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Determination of the gel point of formaldehyde-based wood adhesives by using a multiwave technique
(2023)
Determining the instant of gelation of formaldehyde-based wood adhesives as an assessment parameter for their curing rate is important for optimizing the curing behavior. Due to the stoichiometrically imbalanced networks of formaldehyde-based adhesives, the crossover point of storage G′ and loss modulus G″ cannot unconditionally be assumed as the gel point in oscillatory time sweeps as the material response is frequency-dependent. This study aims to determine the gel point of selected adhesives by the isothermal multiwave oscillatory shear test. A thorough comparison between the gel and the crossover point of G′ and G″ is performed. Rheokinetic analysis showed no significant difference between the activation energies calculated at the gel point determined by a multiwave test and the crossover point obtained by the time sweep test. Hence, for resins with similar curing reactions, a reliable determination of gel point by applying a multiwave test is needed for a comparison of their reactivity.
Sol-gel-controlled size and morphology of mesoporous silica microspheres using hard templates
(2023)
Mesoporous silica microspheres (MPSMs) represent a promising material as a stationary phase for HPLC separations. The use of hard templates provides a preparation strategy for producing such monodisperse silica microspheres. Here, 15 MPSMs were systematically synthesized by varying the sol–gel reaction parameters of water-to-precursor ratio and ammonia concentration in the presence of a porous p(GMA-co-EDMA) polymeric hard template. Changing the sol–gel process factors resulted in a wide range of MPSMs with varying particle sizes from smaller than one to several micrometers. The application of response surface methodology allowed to derive quantitative predictive models based on the process factor effects on particle size, pore size, pore volume, and specific surface area of the MPSMs. A narrow size distribution of the silica particles was maintained over the entire experimental space. Two larger-scale batches of MPSMs were prepared, and the particles were functionalized with trimethoxy(octadecyl) silane for the application as stationary phase in reversed-phases liquid chromatography. The separation of proteins and amino acids was successfully accomplished, and the effect of the pore properties of the silica particles on separation was demonstrated.
High-performance liquid chromatography is one of the most important analytical tools for the identification and separation of substances. The efficiency of this method is largely determined by the stationary phase of the columns. Although monodisperse mesoporous silica microspheres (MPSM) represent a commonly used material as stationary phase their tailored preparation remains challenging. Here we report on the synthesis of four MPSMs via the hard template method. Silica nanoparticles (SNPs) which form the silica network of the final MPSMs were generated in situ from tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl) triethoxysilane (APTES) functionalized p(GMA-co-EDMA) as hard template. Methanol, ethanol, 2-propanol, and 1-butanol were applied as solvents to control the size of the SNPs in the hybrid beads (HB). After calcination, MPSMs with different sizes, morphology and pore properties were obtained and characterized by scanning electron microscopy, nitrogen adsorption and desorption measurements, thermogravimetric analysis, solid state NMR and DRIFT IR spectroscopy. Interestingly, the 29Si NMR spectra of the HBs show T and Q group species which suggests that there is no covalent linkage between the SNPs and the template. The MPSMs were functionalized with trimethoxy (octadecyl) silane and used as stationary phases in reversed-phase chromatography to separate a mixture of eleven different amino acids. The separation characteristics of the MPSMs strongly depend on their morphology and pore properties which are controlled by the solvent during the preparation of the MPSMs. Overall, the separation behavior of the best phases is comparable with those of commercially available columns. The phases even achieve faster separation of the amino acids without loss of quality.
Rapid and robust quality monitoring of the composition of meat pastes is of fundamental importance in processing meat and sausage products. Here, an in-line near-infrared spectroscopy/micro-electro-mechanical-system-(MEMS)-based approach, combined with multivariate data analysis, was used for measuring the constituents fat, protein, water, and salt in meat pastes within a typical range of meat paste recipes. The meat pastes were spectroscopically characterized in-line with a novel process analyzer prototype. By integrating salt content in the calibration set, robust predictive PLSR models of high accuracy (R2 > 0.81) were obtained that take interfering matrix effects of the minor and NIR-inactive meat paste recipe component “salt” into account as well. The nonlinear blending behavior of salt concentration on the spectral features of meat pastes is discussed based on a designed mixture experiment with four systematically varied components.
Monodisperse porous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) particles are widely applied in different fields, as their pore properties can be influenced and functionalization of the epoxy group is versatile. However, the adjustment of parameters which control morphology and pore properties such as pore volume, pore size and specific surface area is scarcely available. In this work, the effects of the process factors monomer:porogen ratio, GMA:EDMA ratio and composition of the porogen mixture on the response variables pore volume, pore size and specific surface area are investigated using a face centered central composite design. Non-linear effects of the process factors and second order interaction effects between them were identified. Despite the complex interplay of the process factors, targeted control of the pore properties was possible. For each response a response surface model was derived with high predictive power (all R2 predicted > 0.85). All models were tested by four external validation experiments and their validity and predictive power was demonstrated.
Porous silica materials are often used for drug delivery. However, systems for simultaneous delivery of multiple drugs are scarce. Here we show that anisotropic and amphiphilic dumbbell core–shell silica microparticles with chemically selective environments can entrap and release two drugs simultaneously. The dumbbells consist of a large dense lobe and a smaller hollow hemisphere. Electron microscopy images show that the shells of both parts have mesoporous channels. In a simple etching process, the properly adjusted stirring speed and the application of ammonium fluoride as etching agent determine the shape and the surface anisotropy of the particles. The surface of the dense lobe and the small hemisphere differ in their zeta potentials consistent with differences in dye and drug entrapment. Confocal Raman microscopy and spectroscopy show that the two polyphenols curcumin (Cur) and quercetin (QT) accumulate in different compartments of the particles. The overall drug entrapment efficiency of Cur plus QT is high for the amphiphilic particles but differs widely between Cur and QT compared to controls of core–shell silica microspheres and uniformly charged dumbbell microparticles. Furthermore, Cur and QT loaded microparticles show different cancer cell inhibitory activities. The highest activity is detected for the dual drug loaded amphiphilic microparticles in comparison to the controls. In the long term, amphiphilic particles may open up new strategies for drug delivery.
Melamine-formaldehyde (MF) resins are widely used as surface finishes for engineered wood-based panels in decorative laminates. Since no additional glue is applied in lamination, the overall residual curing capacity of MF resins is of great technological importance. Residual curing capacity is measured by differential scanning calorimetry (DSC) as the exothermic curing enthalpy integral of the liquid resin. After resin synthesis is completed, the resulting pre-polymer has a defined chemical structure with a corresponding residual curing capacity. Predicting the residual curing capacity of a resin batch already at an early stage during synthesis would enable corrective measures to be taken by making adjustments while synthesis is still in progress. Thereby, discarding faulty batches could be avoided. Here, by using a batch modelling approach, it is demonstrated how quantitative predictions of MF residual curing capacity can be derived from inline Fourier Transform infrared (FTIR) spectra recorded during resin synthesis using partial least squares regression. Not only is there a strong correlation (R2 = 0.89) between the infrared spectra measured at the end of MF resin synthesis and the residual curing capacity. The inline reaction spectra obtained already at the point of complete dissolution of melamine upon methylolation during the initial stage of resin synthesis are also well suited for predicting final curing performance of the resin. Based on these IR spectra, a valid regression model (R2 = 0.85) can be established using information obtained at a very early stage of MF resin synthesis.
We report on the cure characterization, based on inline monitoring of the dielectric parameters, of a commercially available epoxy phenol resin molding compound with a high glass transition temperature (>195 °C), which is suitable for the direct packaging of electronic components. The resin was cured under isothermal temperatures close to general process conditions (165–185 °C). The material conversion was determined by measuring the ion viscosity. The change of the ion viscosity as a function of time and temperature was used to characterize the cross-linking behavior, following two separate approaches (model based and isoconversional). The determined kinetic parameters are in good agreement with those reported in the literature for EMCs and lead to accurate cure predictions under process-near conditions. Furthermore, the kinetic models based on dielectric analysis (DEA) were compared with standard offline differential scanning calorimetry (DSC) models, which were based on dynamic measurements. Many of the determined kinetic parameters had similar values for the different approaches. Major deviations were found for the parameters linked to the end of the reaction where vitrification phenomena occur under process-related conditions. The glass transition temperature of the inline molded parts was determined via thermomechanical analysis (TMA) to confirm the vitrification effect. The similarities and differences between the resulting kinetics models of the two different measurement techniques are presented and it is shown how dielectric analysis can be of high relevance for the characterization of the curing reaction under conditions close to series production.
Monodisperse polystyrene spheres are functional materials with interesting properties, such as high cohesion strength, strong adsorptivity, and surface reactivity. They have shown a high application value in biomedicine, information engineering, chromatographic fillers, supercapacitor electrode materials, and other fields. To fully understand and tailor particle synthesis, the methods for characterization of their complex 3D morphological features need to be further explored. Here we present a chemical imaging study based on three-dimensional confocal Raman microscopy (3D-CRM), scanning electron microscopy (SEM), focused ion beam (FIB), diffuse reflectance infrared Fourier transform (DRIFT), and nuclear magnetic resonance (NMR) spectroscopy for individual porous swollen polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles. Polystyrene particles were synthesized with different co-existing chemical entities, which could be identified and assigned to distinct regions of the same particle. The porosity was studied by a combination of SEM and FIB. Images of milled particles indicated a comparable porosity on the surface and in the bulk. The combination of standard analytical techniques such as DRIFT and NMR spectroscopies yielded new insights into the inner structure and chemical composition of these particles. This knowledge supports the further development of particle synthesis and the design of new strategies to prepare particles with complex hierarchical architectures.
Melamine-formaldehyde resins are widely used for decorative paper impregnation. Resin properties relevant for impregnation are mainly determined already at the stage of resin synthesis by the applied reaction conditions. Thus, understanding the relationship between reaction conditions and technological properties is important. Response surface methodology based on orthogonal parameter level variations is the most suitable tool to identify and quantify factor effects and deduce causal correlation patterns. Here, two major process factors of MF resin synthesis were systematically varied using such a statistical experimental design. To arrive at resins having a broad range of technological properties, initial pH and M:F ratio were varied in a wide range (pH: 7.9–12.1; M:F ratio: 1:1.5–1:4.5). The impregnation behavior of the resins was modeled using viscosity, penetration rate and residual curing capacity as technological responses. Based on the response surface models, nonlinear and synergistic action of process factors was quantified and a suitable process window for preparing resins with favorable impregnation performance was defined. It was found that low M:F ratios (~1:2–1:2.5) and comparatively high starting pHs (~pH 11) yield impregnation resins with rapid impregnation behavior and good residual curing capacity.