Multiphase coatings from complex radiation curable polyurethane dispersions

The waterborne nature of radiation curable polyurethane dispersions largely respond to the current environmental concerns and do not require any additional coalescent since the film formation (drying) and hardening (photo-curing) take place in distinct steps. It is possible to design aqueous dispersions with distinct polymer particle populations resulting in micro-structured coatings with optimized properties over a wide range of curing conditions. Mixed dispersions based on hard and soft acrylated polyurethane particles were used as model systems for the present study. The minimum film formation temperature has been investigated as a function of the hard:soft polymer ratio. The elastic modulus of the dry coatings shows a reinforcing effect consistent with the inclusion of hard domains in a soft continuous matrix. However, the level of reinforcement is not properly predicted by the usual mechanical models and it is qualitatively accounted for by assuming a composition gradient (interphase) between the hard domains and the matrix. The multiple-phase structure was clearly established by Atomic Force Microscopy in agreement with thermal analysis data. Furthermore the local nanoscale mechanical properties were mapped using a new imaging mode based on real-time force–distance curve analysis. Finally, the coatings prepared using this multiple-phase pattern present a clear benefit over conventional homogeneous coatings by offering an improved balance of chemical and mechanical resistance in pigmented systems applied on melamine-coated MDF panels.     

Rapid Determination of Free Fatty Acid in Extra Virgin Olive Oil by Raman Spectroscopy and Multivariate Analysis

We introduce a visible Raman spectroscopic method for determining the free fatty acid (FFA) content of extra virgin olive oil with the aid of multivariate analysis. Oleic acid was used to increase the FFA content in extra virgin olive oil up to 0.80% in order to extend the calibration span. For calibration purposes, titration was carried out to determine the concentration of FFA for the investigated oil samples. As calibration model for the FFA content (FFA%), a partial least squares (PLS) regression was applied. The accuracy of the Raman calibration model was estimated using the root mean square error (RMSE) of calibration and validation and the correlation coefficient (R ²) between actual and predicted values. The calibration curve of actual FFA% obtained by titration versus predicted values based on Raman spectra was established for different spectral regions. The spectral window (945–1600 cm⁻¹), which includes carotenoid bands, was found to be a useful fingerprint region being statistically significant for the prediction of the FFA%. High R ² and small RMSE values for calibration and validation could be obtained, respectively.     

Preparation of Polystyrene/Clay Nanocomposites by Free‐Radical Polymerization in Dispersion

Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.

     

Thermodynamic and Experimental Study of the Mg-Sn-Ag-In Quaternary System

Phase equilibria in the Mg-rich region of the Mg-Sn-Ag ternary system were determined by quenching experiments, differential scanning calorimetry, electron probe micro-analysis, and X-ray diffraction techniques. No ternary compounds were found in the studied isothermal sections. A critical evaluation of the available experimental data and a thermodynamic optimization of the Mg-Sn-Ag-In quaternary system were carried out using the calculation of phase diagrams method. The modified quasichemical model in the pair approximation was used for the liquid solution, which exhibits a high degree of short-range order. The solid phases were modeled with the compound energy formalism. All available and reliable experimental data were reproduced within experimental error limits. A self-consistent thermodynamic database was constructed for the Mg-Sn-Ag-In quaternary system, which can be used as a guide for Mg-based alloys development.     

Numerical modeling of nonisothermal polymer crystallization kinetics: Flow and thermal effects

A numerical model able to simulate polymer crystallization under nonisothermal flows is developed. It is based on the assumption that the trace of the extra‐stress tensor, calculated according to a viscoelastic multimode Upper Convected Maxwell (UCM) model, is the driving force of the flow‐induced extra nucleation. Two distinct sets of Schneider equations are used to describe the growth of thermally and flow induced nuclei. The model is then coupled with the momentum equations and the energy equation. As an application, a shear flow configuration between two plates (Couette flow) is simulated. The relative influence of the mechanical and thermal phenomena on the crystallization development as well as the final morphology distribution is then analyzed as a function of the shearing intensity and the cooling kinetics, in terms of nucleation density and crystallite mean sizes. POLYM. ENG. SCI., 50:2044–2059, 2010. © 2010 Society of Plastics Engineers     

Influence of various process conditions on surface finishes induced by the direct metal deposition laser technique on a Ti–6Al–4V alloy

The direct metal deposition (DMD) with laser is a free-form metal deposition process for manufacturing dense pieces, which allows generating a prototype or small series of near net-shape structures. One of the most critical issues is that produced pieces have a deleterious surface finish which systematically requires post machining steps. This problem has never been fully addressed before.The present work describes investigations on the DMD process, using an Yb-YAG disk laser, and a widely used titanium alloy (Ti–6Al–4V) to understand the influence of the main process parameters on the surface finish quality. The focus of our work was: (1) to understand the physical mechanisms responsible for deleterious surface finishes, (2) to propose different experimental solutions for improving surface finish.In order to understand the physical mechanisms responsible for deleterious surface finishes, we have carried out: (1) a precise characterization of the laser beam and the powder stream; (2) a large number of multi-layered walls using different process parameters (P(W), V(m/min), D_m (g/min), Gaussian or uniform beam distribution); (3) a real time fast camera analysis of melt pool dynamics and melt-pool – powder stream coupling; (4) a characterization of wall morphologies versus process parameters using 2D and 3D profilometry.The results confirm that surface degradation depends on two distinct aspects: the sticking of non-melted or partially melted particles on the free surfaces, and the formation of menisci with more or less pronounced curvature radii. Among other aspects, a reduction of layer thickness and an increase of melt-pool volumes to favor re-melting processes are shown to have a beneficial effect on roughness parameters. Last, a simple analytical model was proposed to correlate melt-pool geometries to resulting surface finishes.     

TP53 Targeted Deep Sequencing of Cell-Free DNA in Esophageal Squamous Cell Carcinoma Using Low-Quality Serum: Concordance with Tumor Mutation

Circulating cell-free DNA (cfDNA) is emerging as a potential tumor biomarker. CfDNA-based biomarkers may be applicable in tumors without an available non-invasive screening method among at-risk populations. Esophageal squamous cell carcinoma (ESCC) and residents of the Asian cancer belt are examples of those malignancies and populations. Previous epidemiological studies using cfDNA have pointed to the need for high volumes of good quality plasma (i.e., >1 mL plasma with 0 or 1 cycles of freeze-thaw) rather than archival serum, which is often the main available source of cfDNA in retrospective studies. Here, we have investigated the concordance of TP53 mutations in tumor tissue and cfDNA extracted from archival serum left-over from 42 cases and 39 matched controls (age, gender, residence) in a high-risk area of Northern Iran (Golestan). Deep sequencing of TP53 coding regions was complemented with a specialized variant caller (Needlestack). Overall, 23% to 31% of mutations were concordantly detected in tumor and serum cfDNA (based on two false discovery rate thresholds). Concordance was positively correlated with high cfDNA concentration, smoking history (p-value = 0.02) and mutations with a high potential of neoantigen formation (OR; 95%CI = 1.9 (1.11–3.29)), suggesting that tumor DNA release in the bloodstream might reflect the effects of immune and inflammatory context on tumor cell turnover. We identified TP53 mutations in five controls, one of whom was subsequently diagnosed with ESCC. Overall, the results showed that cfDNA mutations can be reliably identified by deep sequencing of archival serum, with a rate of success comparable to plasma. Nonetheless, 70% non-identifiable mutations among cancer patients and 12% mutation detection in controls are the main challenges in applying cfDNA to detect tumor-related variants when blindly targeting whole coding regions of the TP53 gene in ESCC.     

Personal multimedia services over a common home and access networking environment

This article presents a new end-to-end architecture model that will enable the deployment of a plethora of different multimedia services from diverse suppliers competitively coexisting over a common access and home networking environment. The model is focused on personal multimedia communication services and terminals. The proposed model is a segmentation of the end-to-end multimedia chain into several business segments. The interfaces among segments and functional entities inside each segment are identified and defined in the work. In order to study the impact level of the results achieved, a comparison with the approximation to NGN provided by current standardization bodies in the field (3GPP and TISPAN) is also included in the article. This comparison highlights the advantages of using this model as a solution to offer PMC services.     

Reduction of ASR-expansion using powders ground from various sources of reactive aggregates

This study assesses the potential of ground reactive aggregates to reduce or suppress expansion associated with ASR. Particular attention is paid to fine admixtures (<80 μm) added to mortars, which contain the reactive aggregates from which the fines were ground. Many varieties of aggregate (quarried and natural, igneous, metamorphic and sedimentary rocks) from different geological settings were subjected to an autoclave test. The replacement of 10–20% of the sand by reactive aggregate powder (RAP) of different surface areas from 11 different reactive aggregates led to the reduction of ASR-expansion by up to 78% compared with control mortars. Increasing the amount of fines led to better performance. No clear relationship was observed between the reactivity degree of the aggregates and the efficiency of their ground powder to reduce expansion. A general trend was found regarding the fineness of ground aggregates: finer particles were more effective in reducing expansion. The reduction of the expansion due to RAP is discussed in terms of parameters affecting its efficiency and of the mechanisms responsible for the reduction.     

The influence of wine polymers on the spontaneous precipitation of calcium tartrate in a model wine solution

The influence of wine polymers on the spontaneous precipitation of calcium tartrate in a model wine system has been examined. Rhamnogalacturonan‐I was identified as the most effective inhibitor (precipitation induction time of 180 min compared with 7 min for the standard model). It is argued that this is a consequence of rhamnogalacturonan‐I's ability to participate in the ‘egg‐box’ type sequestration of calcium ions. The more structurally complex rhamnogalacturonan‐II had only a minor influence on the induction time (22 min). Arabinogalactan proteins and mannoproteins also have little influence with induction times ranging from 12 to 15 min. An ultra‐filtration study of four Chardonnay wines, prepared with and without the use of pectolytic enzymes, was performed in a search for conditions that might maximise the concentration of rhamnogalacturonan‐I. However, rhamnogalacturonan‐I could not be identified in any of the four wines. Implications of these observations, specifically the need to understand the inhibition exerted by specific uronic acids, for winemaking and calcium tartrate precipitation are discussed.