Gilles Régnier

Spatial distribution of molecular orientation in injection molded iPP: influence of processing conditions

In this paper, the influence of processing conditions on the spatial distribution of the molecular orientation was determined within the depth of the thickness of injection molded isotactic polypropylene (iPP) plates. Small 35 μm-thick slices were microtomed from the surface to the core of 1 and 3 mm-thick plates. The orientation functions along the three crystallographic axes were determined on the slices from IR dichroism measurements and WAXS pole figures. It was found that the orientation of the amorphous phase was low and the crystalline orientation had a maximum in the shearing layer, which was solidified during the filling stage. The plate thickness seemed to govern the global level of orientation, while the injection speed determined the thickness of the shearing layer without changing the maximum of orientation. Changing the mold temperature from 20 to 40 °C did not modify the molecular orientation. A specific bimodal crystalline orientation was found in the shearing layer. This crystalline structure continued in the post-filling layer, but the local symmetry axes tilted towards the core.

ANALYSIS OF THE PRESSURE EFFECT ON THE CRYSTALLIZATION KINETICS OF POLYPROPYLENE: DILATOMETRIC MEASUREMENTS AND THERMAL GRADIENT MODELING

Dilatometric measurements in isobaric cooling mode were performed to study the pressure effects on the crystallization kinetics of polypropylene (PP) up to 100 MPa. The experimental specific volume curves were analyzed by taking into account the thermal gradient that appears in the sample even for relatively low cooling rates. The Tait equation was used to describe the specific volume of the purely amorphous phase, and linear variations of the purely crystalline phase specific volume are considered. The relative crystal linity was modeled using the Nakamura equation, which is relevant for non-constant cooling rates. Considering an Avrami exponent of 3, the Nakamura rate constant was obtained first at atmospheric pressure and then generalized for higher pressures considering the equilibrium melting temperature variation. The obtained intrinsic specific volume was validated by computing the thermal gradient in the sample and comparing the calculated average specific volume to the experimental one.

PVT measurement methodology for semicrystalline polymers to simulate injection-molding process

This article discusses the specific volume-measurement methods for semicrystalline polymers needed in order to obtain reliable data. Particularly, the effect of the cooling rate is analyzed, taking into account the thermal gradient in a cylindrical sample. Experimental results for a polypropylene form the basis for the study. In a first step our thermal model was validated by comparing the calculated results with the experimental ones for a temperature range higher than the crystallization zone with different cooling rates and by analyzing the stabilization time of the measured specific volume after cessation of the cooling. Secondly, specific-volume evolutions from 220°C to 50°C for different cooling rates and different pressures were analyzed, revealing that when the data are corrected to eliminate the thermal gradient effect, the transition zone is much narrower than the experimental one. Moreover, the effect of the pressure and the cooling rate on the relative crystallinity function—that is, on the crystallization kinetics—can be more accurately evaluated.

Induced crystallization and orientation of poly(ethylene terephthalate) during uniaxial and biaxial elongation

Stretching PET at a high strain rate above the glass transition temperature has a positive effect on the strength of the material. In a recent paper [1] , we presented the influence of stretch and blow molding parameters on the properties of the final product, especially on the crystallinity induced by stretching. In this paper, we focus on the effects of loading, temperature, elongation and strain rate on macromolecular orientation and crystallization kinetics. We present experimental results from uniaxial and biaxial elongation tests carried out on injected PET specimens. To minimize the effect of quiescent crystallization, specimens are quickly heated with infrared lamps before the test and temperature is regulated during the test. Both uniaxial and biaxial tests are analyzed using a cross correlation technique [2] that compares a picture used as reference and the picture of the deformed specimen. This technique allows us to determine all strain components at each point of the specimen, even when the strain field is not homogeneous. In a second part, we present measurements of macromolecular orientation and crystallinity ratio performed after each test. The infrared dichroism technique is used to determine the orientation of the microscopic morphology of PET before and after the testing. DSC measurements and density measurements are carried out to calculate the crystallinity ratio. Influences of strain rate, temperature and strain path sequence are evaluated in order to build a database for recent models of induced crystallization [3],[4],[5] .

The CryoCapsule: simplifying correlative light to electron microscopy.

Correlating complementary multiple scale images of the same object is a straightforward means to decipher biological processes. Light microscopy and electron microscopy are the most commonly used imaging techniques, yet despite their complementarity, the experimental procedures available to correlate them are technically complex. We designed and manufactured a new device adapted to many biological specimens, the CryoCapsule, that simplifies the multiple sample preparation steps, which at present separate live cell fluorescence imaging from contextual high‐resolution electron microscopy, thus opening new strategies for full correlative light to electron microscopy. We tested the biological application of this highly optimized tool on three different specimens: the in vitro Xenopus laevis mitotic spindle, melanoma cells over‐expressing YFP‐langerin sequestered in organized membranous subcellular organelles and a pigmented melanocytic cell in which the endosomal system was labeled with internalized fluorescent transferrin.

A mesofluidic multiplex immunosensor for detection of circulating cytokeratin-positive cells in the blood of breast cancer patients

We have recently reported the analytical performance of an immunosensor comprising one mm-scale parallel plate laminar flow chamber and applied to capture MCF7 breast cancer cells (Ehrhart et al., Biosens. Bioelectr. 24, 467, 2008). Herein we present a new multiplex immunosensor embodying four parallel plate laminar flow chambers that fit onto a standard, functionalized, microscopy glass slide. The four surfaces are coated with long alkyl chain spacers of 21-aminohenicosyl trichlorosilane (AHTS) and then grafted with a monoclonal anti-human epithelial cell adhesion molecule (EpCAM) antibody specific of target cells to immobilize. We first demonstrate a significantly (P < 0.01) improved capacity of each of the four flow chambers of the multiplex immunosensor to capture MCF7 cells compared to the previous single chamber device. Second, in addition to an increase of cell immobilization, the multiplex device offers a versatile tool easily grafted with various purified antibodies onto the four surfaces. Third, we obtained high cell capture rate and efficiency of various numbers of MCF7 cells spiked in buffer containing an equal number of background leukocytes. And fourth, we demonstrate isolation efficiency of circulating tumor cells (CTCs) from peripheral blood drawn from a small cohort of patients with localized or metastatic breast cancer. This new multiplex immunosensor could be tested for its potential to capture different subpopulations of CTCs.

Limitations of Simple Flow Models for the Simulation of Nanoimprint

Abstract A quick evaluation of the forces involved in nanoimprint would be very helpful in the prevention of mold deflection. Unfortunately, it is shown here that assuming simplified flows may lead to quite incorrect evaluations of these forces, even for simple periodic patterns and a Newtonian behavior. The mere use of the classical result of the lubrication theory does not account for the range of thickness-to-width ratios that may be involved, especially at the beginning of the process. An improved squeeze model includes this effect, but still underestimates the imprint force. Moreover, finite element simulations demonstrate limitations of two more elaborate models that are found in the literature. These simulations also show that two flow modes can be defined, according to whether or not the polymer touches the mold sidewalls. A deeper analysis of these two modes may help the definition of a more appropriate simplified model in the future.

Preparation and characterization of poly(ethylene terephthalate) films coated by chitosan and vermiculite nanoclay

Chitosan (CS) layers are coated on a poly(ethylene terephthalate) (PET) film in order to decrease the oxygen permeability through the polymeric films for food packaging applications. Oxygen transmission rate (OTR) of the 130 μm PET films can be decreased from 11 to only 0.31 cm3/m².day with a coated layer of 2 μm of CS. Additional decrease is obtained with the addition of vermiculite (VMT) to CS matrix in high proportion (40 to 50 w/w%). The OTR of the coated PET films decreased to very low values, below the detection limit of commercial instrumentation (≤0.008 cm3/m2 day). This high-barrier behavior is believed to be due to the brick wall nanostructure, which produces an extremely tortuous path for oxygen molecules.

Influence of temperature on dielectric properties of PA-12/CNT composites

Polyamide12 (PA12)/multiwalled nanotubes (MWNT) composites were characterized in terms of complex permittivity and conductivity. Measurements were achieved on a LCR meter in a frequency range between 102 and 106 Hz. Samples were placed between plate-plate geometry electrodes and heated at temperature higher than melt temperature. Electrical and dielectric properties show different behaviours depending of the MWNT content, implying that different conduction mechanisms are involved.

Relationship between microstructure and elastic properties of semi-crystalline polymers

Actually semi-crystalline materials are widely used as structural materials. During the part forming, the stretching or the shearing of the polymer melt under strong cooling conditions lead to generate specific crystalline morphologies such as deformed spherulites, shish– kebab or more complex crystalline macrostructure like in polypropylene for example [1]. Moreover crystallinity variations along the part and in the part depth can be observed. The crystalline orientation is responsible for possible anisotropic behavior while variations of the amount of crystallinity induce strong variations of the mechanical properties. There is an industrial need of developing behavior laws for the prediction of these mechanical properties. Actually, simulation based on molecular models allows the prediction of the final molecular orientation [2, 3, 4]. It stills a huge gap between predicted crystalline morphology of the polymer and the prediction of their mechanical properties. Even thought semicrystalline polymer are closer to composite even nano-compsite material few works are done to predict their properties as it the case of composite or filled polymer. Our work deals with te elastic properties. In his works of Halpin and Kardos [5] proposed determine the elastic moduli of semi-crystalline polymers. The lamellae are supposed to be fibers. An adjustable parameter in this model was linked to crystallite shape ratio. However, this model is well adapted for low volume fraction. This is not the case of semi-crystalline materials, for which the crystallinity can often reach 60 to 70%.