Morphological comparison of isotactic polypropylene parts prepared by micro‐injection molding and conventional injection molding

The morphological feature of microparts evolved during micro‐injection molding may differ from that of the macroparts prepared by conventional injection molding, resulting in specific physical properties. In this study, isotactic polypropylene (iPP) microparts with 200 µm thickness and macroparts with 2000 µm thickness were prepared, and their morphological comparison was investigated by means of polarized light microscopy (PLM), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WAXD). The results presented some similarities and differences. PLM observations showed that the through‐the thickness‐morphology of micropart exhibited a similar “skin–core” structure as macropart, but presented a large fraction of shear layer in comparison to the macropart which presented a large fraction of core layer. The SEM observation of shear layer of micropart featured highly oriented shish‐kebab structure. The micropart had a more homogeneous distribution of lamellae thickness. The degree of crystallinity of the micropart was found to be higher than that of the macropart. High content of β‐crystal was found in micropart. The 2D WAXD pattern of the core layer of macropart showed full Debye rings indicating a random orientation, while the arcing of the shear layer indicates a pronounced orientation. The most pronounced arcing of the micropart indicates the most pronounced orientation of iPP chains within lamellae. Copyright © 2011 John Wiley & Sons, Ltd.     

Morphology evolution and crystalline structure of controlled‐rheology polypropylene in micro‐injection molding

In this paper, the microstructural evolution of controlled‐rheology polypropylene (CRPP) with different melt viscoelasticities was investigated by polarized optical microscopy, scanning electronic microscopy, differential scanning calorimeter, and wide‐angle X‐ray diffraction. It is found that a typical “skin‐core” structure formed in CRPP microparts and the thickness of oriented layer of CRPP microparts decreases notably with the addition of peroxide. The thickness of oriented layer and the distribution of different layers strongly depend on the melt flow properties and the corresponding relaxation time (λ). Furthermore, the mechanisms of the suppressed formation of oriented layers during the micro‐injection molding process are discussed mainly from the viewpoint of rheology and thermodynamics. It is revealed that the shear‐induced orientation is one of the key factors for the formation of oriented molecular structure (row nuclei). The final thickness of the oriented layer is the result of the competition between the orientation behavior and the disorientation behavior. Copyright © 2015 John Wiley & Sons, Ltd.     

Creep behavior of ultra‐thin polymer films

A novel microbubble inflation method has been used to determine the creep compliance of poly(vinyl acetate) and polystyrene ultra‐thin films (13–300 nm thick) at temperatures from below to above the glass temperature. We present results that suggest that time‐temperature and time‐thickness superposition hold in the glassy relaxation regime. Although time‐temperature superposition is found for the entire response curve for each thickness, we also find that time‐thickness superposition fails as the long‐time compliance is approached. This effect occurs because of a strong stiffening as the film thickness decreases. We also show first evidence of stiffening in the glassy regime of free standing films of polystyrene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1952–1965, 2008     

Structure and properties of polyethylene prepared via low‐frequency vibration‐assisted injection molding

A self‐made low‐frequency vibration‐assisted injection‐molding (VAIM) device was adopted to explore the relationship between mechanical property and morphology for high‐density polyethylene injected moldings. The main processing variables for the VAIM are vibration frequency and vibration pressure amplitude, and tensile properties and morphology were investigated under different VAIM processing conditions with conventional injection molding for comparison. The moldings prepared by VAIM exhibit a very well defined laminated morphology composed of a layered structure with enhanced crystallinity. Increased with vibration frequency at constant vibration pressure amplitude, the shish‐kebab structure is exhibited in the shear layer of the specimen prepared by VAIM, whereas row nucleation lamella exists in the same layer produced by enhanced vibration pressure amplitude at a constant vibration frequency. These oriented structures and enhanced crystallinity, confirmed by scanning electron microscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry, serve to obtain stronger injection moldings. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 13–21, 2005     

Reinforcement of solid‐melt interfaces for semicrystalline polymers in a sequential two‐staged injection molding process

The solid‐melt interfaces between polyethylene (PE) and polyamide 6 (PA6) reinforced by in situ reactive compatibilization in a sequential two‐staged injection molding process has been studied in this work. The effects of the maleic anhydride grafted PE content and processing parameters, such as injection pressure, injection speed, melt temperature, and mold temperature, on the interfacial adhesion were investigated experimentally. The results of the interfacial adhesion characterized by lap shear measurement showed that the interfacial temperature and heat transfer between PE and PA6 interfaces play a very significant role in the bonding process. The fracture surfaces of the specimens prepared at different calculated interfacial temperature were investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), which suggested that the fracture failure changes from adhesive to cohesive failure with increasing interfacial temperature. The contribution of crystalline parts of the in situ formed copolymers to the enhancement in interfacial adhesion also was determined by DSC analysis. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1112–1124, 2009     

Glycyl‐L‐alanine: a multi‐temperature neutron study

Neutron diffraction data have been collected at 12, 50, 150 and 295 K for the dipeptide glycyl‐L‐alanine, C₅H₁₀N₂O₃, in order to obtain accurate positional and anisotropic displacement parameters for the H atoms. The values of these parameters serve as a benchmark for assessing the equivalent parameters obtained from a so‐called Hirshfeld‐atom refinement of X‐ray diffraction data described elsewhere [Capelli et al. (2014). IUCrJ, 1 , 361–379]. The flexibility of the glycyl‐L‐alanine molecule in the solid and the hydrogen‐bonding interactions as a function of temperature are also considered.     

Influence of substrate chemistry and the network homogeneity of ultra‐thin cross‐linked polymer films cured at their surface on the main relaxations temperatures probing by microthermal analysis

Thin 200‐nm epoxy–amine mixtures were cured on silicon wafers with different surface chemistry to quantify the effect of the chemistry on the glass transition temperature evolution in ultra‐thin thermosetting films. Two surface treatments were investigated: the first one only consisted in the activation of the silanols groups at the silicon surface, whereas the second one consisted in the grafting 3‐aminopropyltrimethoxysilane (APTMS) monolayer on the silicon wafers. The epoxy films were deposited on these chemistry modified wafers by spin coating a toluene solution of DGEBA–amine mixture at stoichiometric ratio. The same cure processing was used for both samples. Thin films were analysed not only using microthermal and thermomechanical analysis to determine the relaxation transitions temperatures of these films but also using FTIR in infrared reflection absorption spectroscopy mode to determine the curing rate of these networks. It was found that all these thin films showed two different glass transitions, the first one at 96 °C and was independent of the surface treatments, whereas the second one increasing from 142 °C for the oxidised wafers surface to 167 °C for the aminosilane grafted on the silicon wafer. The substrate chemistry extent on the film network structure, the interfacial bonds and interactions are discussed. This work also illustrates the interest in using microthermal analysis to obtain relevant temperature glass transition of thin film at sub‐micrometre scale, strongly dependant of local structure and chemistry composition. Copyright © 2009 John Wiley & Sons, Ltd.     

Depth profiling in secondary ion mass spectrometry for ultra‐thin layer with nanometer order thickness by mesa‐structure fabrication

We attempted to make an accurate depth profiling in secondary ion mass spectrometry (SIMS) including backside SIMS for ultra‐thin nanometer order layer. The depth profiles for HfO₂ layers that were 3 and 5 nm thick in a‐Si/HfO₂/Si were measured using quadrupole and magnetic sector type SIMS instruments. The depth profiling for an ultra‐thin layer with a high depth resolution strongly depends on how the crater‐edge and knock‐on effects can be properly reduced. Therefore, it is important to control the analyzing conditions, such as the primary ion energy, the beam focusing size, the incidence angle, the rastered area, and detected area to reduce these effects. The crater‐edge effect was significantly reduced by fabricating the sample into a mesa‐shaped structure using a photolithography technique. The knock‐on effect will be serious when the depth of the layer of interest from the surface is located within the depth of the ion mixing region due to the penetration of the primary ions. Finally, we were able to separately assign the origin of the distortion to the crater‐edge effect and knock‐on effect. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural transformation from shish‐kebab crystals to micro‐fibrils through hot stretching process of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution

Structural evolution of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution via hot stretching process was investigated by in situ small‐angle X‐ray scattering, in situ wide‐angle X‐ray diffraction measurements, scanning electron microscopy, and differential scanning calorimetry. With the increase of stretching strain, the long period continuously increases at relative lower stretching temperature, while it first increases and then decreases rapidly at relative higher stretching temperature. The kebab thickness almost keeps constant during the whole hot‐stretching process and the kebab diameter continually decreases for all stretching temperatures. Moreover, the length of shish decreases slightly and the shish quantity increases although there is almost no change in the diameter of shish crystals during the hot stretching process. The degree of crystal orientation at different temperatures is as high as above 0.9 during the whole stretching process. These results indicate that the shish‐kebab crystals in ultra‐high molecular weight polyethylene fibers can transform continuously into the micro‐fibril structure composed mostly of shish crystals through the hot stretching process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 225–238     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

Evaluation of needle trap micro‐extraction and solid‐phase micro‐extraction: Obtaining comprehensive information on volatile emissions from in vitro cultures

Volatile organic compounds (VOCs) emitted from in vitro cultures may reveal information on species and metabolism. Owing to low nmol L⁻¹ concentration ranges, pre‐concentration techniques are required for gas chromatography–mass spectrometry (GC–MS) based analyses. This study was intended to compare the efficiency of established micro‐extraction techniques – solid‐phase micro‐extraction (SPME) and needle‐trap micro‐extraction (NTME) – for the analysis of complex VOC patterns. For SPME, a 75 μm Carboxen®/polydimethylsiloxane fiber was used. The NTME needle was packed with divinylbenzene, Carbopack X and Carboxen 1000. The headspace was sampled bi‐directionally. Seventy‐two VOCs were calibrated by reference standard mixtures in the range of 0.041–62.24 nmol L⁻¹ by means of GC–MS. Both pre‐concentration methods were applied to profile VOCs from cultures of Mycobacterium avium ssp. paratuberculosis. Limits of detection ranged from 0.004 to 3.93 nmol L⁻¹ (median = 0.030 nmol L⁻¹) for NTME and from 0.001 to 5.684 nmol L⁻¹ (median = 0.043 nmol L⁻¹) for SPME. NTME showed advantages in assessing polar compounds such as alcohols. SPME showed advantages in reproducibility but disadvantages in sensitivity for N‐containing compounds. Micro‐extraction techniques such as SPME and NTME are well suited for trace VOC profiling over cultures if the limitations of each technique is taken into account.     

Surface roughness and electrical conductivity of the SnO2 ultra‐thin layers investigated by X‐ray reflectivity

Spray pyrolysis technique was applied to deposit two sets of ultra‐thin layers of tin dioxide (SnO₂). For the first and second sets, 0.01 and 0.05 molar precursor solutions were prepared, respectively. In both sets, utilizing the X‐ray reflectivity (XRR) technique, the effect of precursor concentration (PC) and precursor volume (PV) on the layer structure are investigated. The layer thickness of the samples, in each set, is a PV‐dependent parameter. For the same PV, samples with higher PC have a larger thickness and higher density. The electron density profiles deduced from XRR data analyses establish a link between measured values of sheet resistance and electron densities. The samples with higher PV and PC show less sheet resistance. The quantum size effect was utilized to show that the surface roughness for layers of more than almost 200 Å of samples in set two plays no role in the layer conductivity. Meanwhile, the same effect explains, adequately, the role of the surface roughness in the resistivity of the ultra‐thin layers in Set 1.     

Dispersive micro‐solid‐phase extraction combined with online preconcentration by capillary electrophoresis for the determination of glycopyrrolate stereoisomers in rat plasma

A simple and sensitive analytical method for four isomers of glycopyrrolate in rat plasma was developed using cation‐selective exhaustive injection‐sweeping cyclodextrin‐modified electrokinetic chromatography (CSEI‐Sweeping‐CDEKC) for online enrichment combined with dispersive micro‐solid‐phase extraction pretreatment. The CSEI‐Sweeping‐CDEKC was conducted on an uncoated fused silica capillary (40.2 cm × 75 μm) with an applied voltage of –20 kV. The electrophoretic analysis was carried out in 30 mM phosphate solution at pH 2.0 containing 20 mg/mL sulfated‐β‐cyclodextrin and 5% acetonitrile. Under these optimized conditions, the detection limit for racemic glycopyrrolate was found to be 2.0 ng/mL and this method could increase 495‐fold detection sensitivity compared with the traditional injection method. Additionally, the parameters that affected the extraction efficiency of dispersive micro‐solid‐phase extraction were also examined systematically. The glycopyrrolate isomers in rat plasma samples as low as 0.0625 μg/mL were able to be separated and detected by capillary electrophoresis with the aid of CSEI‐sweeping. The findings of this study show that the dispersive micro‐solid‐phase extraction pretreatment coupled with CSEI‐Sweeping‐CDEKC is a rapid and convenient method for analyzing glycopyrrolate isomers in rat plasma.     

Effect of molding parameters on the properties of PP/PP sandwich injection moldings

The basic characteristics of a sandwich injection molded product depend on the properties of the respective resins that comprise the skin and core layers, and the skin/core resin volume ratio. The characteristics of the core layer resin and the skin/core ratio in particular may vary depending on the injection molding conditions. This report considers the influences that the molding conditions such as injection speed, cylinder temperature, and mold temperature confer on the mechanical properties of the sandwich moldings. The study employed, skin/core resin combinations involving similar and dissimilar materials i.e. homopolymer PP/homopolymer PP and homopolymer PP/copolymer PP, respectively. It was demonstrated that core cylinder temperature and mold temperature could be used to adjust the mechanical properties of sandwich injection moldings. In the case of single material sandwich moldings, injection speed seemed to play no significant role, even though it was clearly demonstrated that core volume increases with injection speed. However, core injection speed plays a significant role in the dual material system by lowering or increasing the mechanical strength of moldings as the case may be. Thus, the dormant or active role of injection speed depending on the material system has been highlighted.     

Estimation of the breakthrough volume of selected steroids for C‐18 solid‐phase extraction sorbent using retention data from micro‐thin layer chromatography

SPE method is a very popular technique, and is commonly used for the prepurification, concentration, and isolation of different organic compounds from variable matrices. In this work, the optimization of SPE process was carried out. The breakthrough volume of solid sorbents based on octadecylsilane was determined and three methods were compared: (1) calculation one – the breakthrough volume was calculated using retention factor k determined with micro‐TLC method, frontal analysis – (2) breakthrough volume was determined as volume of whole elution peak, and (3) breakthrough volume was determined as the center of peak gravity. For calculation method, the k values of key estrogens and progestogens were derived from the micro‐TLC experiment reported previously. By combining these three methods, we can point the start of elution, the maximum concentration of analyte in eluate, and the whole eluent volume, which is necessary to achieve an appropriate selectivity and high extraction recovery. Proposed calculation method allows to estimate the beginning of the steroid peak, when the analyte appears in the eluate flowing from the sorbent. Such observation advances the SPE optimization protocol that was described before and was based on the correlation between raw k_SPE and k_micro‐TLC data.     

Preparation and characterization of nanometer‐thin freestanding polymer foils for laser‐ion acceleration

We report on the production and characterization of polymer‐based ultra‐thin (sub 10 nm) foils suited for experiments on laser‐ion acceleration in the regime of radiation pressure acceleration. Beside the remarkable mechanical stability compared with commonly used diamond‐like‐carbon foils, a very homogeneous layer thickness and a small surface roughness have been achieved. We describe the technical issues of the production process as well as detailed studies of the mechanical stability and surface roughness tests. The capability of producing uniform targets of large area is essential for advanced laser‐ion acceleration projects which are dealing with high repetition rate and extended measurement series, but might also be useful for other applications which require ultra‐thin and freestanding substrates of high quality. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1355–1360     

A refined cavity construction algorithm for the conductor‐like screening model

A cavity construction algorithm based on the triangulation of an iso‐surface is introduced as a new standard for dielectric continuum solvation calculations with the Conductor‐like Screening Model COSMO. It overcomes deficiencies which have become apparent for the original COSMO standard cavity, especially in concave regions of the molecular shaped cavity. The new standard, called FINE Cavity, is described in this article with several application examples. The earlier COSMO cavity construction algorithms are described for comparison. © 2018 Wiley Periodicals, Inc.     

A high‐throughput screening method for determination of multi‐antibiotics in animal feed

A high‐throughput method based on ultrasonic‐assisted extraction, 96‐well plate thin‐film microextraction was established to determinate 18 antibiotics in animal feed. In this method, the extraction was implemented by ultrasonic‐assisted extraction for 30 min with disodium ethylenediaminetetraacetic acid‐McIlvaine buffer (pH 5) containing 6% sodium chloride w/v, purified by thin‐film microextraction and combined with 96‐well plate system to improve the efficiency. Optimization of thin‐film microextraction conditions was performed by methods of single factor and response surface, and finalized as: condition time: 20 min; adsorption time: 55 min; washing time: 5 s with water; desorption time: 30 min with acetonitrile/water (8:2, v/v) containing 0.1% formic acid v/v. Evaluation of different extractive phases showed that polystyrene‐divinylbenzene‐polyacrylonitrile was the optimum coating. The analysis was performed by ultra‐high performance liquid chromatography with tandem mass spectrometry. Recovery, inter‐ and intraday precision, linearity, limit of detection, and quantitation were evaluated. The average recoveries of 18 antibiotics were 66.6–93.5% at three spiked levels, intraday precision was 1–8.4%, and interday precision was 3.0–16.4%. The linearity was good for r² > 0.99. Limits of detection and quantification were found in the range of 1–14 and 4–48 µg/kg, respectively.     

A ToF‐SIMS investigation of a buried polymer/polymer interface exposed by ultra‐low‐angle microtomy

The interfacial region of a model multilayer coating system on an aluminium substrate has been investigated by high‐resolution time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Employing ultra‐low‐angle microtomy (ULAM), the interface between a poly(vinylidene difluoride) (PVdF)‐based topcoat and a poly(urethane) (PU)‐based primer ‘buried’ >20 µm below the PVdF topcoat's air/coating surface was exposed. Imaging ToF‐SIMS and subsequent post‐processing extraction of mass spectra of the ULAM‐exposed interface region and of the PVdF topcoat and PU primer bulks indicates that the material composition of the polymer/polymer interface region is substantially different to that of the bulk PVdF and PU coatings. Analysis of the negative ion mass spectra obtained from the PVdF/PU interface reveals the presence of a methacrylate‐based component or additive at the interface region. Reviewing the topcoat and primer coating formulations reveals that the PVdF topcoat formulation contains methyl methacrylate (MMA)–ethyl acrylate (EA) acrylic co‐polymer components. Negative ion ToF‐SIMS analysis of an acrylic co‐polymer confirms that it is these components that are observed at the PVdF/PU interface. Post‐processing extraction of ToF‐SIMS images based on the major ions of the MMA–EA co‐polymers reveals that these components are observed in high concentration at the extremities of the PVdF coating, i.e. at the polymer/polymer interface, but are also observed to be distributed evenly throughout the bulk of the PVdF topcoat. These findings confirm that a fraction of the MMA–EA acrylic co‐polymers in the formulation segregate to the topcoat/primer interface where they enhance the adhesive properties exhibited by the PVdF topcoat towards the underlying PU primer substrate. Copyright © 2004 John Wiley & Sons, Ltd.     

Unexpected molecular weight dependence of shish kebab in water‐assisted injection molded HDPE

As a part of continuous efforts to systematically understand the morphological development in water‐assisted injection molding, high density polyethylene with different molecular weights was molded in this study. Unexpectedly, it was found that shish kebab with high lamellar and molecular orientations was formed in the sample with a lower molecular weight (LMW) rather than in the higher one, especially in the water channel layer. Present finding is obviously inconsistent with the general consensus, that is, higher molecular weight (HMW) polymer is much easier to form preferential orientation in flow field than LMW one. Such anomalous phenomenon is explained by the fact that even though melts experienced the same processing, lower shear rate is practically achieved in HMW sample due to its high viscosity. The result indicates that the flow history in industrial processing method is far from that in laboratory one. Copyright © 2012 John Wiley & Sons, Ltd.