties, phase morphology, and crystallization behavior for EAA/PC binary blends was first studied. The equilibrium torque increased with the DBTO content increasing in EAA/PC blends on Haake torque rheometer, indicating the in situ formation of the graft copolymer. Scanning electron microscopy (SEM) studies of cryogenically fractured surfaces showed a significant change at the distribution and dispersion of the dispersed phase in the presence of DBTO, compared with the EAA/PC blend without the catalyst. Differential scanning calorimetry (DSC) studies suggested that the heat of fusion of the EAA phase in PC/EAA blends with or without DBTO reduced with the formation of the copolymer compared with pure EAA. Then morphological studies and crystallization behavior of the uncompatibilized and compatibilized blends of PC/PE were studied as functions of EAA phase concentration and DBTO content. Morphological observations in PC/PE blends also revealed that on increasing the EAA content or adding the catalyst DBTO, the number of microvoids was reduced and the interface was intensive as compared to the uncompatibilized PC/PE blends. Crystallization studies indicated that PE crystallized at its bulk crystallization temperature. The degree of crystallinity of PE phase in PC/PE/EAA blends was also reduced with the addition of EAA and DBTO compared to the uncompatibilized blends of PC/PE, indicating the decrease in the degree of crystallinity was more in the presence of PC‐graft‐EAA. Copyright © 2007 John Wiley & Sons, Ltd.     

Charge carrier formation in polythiophene/fullerene blend films studied by transient absorption spectroscopy

We report herein a comparison of the photophysics of a series of polythiophenes with ionization potentials ranging from 4.8 to 5.6 eV as pristine films and when blended with 5 wt % 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]C61 (PCBM). Three polymers are observed to give amorphous films, attributed to a nonplanar geometry of their backbone while the other five polymers, including poly(3-hexylthiophene), give more crystalline films. Optical excitation of the pristine films of the amorphous polymers is observed by transient absorption spectroscopy to give rise to polymer triplet formation. For the more crystalline pristine polymers, no triplet formation is observed, but rather a short-lived (approximately 100 ns), broad photoinduced absorption feature assigned to polymer polarons. For all polymers, the addition of 5 wt % PCBM resulted in 70-90% quenching of polymer photoluminescence (PL), indicative of efficient quenching of polythiophene excitons. Remarkably, despite this efficient exciton quenching, the yield of dissociated polymer+ and PCBM- polarons, assayed by the appearance of a long-lived, power-law decay phase assigned to bimolecular recombination of these polarons, was observed to vary by over 2 orders of magnitude depending upon the polymer employed. In addition to this power-law decay phase, the blend films exhibited short-lived decays assigned, for the amorphous polymers, to neutral triplet states generated by geminate recombination of bound radical pairs and, for the more crystalline polymers, to the direct observation of the geminate recombination of these bound radical pairs to ground. These observations are discussed in terms of a two-step kinetic model for charge generation in polythiophene/PCBM blend films analogous to that reported to explain the observation of exciplex-like emission in poly(p-phenylenevinylene)-based blend films. Remarkably, we find an excellent correlation between the free energy difference for charge separation (deltaG(CS)rel) and yield of the long-lived charge generation, with efficient charge generation requiring a much larger deltaG(CS)rel than that required to achieve efficient PL quenching. We suggest that this observation is consistent with a model where the excess thermal energy of the initially formed polaron pairs is necessary to overcome their Coulombic binding energy. This observation has important implications for synthetic strategies to optimize organic solar cell performance, as it implies that, at least devices based on polythiophene/PCBM blend films, a large deltaG(CS)rel (or LUMO level offset) is required to achieve efficient charge dissociation.     

Preparation and electric property of PA/PVDF blend for energy storage material

This paper selected typical polar polymers which are polyvinylidene fluoride (PVDF) and polyamide (PA) to prepare PA/PVDF blend for energy storage material. Three kinds of PA (PA6, PA66 and PA11) with representative characters were chosen as the main research polymers for blending with PVDF. The electrical properties of three kinds of all-polymeric blends were tested and the microstructure was characterized by X-ray diffractometer (XRD), Fourier transform infrared instrument (FTIR), Scanning electron microscope (SEM) and Differential scanning calorimetry (DSC). Our finding suggests that the created high-ε polymeric blends represent a novel type of material that is easy to process. In addition, the dielectric constant and breakdown strength of PA/PVDFs are relatively high so that it can be applied to electronic components.     

A novel extremophile strategy studied by Raman spectroscopy

A case is made for the classification of the colonisation by Dirina massiliensis forma sorediata of pigments on ancient wall-paintings as extremophilic behaviour. The lichen encrustations studied using FT-Raman spectroscopy have yielded important molecular information which has assisted in the identification of the survival strategy of the organism in the presence of significant levels of heavy metal toxins. The production of a carotenoid, probably astaxanthin, at the surface of the lichen thalli is identified from its characteristic biomolecular signatures in the Raman spectrum, whereas the presence of calcium oxalate dihydrate (weddellite) has been identified at both the upper and lower surfaces of the thalli and in core samples taken from depths of up to 10mm through the encrustation into the rock substrate. The latter observation explains the significant disintegrative biodeteriorative effect of the colonisation upon the integrity of the wall-paintings and can be used to direct conservatorial and preservation efforts of the art work. A surprising result proved to be the absence of Raman spectroscopic evidence for the complexation of the metal pigments by the oxalic acid produced by the metabolic action of the organisms, unlike several cases that have been reported in the literature.     

Synthetic polyisoprenes studied by Fourier transform Raman spectroscopy

Fourier transform Raman spectra are presented for the cis-1,4 and trans-1,4 isomers of polyisoprenes Vibrational intensities are used to determine quantitatively the amounts of each isomer in the microstructure. Improvements over previous work are suggested for the quantitative assessment of 1,4 microstructure. Also, changes in the Raman spectrum due to oxidative degradation show that preferential oxidative degradation for the vinyl-3,4 units occurs. The α and β forms of trans-1,4 polyisoprene were studied the ν(CC) bands resolved were identified 4 cm⁻¹ apart. A study of the copolymerization of methyl methacrylate with isoprene showed that the 1,4 form is the most favoured form produced on copolymerization. Accurate cis-1,4 and trans-1,4 microstructural information could not, however, be determined.     

Sphingomyelin/phosphatidylcholine and cholesterol interactions studied by imaging mass spectrometry

Label-free imaging mass spectrometry is utilized the first time to study lipid-lipid interactions in a model membrane system. Ternary lipid mixtures of cholesterol (CH), sphingomyelin (SM), and phosphatidylcholine (PC) on supported Langmuir-Blodgett films are investigated as a mimic of the cellular membrane. The unique chemical specificity and imaging capability allow identification and localization of each lipid molecule in the membranes. The SM and PC in each ternary mixture vary in their acyl chain saturation with both, either, or neither one double bonded at the same position of their acyl chain. For the ternary mixtures with SM and PC both saturated or unsaturated, all the lipids are evenly distributed in the molecule-specific images. However, domain structures were observed for the two mixtures with either SM or PC unsaturated. In both films, the saturated lipid, whether it is SM or PC, colocalized with CH while the unsaturated lipid was excluded from the CH domains. These results strongly suggest that acyl chain saturation, rather than the specific interactions between SM and CH, is the dominating factor for SM colocalization with CH in the raft areas of the cellular membranes.     

Morphology development in PS/LLDPE blend during and after elongational deformation

The morphology development within a PS/LLDPE blend with 5 wt % of LLDPE at various stages of uniaxial deformation and after cessation of the flow was studied. Under given deformation conditions the dispersed LLDPE particles stretch and form highly elongated fibrils in agreement with a modified capillary number model. The morphology development after deformation was investigated for two different modes—relaxation and recovery. It was found that the stress in the sample is the crucial parameter determining the morphology development. During the first part of relaxation the stress in the sample is sufficient to hold the particles in the highly elongated state and, therefore, Rayleigh breakup takes place according to the Tomotika theory. It results in considerably finer phase structure. Contrary to this, in the absence of the stress in the sample, that is, in the recovery mode, the fibrils start to shrink immediately after the deformation and after a certain time the spherical morphology is restored. During elongation and recovery no evidence of coalescence was observed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 16–27, 2008     

PDMS melts on mica studied by confocal Raman scattering

We report surprising surface-induced torsional alignment of polydimethylsiloxane (PDMS) chains in contact with the muscovite (001) mica surface with and without confinement. The alignment was measured by polarized confocal Raman spectroscopy over diffraction-limit circular spots with approximately 0.3 microm diameter. Our discussion here focuses on the intense symmetric methyl-group vibration centered at 2907 cm(-1), whose Raman scattering intensity is found to depend on whether incident light is polarized in the x or y direction of the surface, the x direction being parallel to one of the mica optical axes. Furthermore, the Raman peak broadens significantly relative to that of bulk PDMS while remaining Lorentzian in shape, implying slower but homogeneous vibrational dephasing. However, the preferred orientation differs, apparently stochastically, from spot to spot on the surface. Possible origins of this heterogeneous surface-induced structure are discussed.     

Effect of random and block copolymer additives on a homopolymer blend studied by small-angle neutron scattering

Small-angle neutron scattering (SANS) has been employed to study a blend of polystyrene and polybutadiene modified by copolymer additives. SANS data from the one-phase region approaching the phase boundary has been acquired for blends modified by random and diblock copolymers that have equal amounts of styrene and butadiene monomers as well as a random copolymer with an unequal monomer composition. The binary blend is near the critical composition, and the copolymer concentrations are low at 2.5% (w/w). The data have been fitted with the random-phase approximation model (binary and multicomponent versions) to obtain Flory–Huggins interaction parameters (χ) for the various monomer interactions. These results are considered in the context of previous light scattering data for the same blend systems. The SANS cloud points are in good agreement with previous results from light scattering. The shifts in the phase boundary are due to the effects of the additives on the χ parameter at the spinodal. All the additives appear to lower the χ parameter between the homopolymers; this is in conflict with the predicted Flory–Huggins behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3191–3203, 2004     

The hydrogen-bond network in propylene-glycol studied by Raman spectroscopy

In the present work, we report a polarized Raman study versus temperature of the complex O–H stretching vibrational band (3800–3000 cm⁻¹) performed in a glass forming liquid, namely propylene-glycol (PG), with chemical formula given by H[OCH(CH₃)CH₂]OH. The spectra were collected in bulk and confined state within a sol–gel controlled porous glass having highly interconnected 25 Å diameter pores and characterized by a huge number of silanol groups (Si–OH), able to interact with PG molecules via hydrogen bond. The goal was to investigate how the hydrophilic nature of the surface influenced the molecular mobility of this hydrogen-bonded system, by monitoring intra- and inter-molecular host–host and host–guest interactions. The analysed O–H spectral region was decomposed into Gaussian symmetrical profiles, each of them associated to a well-defined aggregate, triggered by the presence of H-bond. Passing from the bulk state to the confined one, a clear change of the dynamical properties has been revealed and related to the interactions with the surface. The observed results were discussed on the basis of current models for associated liquids.     

The Effects of Dispersed Phase Morphology Induced by Flow on the Bulk Viscosity of HDPE/PA Blends

The apparent shear viscosity (ηa) of a blend composed of 97 wt % nigh-density polyethylene (HDPE) and 3 wt % polyamide (PA-66) was measured by capillary rheometry at different shear rates, below, near and above the melting point of PA-66, i.e. 240℃, 260℃and 280℃, respectively. At 260℃and a high shear rate,ηa of the blend reduced abnormally; and at 260℃, was lower than that at 280℃. The images of etched surface of extrudate observed by the SEM showed different dispersed phase morphology, induced by flow at different temperatures. It is suggested that the formation of fibrillar morphology of dispersed phase is a key factor for the abnormal reduction ofηa for the HDPE/PA blend.     

Correlation of Morphology Evolution with Superior Mechanical Properties in PA6/PS/PP/SEBS Blends Compatibilized by Multi-phase Compatibilizers

In this study,the maleic anhydride(MAH)and styrene(St)dual monomers grafted polypropylene(PP)and poly[styrene-b-(ethylene-co-butylene)-b-styrene](SEBS),i.e.PP-g-(MAH-co-St)and SEBS-g-(MAH-co-St)are prepared as multi-phase compatibilizers and used to compatibilize the PA6/PS/PP/SEBS(70/10/10/10)model quaternary blends.Both PS and SEBS are encapsulated by the hard shell of PP-g-(MAH-co-St)in the dispersed domains(about 2μm)of the PA6/PS/PP-g-(MAH-co-St)/SEBS(70/10/10/10)quaternary blend.In contrast,inside the dispersed domains(about 1μm)of the PA6/PS/PP/SEBS-g-(MAH-co-St)(70/10/10/10)quaternary blend,the soft SEBS-g-(MAH-co-St)encapsulates both the hard PS and PP phases and separates them.With increasing the content of the compatibilizers equally,the morphology of the PA6/PS/(PP+PP-g-(MAH-co-St))/(SEBS+SEBS-g-(MAH-co-St))(70/10/10/10)quaternary blends evolves from the soft(SEBS+SEBS-g-(MAH-co-St))encapsulating PS and partially encapsulating PP(about 1μm),then to PS exclusively encapsulated by the soft SEBS-g-(MAH-co-St)and then separated by PP-g-(MAH-co-St)inside the smaller domains(about 0.6μm).This morphology evolution has been well predicted by spreading coefficients and explained by the reaction between the matrix PA6 and the compatibilizers.The quaternary blends compatibilized by more compatibilizers exhibit stronger hierarchical interfacial adhesions and smaller dispersed domain,which results in the further improved mechanical properties.Compared to the uncompatibilized blend,the blend with both 10 wt%PP-g-(MAH-co-St)and 10 wt%SEBS-g-(MAH-co-St)has the best mechanical properties with the stress at break,strain at break and impact failure energy improved significantly by 97%,71%and 261%,respectively.There is a strong correlation between the structure and property in the blends.     

PHBV-GMA与PHBV-GMA/PPC共混物中接枝物的热性能与形态结构

以甲基丙烯酸缩水甘油酯(GMA)单体对聚(3-羟基丁酸酯-3-羟基戊酸酯)(PHBV)接枝改性,得到的产物PHBV-GMA与封端后的聚碳酸亚丙酯(PPC)反应性共混。索氏抽提器提取PHBV-GMA和PHBV-GMA/PPC共混物,分别得到两种接枝产物PHBV-g-GMA和PHBV-g-PPC,用差示扫描量热法(DSC)、偏光显微镜(POM)以及原子力显微镜(AFM)研究其热性能和形态结构。结果发现,GMA接枝后,对PHBV结晶有成核效应。PPC接枝PHBV后,接枝物PHBV-g-PPC结晶度降低,球晶尺寸减小,PHBV和PPC两种大分子间的相分离程度降低,相容性明显提高。