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The powder coating of veneered particle boards by the sequence electrostatic powder application -powder curing via hot pressing is studied in order to create high gloss surfaces. To obtain an appealingaspect, veneer Sheets were glued by heat and pressure on top of particle boards and the resulting surfaceswere used as carrier substrates for powder coat finishing. Prior to the powder coating, the veneeredparticle board surfaces were pre-treated by sanding to obtain good uniformity and the boards werestored in a climate chamber at controlled temperature and humidity conditions to adjust an appropriate electrical surface resistance. Characterization of surface texture was done by 3D microscopy. The surfaceelectrical resistance was measured for the six veneers before and after their application on the particleboard surface. A transparent powder top-coat was applied electrostatically onto the veneered particleboard surface. Curing of the powder was done using a heated press at 130◦C for 8 min and a smooth, glossy coating was obtained on the veneered surfaces. By applying different amounts of powder thecoating thickness could be varied and the optimum amount of powder was determined for each veneer type.
In the powder coating of veneered particle boards the highly reactive hybrid epoxy/polyester powder transparent Drylac 530 Series from TIGER Coatings GmbH & Co. KG, Wels, Austria was used. Curing is accelerated by a mixture of catalysts reaching curing times of 3 min at 150 °C or 5 min at 135 °C which allows for energy and time savings making Drylac Series 530 powder suitable for the coating of temperaturesensitive substrates such as MDF and wood.
Decorative laminates based on melamine formaldehyde (MF) resin impregnated papers are used at great extent for surface finishing of engineered wood that is used for furniture, kitchen, and working surfaces, flooring and exterior cladding. In all these applications, optically flawless appearance is a major issue. The work described here is focused on enhancing the cleanability and antifingerprint properties of smooth, matt surface-finished melamine-coated particleboards for furniture fronts, without at the same time changing or deteriorating other important surface parameters such as hardness, roughness or gloss. In order to adjust the surface polarity of a low pressure melamine film, novel interface-active macromolecular compounds were prepared and tested for their suitability as an antifingerprint additive. Two hydroxy-functional surfactants (polydimethysiloxane, PDMS-OH and perfluoroether, PF-OH) were oxidized under mild conditions to the corresponding aldehydes (PDMS-CHO and PF-CHO) using a pyridinium chlorochromate catalyst. With the most promising oxidized polymeric additive, PDMS-CHO, the contact angles against water, n-hexadecane, and squalene increased from 79.8°, 26.3° and 31.4° for the pure MF surface to 108.5°, 54.8°, and 59.3°, respectively, for the modified MF surfaces. While for the laminated MF surface based on the oxidized fluoroether the gloss values were much higher than required, for the surfaces based on oxidized polydimethylsiloxane the technological values as well as the lower gloss values were in agreement with the requirements and showed much improved surface cleanability, as was also confirmed by colorimetric measurements.
Here, we report the continuous peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto a standard polyolefin by means of reactive extrusion to produce a functionalized liquid ethylene propylene copolymer (EPM). The effects of the process parameters governing the grafting reaction and their synergistic interactions are identified, quantified and used in a mathematical model of the extrusion process. As process variables the VTMS and peroxide concentrations and the extruder temperature setting were systematically studied for their influence on the grafting and the relative grafting degree using a face-centered central composite design (FCD). The grafting degree was quantified by 1H NMR spectroscopy. Response surface methodology (RSM) was used to calculate the most efficient grafting process in terms of chemical usage and graft yield. With the defined processing window, it was possible to make precise predictions about the grafting degree with at the same time highest possible relative degree of grafting.
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.
For optimization of production processes and product quality, often knowledge of the factors influencing the process outcome is compulsory. Thus, process analytical technology (PAT) that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality. The present study aims at characterizing a well-known industrial process, the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters (FAME) for usage as biodiesel in a continuous micro reactor set-up. To this end, a design of experiment approach is applied, where the effects of two process factors, the molar ratio and the total flow rate of the reactants, are investigated. The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield. The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression. The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis. A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination (R²) of 0.9608. Thus, we applied a PAT approach to generate further insight into this established industrial process.
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.
Mesoporous silica microspheres (MPSMs) find broad application as separation materials in high liquid chromatography (HPLC). A promising preparation strategy uses p(GMA-co-EDMA) as hard templates to control the pore properties and a narrow size distribution of the MPMs. Here six hard templates were prepared which differ in their porosity and surface functionalization. This was achieved by altering the ratio of GMA to EDMA and by adjusting the proportion of monomer and porogen in the polymerization process. The various amounts of GMA incorporated into the polymer network of P1-6 lead to different numbers of tetraethylene pentamine in the p(GMA-co-EDMA) template. This was established by a partial least squares regression (PLS-R) model, based on FTIR spectra of the templates. Deposition of silica nanoparticles (SNP) into the template under Stoeber conditions and subsequent removal of the polymer by calcination result in MPSM1-6. The size of the SNPs and their incorporation depends on the pore parameters of the template and degree of TEPA functionalization. Moreover, the incorporated SNPs construct the silica network and control the pore parameters of the MPSMs. Functionalization of the MPSMs with trimethoxy (octadecyl) silane allows their use as a stationary phase for the separation of biomolecules. The pore characteristics and the functionalization of the template determine the pore structure of the silica particles and, consequently, their separation properties.
The hard template method for the preparation of monodisperse mesoporous silica microspheres (MPSMs) has been established in recent years. In this process, in situ-generated silica nanoparticles (SNPs) enter the porous organic template and control the size and pore parameters of the final MPSMs. Here, the sizes of the deposited SNPs are determined by the hydrolysis and condensation rates of different alkoxysilanes in a base catalyzed sol–gel process. Thus, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate (TPOS) and tetrabutyl orthosilicate (TBOS) were sol–gel processed in the presence of amino-functionalized poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (p(GMA-co-EDMA)) templates. The size of the final MPSMs covers a broad range of 0.5–7.3 µm and a median pore size distribution from 4.0 to 24.9 nm. Moreover, the specific surface area can be adjusted between 271 and 637 m2 g−1. Also, the properties and morphology of the MPSMs differ according to the SNPs. Furthermore, the combination of different alkoxysilanes allows the individual design of the morphology and pore parameters of the silica particles. Selected MPSMs were packed into columns and successfully applied as stationary phases in high-performance liquid chromatography (HPLC) in the separation of various water-soluble vitamins.
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.
Clay minerals play an increasingly important role as functional fillers and reinforcing materials for clay polymer nanocomposites (CPN) in advanced applications. Among the prerequisites necessary for polymer improvement by clay minerals are homogeneous and stable Distribution of the clay mineral throughout the CPN, good compatibility of the reinforcement with the Matrix component and suitable processability. Typically, clay minerals are surface-modified with organic interface active compounds like detergents or silanes to obtain favorable properties as filler. They are incorporated into the polymer matrix using manufacturing Equipment like extruders, batch reactors or other mixing machines. In order for the surface modification to survive the stresses and strains during incorporation, the modified clay minerals must display sufficient thermal and mechanical stability to retain the compatibilizing effect. In the present study, thermogravimetry was used in combination with isoconversional kinetic analysis to determine the thermal stability of a silane-modified clay mineral based on bentonite. These findings were compared with the stability of the same clay mineral that was only surfactant-modified. It was found that silane modification leads to significantly improved thermal stability, which depends strongly on the type of silane employed.
Recycling of poly(ethylene terephthalate) (PET) is of crucial importance, since worldwide amounts of PETwaste increase rapidly due to its widespread applications. Hence, several methods have been developed, like energetic, material, thermo-mechanical and chemical recycling of PET. Most frequently, PET-waste is incinerated for energy recovery, used as additive in concrete composites or glycolysed to yield mixtures of monomers and undefined oligomers. While energetic and thermo-mechanical recycling entail downcycling of the material, chemical recycling requires considerable amounts of chemicals and demanding processing steps entailing toxic and ecological issues. This review provides a thorough survey of PET-recycling including energetic, material, thermo-mechanical and chemical methods. It focuses on chemical methods describing important reaction parameters and yields of obtained reaction products. While most methods yield monomers, only a few yield undefined low molecular weight oligomers for impaired applications (dispersants or plasticizers). Further, the present work presents an alternative chemical recycling method of PET in comparison to existing chemical methods.
The intelligent recycling of plastics waste is a major concern. Because of the widespread use of polyethylene terephtalate, considerable amounts of PET waste are generated that are ideally re-introduced into the material cycle by generating second generation products without loss of materials performance. Chemical recycling methods are often expensive and entail environmentally hazardous by-products. Established mechanical methods generally provide materials of reduced quality, leading to products of lower quality. These drawbacks can be avoided by the development of new recycling methods that provide materials of high quality in every step of the production cycle. In the present work, oligomeric ethylene terephthalate with defined degrees of polymerization and defined molecular weight is produced by melt-mixing PET with different quantities of adipic acid as an alternative pathway of recycling PET with respect to conventional methods, offering ecofriendly and economical aspects. Additionally, block-copolyesters of defined block length are designed from the oligomeric products.
Ethylene terephthalate and ethylene naphthalate oligomers of defined degree of polymerization were synthesized via chemical recycling of the parent polymers. The oligomers were used as defined building blocks for the preparation of novel block-co-polyesters having tailored sequence compositions. The sequence lengths were systematically varied using Design of Experiments. The dispersive surface energy and the specific desorption energy of the co-polymers were determined by inverse gas chromatography. The study shows that polyethylene terephthalate-polyethylene naphthalate (PET-PEN) block-co-polyesters of defined sequence lengths can be prepared. Furthermore, the specific and dispersive surface energies of the obtained block-co-polyesters showed a linear dependence on the oligomer molecular weight and it was possible to regulate and control their interfacial properties. In contrast, with the corresponding random-block-co-polyesters no such dependence was found. The synthesized block-co-polyesters could be used as polymeric modifying agents for stabilizing PET-PEN polymer blends.
The interfacial compatibility between polymers and nanoclay fillers as well as the thermostability of both components are important characteristics for processing them into polymer composites. While the polymer component is often grafted using common polymerization reactions, the nanoclay component is usually surface modified by surfactant treatment to improve compatibility. In the present study, the polymer ethylene vinyl alcohol and a nanoclay filler based on natural bentonite are both surface modified by different silanes, 3-glycidoxypropyltrimethoxysilane and methacryloxymethyltrimethoxysilane and their interfacial properties are investigated by inverse gas chromatography. The silane-modified samples had improved interfacial properties as reflected by a significant increase in dispersive and specific surface energies. Lewis acidities were determined using chloroform and 1,4-dioxane as polar probes and showed a good match between polymer and nanofiller interfaces. Lewis acidity was generally lower after silane-modification. Silanization yielded increased thermal stability of the treated samples. Thus, silanization led to improved compatibility and enhanced thermal stability which facilitates further processing.
Powder coatings provide several advantages over traditional coatings: environmental friendliness, freedom of design, robustness and resistance of surfaces, possibility to seamlessly all-around coating, fast production process, cost-effectiveness. In the last years these benefits of the powder coating technology have been adopted from metal to heat-sensitive natural fibre/ wood based substrates (especially medium density fibre boards- MDF) used for interior furniture applications. Powder coated MDF furniture parts are gaining market share already in the classic furniture applications kitchen, bathroom, living and offices. The acceptance of this product is increasing as reflected by excellent growth rates and an increasing customer base. Current efforts of the powder coating industry to develop new powders with higher reactivity (i.e. lower curing temperatures and shorter curing times; e.g. 120°C/5min) will enable the powder coating of other heat-sensitive substrates like natural fibre composites, wood plastic composites, light weight panels and different plastics in the future. The coating could be applied and cured by the conventional powder coating process (electrostatic application, and melting and curing in an IR-oven) or by a new powder coating procedure based on the in-mould-coating (IMC) technique which is already established in the plastic industry. Extra value could be added in the future by the functional powder toner printing of powder coated substrates using the electrophotographic printing technology, meeting the future demand of both individualization of the furniture part surface by applying functional 3D textures and patterns and individually created coloured images and enabling shorter delivery times for these individualized parts. The paper describes the distinctiveness of powder coating on natural fibre/ wood based substrates, the requirements of the substrate and the coating powder.
Despite the significant potential offered by the powder coating process for finishing wood-based materials, until now it has been used almost exclusively for coating Medium Density Fiber Board (MDF). A research project aims to develop processes and substrate materials that will allow lightweight boards to be powder coated.
The powder coating of wood products as an emerging environmentally sustainable coating technology holds promise in terms of novel product quality features for engineered wood like medium-density fiberboards (MDFs). However, one major limitation currently impeding widespread application of powder coating technology is the availability of MDF panels that are suitable for this process. Typically, special-grade MDF panels are required that are more costly than standard-grade MDF panels to provide reliable coating quality, which makes powder coating economically unattractive for many users. Methods are needed that allow extending the range of available MDF grades. In the present study, three surface pretreatment approaches for MDFs were studied to increase the processability of standard-grade MDF in the powder coating process: atmospheric plasma pretreatment, infrared irradiation, and moisture equilibration in a climate chamber prior to electrostatic powder application. While atmospheric plasma treatment had no beneficial effect on the use of standard-grade MDF panels, both infrared preheating and preconditioning of the panels under controlled temperature–humidity conditions demonstrated that the range of MDF panels suitable for powder coating can be significantly extended by appropriate selection of the pretreatment procedure.
Processing
(2014)
In this chapter, some relevant aspects and illustrative examples of online monitoring tools as the basis for process control in the manufacturing and processing of thermosetting resins are briefly discussed. In principle, any chemical or physical information made accessible by sensors can be used for online monitoring of resin formation, resin location in the mold, and resin cure. For instance, changes in the flow properties of the reaction mixture are often routinely recorded in dependence of the reaction time during resin synthesis as a measure for the degree of conversion of raw materials into macromolecules or oligomers by applying rheometry in an in-process environment. Typically, a small sample of the reaction mixture is by-passed, subjected to rheological measurement, and re-introduced into the bulk reactor. In a similar way, pH measurements, turbidimetric measurements, or other analyses are performed. Although rheometry may not always be suitable for following resin cure (especially in cases where there is a very rapid increase in viscosity after initiation of the cure), [1] naturally, the method can in principle also be used in the subsequent processing of the thermosets, for instance in the curing of wood glue applied to wood specimen [2]. Similarly, pH changes during thermoset curing can be followed. Hence, an encyclopedic and comprehensive approach to present process control methods would systematically proceed according to the involved physical measurement principle. However, since only a very Brief sketch of means for monitoring thermoset processing can be given here, only a small, personally biased selection of important methods and application examples is addressed in the following sections. These examples hopefully illustrate some of the general strategies and solutions to problems that are typically encountered when processing thermosets.
Cyanate esters
(2014)
Cyanate ester resins are an important class of thermosetting compounds that have experienced an ever-increasing interest as matrix systems for advanced polymer composite materials, which among other applications, are especially suitable for highly demanding functions in the aerospace or microelectronics industries. Other names for cyanate ester resins are cyanate resins, cyanic esters, or triazine resins. The various types of cyanate ester monomers share the aOCN functional group that trimerizes in the course of resin formation to yield a highly branched heterocyclic polymeric network based on the substituted triazine core structure. The basic reaction sequence leading to the typical cyanate ester polymer molecule is depicted in Figure 11.1. The curing reaction may take place with or without catalyst.
Decorative laminates are the most important class of surface-finished engineered wood products. However, while there are numerous scientific publications published dealing with the technology of wood, wood-based products and also liquid coating systems, there is practically no scientific research work available in the field of paper-based laminates. In view of an ever increasing global competition it is time to systematically apply and pursue scientific approaches in this field. The present work is based on a knowledge-based manufacturing paradigm. The application of scientific methodology (e.g. instrumental analysis, process analytics, design of experiments, chemometrics, process modeling) to the preparation of decorative laminates covering the whole process chain from resin synthesis to paper impregnation and to final laminate should enable a targeted design of material functionality.
Cyanate ester resins
(2022)
Cyanate ester resins are an important class of thermosetting compounds that experience an ever-increasing interest as matrix systems for advanced polymer composite materials, which among other application fields are especially suitable for highly demanding applications in the aerospace or microelectronics industries. Other names for cyanate ester resins are cyanate resins, cyanic esters, or triazine resins. The various types of cyanate ester monomers share the –OCN functional group that trimerizes in the course of resin formation to yield a highly branched heterocyclic polymeric network based on the substituted triazine core structure.
Process analysis and process control have attracted increasing interest in recent years. The development and application of process analytical methods are a prerequisite for the knowledge-based manufacturing of industrial goods and allow for the production of high-value products of defined, constantly good quality. Discussed in this chapter are the measurement principle and some relevant aspects and illustrative examples of online monitoring tools as the basis for process control in the manufacturing and processing of thermosetting resins. Optical spectroscopy is featured as one of the main process analytical methods applicable to, among other applications, online monitoring of resin synthesis. In combination with chemometric methods for multivariate data analysis, powerful process models can be generated within the framework of feedback and feed-forward control concepts. Other analytical methods covered in this chapter are those frequently used to control further processing of thermosets to the final parts, including dielectric analysis, ultrasonics, fiber optics, and Fiber Bragg Grating sensors.
Unsaturated polyester resins (UPR) and vinyl ester resins (VER) are among the most commercially important thermosetting matrix materials for composites. Although comparatively low cost, their technological performance is suitable for a wide range of applications, such as fiber-reinforced plastics, artificial marble or onyx, polymer concrete, or gel coats. The main areas of UPR consumption include the wind energy, marine, pipe and tank, transportation, and construction industries. This chapter discusses basic UPR and VER chemistry and technology of manufacturing, and consequent applications. Some important properties and performance characteristics are discussed, such as shrinkage behavior, flame retardance, and property modification by nanoparticles. Also briefly introduced and described are the practical aspects of UPR and VER processing, with special emphasis on the most widely used technological approaches, such as hand and spray layup, resin infusion, resin transfer molding, sheet and bulk molding, pultrusion, winding, and centrifugal casting.
Unsaturated polyester resins (UPR) and vinyl ester resins (VER) are among the most commercially important thermosetting matrix materials for composites. Although comparatively low cost, their technological performance is suitable for a wide range of applications, such as fiber-reinforced plastics, artificial marble or onyx, polymer concrete, or gel coats. The main areas of UPR consumption include the wind energy, marine, pipe and tank, transportation, and construction industries.
This chapter discusses basic UPR and VER chemistry and technology of manufacturing, and consequent applications. Some important properties and performance characteristics are discussed, such as shrinkage behavior, flame retardance, and property modification by nanoparticles. Also briefly introduced and described are the practical aspects of UPR and VER processing, with special emphasis on the most widely used technological approaches, such as hand and spray layup, resin infusion, resin transfer molding, sheet and bulk molding, pultrusion, winding, and centrifugal casting.
Melamine formaldehyde (MF) resins are widely used for the gluing and surface coating of wood-based consumer products in the interior design of living environments. MF resins are especially relevant in decorative laminate applications because of their good performance-to-price ratio. In their industrial processing, an important intermediate state is the liquid MF prepolymer that is used for decorative paper impregnation. Here, the drying of impregnated papers is investigated with respect to premature curing. A new method to quantify water release upon drying that allows estimation of the degree of undesired precuring is described. Since curing proceeds via polycondensation, crosslinking brings about the release of water molecules. By thermogravimetric analysis (TGA), drying was studied in terms of water release due to physical drying (elimination of “dilution water”) and chemical crosslinking of the prepolymer to a three-dimensional MF network (elimination of chemically liberated water). The results obtained by TGA/IR spectroscopic analysis of the liberated volatiles show that the emission of water from b-stage MF can be clearly analytically separated into a physical (evaporation of dilution water) and a chemical (liberation via condensation) sequence. TGA experiments were correlated with curing experiments performed with differential scanning calorimetry (DSC) to estimate the residual crosslinking capacities of the impregnated papers. The drying conditions used during the preparation of impregnated decorative papers seemed to significantly affect their remaining reactivity only when harsh drying conditions were used. Upon heat exposure for prolonged time, precuring of the oligomer units results in a shift of the temperature maxima in TGA.
A series of novel biomedical TPCUs with different percentages of hard segment and a silicone component in the soft segment were synthesized in a multi stage one-pot method. The kinetic profiles of the urethane formation in TPCU-based copolymer systems were monitored by rheological, in line FTIR spectroscopic (React IR) and real-time calorimetric (RC1) methods. This process-analytically monitored multi step synthesis was successfully used to optimize the production of medical-grade TPCU elastomers on preparative scale (in lots of several kg) with controlled molecular structure and mechanical properties. Various surface and bulk analytical methods as well as systematic studies of the mechanic response of the elastomer end-products towards compression and tensile loading were used to estimate the bio-stability of the prepared TPCUs in vitro after 3 months. The tests suggested that high bio-stability of all polyurethane formulations using accelerating in vitro test can be attributed to the synthetic design as well as to the specific techniques used for specimen preparation, namely: (1) the annealing for reducing residual polymer surface stress and preventing IES, (2) stabilization of the morphology by long time storage of the specimens after processing before being immersed in the test liquids, (3) purification by extraction to remove the shot chain oligomers which are the most susceptible to degradation. All mechanical tests were performed on cylindrical and circular disc specimens for modelling the thickness of the meniscus implants under application-relevant stress conditions.
Self-healing thermosets
(2022)
This chapter discusses the basic extrinsic, intrinsic, and combined extrinsic/intrinsic strategies for equipping thermosetting polymers with self-healing properties. The main focus will be on the presentation of a holistic optimization of thermosetting materials, that is, on a simultaneous optimization of both self-healing and other, specialized material properties. Due to their very rigid, highly cross-linked three-dimensional structure, thermosetting polymers require special chemical strategies to achieve self-healing properties. The main chemical strategies available for this will be briefly outlined. The examples given illustrate interesting and/or typical procedures and serve as an inspiration to find solutions for your own applications. They summarize important recent development in research and technology aiming toward multifunctional truly smart self-healing thermosetting materials. An important aspect in this topic area is also how precisely the self-healing effects are analytically checked, quantified, and evaluated. A range of measuring methods is available for this purpose. In this chapter, the most important analytical tools for testing self-healing properties are briefly introduced and highlighted with some illustrative examples.
Vitamin E (VitE) additives are important in treating osteoarthritis inclusive cartilage regeneration due to their antioxidant and anti-inflammatory properties. The present research study focuses on the ability of biological antioxidant VitE (alpha-tocopherol isoform) to reduce or minimize oxidative degradation of soft implantable polyurethane (PU) elastomers after extended periods of time (5 months) in vitro. The effect of the oxidation storage media on the morphology of the segmented PUs was evaluated by mechanical softening, crystallization and melting behavior of both soft and hard segments (SS, HS) using dynamic mechanical analysis (DMA). Bulk mechanical properties of the potential implant materials during ageing were predicted from comprehensive mechanical testing of the biomaterials under tension and compression cyclic loads. 5-months in vitro data suggest that the prepared siloxane-poly(carbonate urethane) formulations have sufficient resistance against degradation to be suitable materials for chondral long term bio-stable implants. Most importantly, the positive effect of incorporating VitE (0.5 or 1.0% w/w) as bio-antioxidant and lubricant on the bio-stability was observed for all PU types. VitE-additives protected the surface layer from erosion and cracking during chemical oxidation in vitro as well as from thermal oxidation during extrusion re-processing.
Comments on “Solubility parameter of chitin and chitosan”, Carbohydrate Polymers 36 (1998) 121–127
(2017)
Results on the solubility parameters of chitin and chitosan presented in the paper DOI: 10.1016/S0144-8617(98)00020-4 were recalculated and data evaluation was redone. A number of misprints, erroneous calculations and data evaluations were found with respect to Hansen as well as total solubility parameters as derived according to group contribution methods by Hoftyzer-Van Krevelen and Hoy’s system. Revised numerical data are presented.
The fiber deformations of once-dried, bleached and never-dried unbleached kraft pulps were studied with respect to their behavior in high- and low-consistency refining. The pulps were stained with congo red to experimentally highlight areas where the arrangement of the fibrils was altered by refining such as dislocated zones or slip planes. The stained fibers were analyzed with conventional Metso Fiberlab but also with a novel prototype measurement device utilizing a color imaging setup. The local intensity of the stain in the fiber was expressed as degree of overall damage (Overall fiber damage index, OFDI). The rewetted zero span tensile index (RWZSTI) was used to verify the OFDI with respect to the pulp strength. High consistency refining resulted in a clear increase in the number of kinks which negatively influenced the pulp strength. The OFDI which was used to detect the intensity of local fiber defects also responded accordingly. A higher OFDI resulted in a lower pulp strength. Low consistency refining removed a significant amount of kinks and resulted in an increase in fiber swelling. A slight increase in fibrillation and a significant increase in flake-like fines were also observed. The OFDI, however, was not reduced in low consistency refining as it would be expected by the removal of less severe dislocations. One reason proposed here is that low consistency refining created new fiber pores that allowed the dye to penetrate into the fiber wall similarly as it does in the zones of the dislocations.
Three different polyols (soluble starch, sucrose, and glycerol) were tested for their potential in the chemical modification of melamine formaldehyde (MF) resins for paper impregnation. MF impregnated papers are widely used as finishing materials for engineered wood. These polyols were selected because the presence of multiple hydroxy groups in the molecules was suspected to facilitate cocondensation with the main MF framework. This should lead to good resin performance. Moreover, they are readily produced from natural feedstock. They are available in large quantities and may serve as economically feasible, environmentally harmless alternative co-monomers suitable to substitute a portion of fossil-based starting material. In the presented work, a number of model resins were synthesized and tested for covalent incorporation of the natural polyol into the MF Framework. Spectroscopic evidence of chemical incorporation of glycerol was found by applying by 1H, 13C, 1H/13C HSQC, 1H/13C HMBC, and 1H DOSY methods. It was furthermore found that covalent incorporation of glycerol in the network took place when glycerol was added at different stages during synthesis. Further, all resins were used to prepare decorative laminates and the performance of the novel resins as surface finishing was evaluated using standard technological tests. The technological performance of the various modified thermosetting resins was assessed by determining flow viscosity, molar mass distribution, the storage stability, and in a second step laminating impregnated paper to particle boards and testing the resulting surfaces according to standardized quality tests. In most cases, the average board surface properties were of acceptable quality. Our findings demonstrate the possibility to replace several percent of the petrol-based product melamine by compounds obtained from renewable resources.
Silicones
(2014)
Silicones are found in a variety of applications with requirements that range from long life at elevated temperatures to fluidity at low temperatures. This chapter first considers silicone elastomers and their application in room temperature vulcanizing (RTV) and heat curing systems (HTV). Also, new technologies for UV curing are introduced. Coverage of RTVs includes both one-component and two-component systems and the different cure chemistries of each, and is followed by a separate discussion of silicone laminates. Due to the high importance of silicone fluids, they are also discussed. Fluids include polishes, release agents, surfactants, and dielectric fluids.
Silicones
(2022)
Silicones are found in a variety of applications with requirements that range from long life at elevated temperatures to fluidity at low temperatures. This chapter first considers silicone elastomers and their application in room temperature vulcanizing (RTV) and heat curing systems (HTV). Also, new technologies for UV curing are introduced. Coverage of RTVs includes both one-component and two-component systems and the different cure chemistries of each and is followed by a separate discussion of silicone laminates. Due to the high importance of silicone fluids, they are also discussed. Fluids include polishes, release agents, surfactants, and dielectric fluids.
A systematic study using a central composite design of experiments (DoE) was performed on the oxygen plasma surface modifications of two different polymers—Pellethane 2363-55DE, which is a polyurethane, and vinyltrimethoxysilane-grafted ethylene-propylene (EPR-g-VTMS), a cross-linked ethylene-propylene rubber. The impacts of four parameters—gas pressure, generator power, treatment duration, and process temperature—were assessed, with static contact angles and calculated surface free energies (SFEs) as the main responses in the DoE. The plasma effects on the surface roughness and chemistry were determined using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Through the sufficiently accurate DoE model evaluation, oxygen gas pressure was established as the most impactful factor, with the surface energy and polarity rising with falling oxygen pressure. Both polymers, though different in composition, exhibited similar modification trends in surface energy rise in the studied system. The SEM images showed a rougher surface topography after low pressure plasma treatments. XPS and subsequent multivariate data analysis of the spectra established that higher oxidized species were formed with plasma treatments at low oxygen pressures of 0.2 mbar.
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.
Comparative analysis of the chemical and rheological curing kinetics of formaldehyde-based wood adhesives is crucial for assessing their respective performance. Differential scanning calorimetry (DSC) and rheometry are the conventional techniques used for monitoring the curing processes leading to crosslinking polymerization of the adhesives. However, the direct comparison of these techniques is inappropriate due to the intrinsic differences in their underlying procedures. To address this challenge, the two adhesive samples were sequentially cured, firstly with rheometry and followed by DSC. The observed higher curing degree in the subsequent DSC procedure underpins the incomplete curing of the samples during initial rheometry. Furthermore, the comparative assessment of the activation energies, molar ratios, and active groups of the two adhesives highlights the importance of the pre-exponential factor in addition to the activation energies, as it attributes to the probability of active groups coinciding at the appropriate spatial arrangement.
Crosslinked thermoplastics
(2014)
Cross-linked thermoplastics represent an important class of materials for numerous applications such as heat-shrinkable tubing, rotational molded parts, and polyolefin foams. By cross-linking olefins, their mechanical performance can be significantly enhanced. This chapter covers the three main methods for the cross-linking of thermoplastics: radiation cross-linking, chemical cross-linking with organic peroxides, and cross-linking using silane-grafting agents. It also considers the major effects of the cross-linking procedure on the performance of the thermoplastic materials discussed.
Cross-linked thermoplastics
(2022)
Cross-linked thermoplastics represent an important class of materials for numerous applications such as heat-shrinkable tubing, rotational molded parts, and polyolefin foams. By cross-linking olefins, their mechanical performance can be significantly enhanced. This chapter covers the three main methods for the cross-linking of thermoplastics: radiation cross-linking, chemical cross-linking with organic peroxides, and cross-linking using silane-grafting agents. It also considers the major effects of the cross-linking procedure on the performance of the thermoplastic materials discussed.
Film formation of self synthesized Polymer EPM–g–VTMDS (ethylene–propylene rubber, EPM, grafted with vinyltetramethyldisiloxane, VTMDS) was studied regarding bonding to adhesion promoter vinyltrimethoxysilane (VTMS) on oxidized 18/10 chromium/nickel–steel (V2A) stainless steel surfaces. Polymer films of different mixed solutions including commercial siloxane and silicone, dimethyl, vinyl group terminated crosslinker (HANSA SFA 42100, CAS# 68083-19-2, 0.35 mmol Vinyl/g) and platinum, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex Karstedt's catalyst (ALPA–KAT 1, CAS# 68478-92-2) were spin coated on V2A stainless steel surfaces with adsorbed VTMS thin layers in order to analyze film formation of EPM–g–VTMDS at early stages. Surface topography and chemical bonding of the high performance polymers on different oxidized V2A surfaces were investigated with X–ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and surface enhanced Raman spectroscopy (SERS). AFM and SEM as well as XPS results indicated that the formation of the polymer film proceeds via growth of polymer islands. Chemical signatures of the essential polymer contributions, linker and polymer backbones, could be identified using XPS core level peak shape analysis and also SERS. The appearance of signals which are related to Si–O–Si can be seen as a clear indication of lateral crosslinking and silica network formation in the films on the V2A surface.
The effect of hard segment content and diisocyanate structure on the transparency and mechanical properties of soft poly(dimethylsiloxane) (PDMS)-based urea elastomers (PSUs) was investigated. A series of PSU elastomers were synthesized from an aminopropyl-terminated PDMS (M¯n: 16,300 g·mol−1), which was prepared by ring chain equilibration of the monomers octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). The hard segments (HSs) comprised diisocyanates of different symmetry, i.e., 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI), 4,4′-methylenebis(phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI), and trans-1,4-cyclohexane diisocyanate (CHDI). The HS contents of the PSU elastomers based on H12MDI and IPDI were systematically varied between 5% and 20% by increasing the ratio of the diisocyanate and the chain extender APTMDS. PSU copolymers of very low urea HS contents (1.0–1.6%) were prepared without the chain extender. All PSU elastomers and copolymers exhibited good elastomeric properties and displayed elongation at break values between 600% and 1100%. The PSUs with HS contents below 10% were transparent and became increasingly translucent at HS contents of 15% and higher. The Young’s modulus (YM) and ultimate tensile strength values of the elastomers increased linearly with increasing HS content. The YM values differed significantly among the PSU copolymers depending on the symmetry of the diisocyanate. The softest elastomer was that based on the asymmetric IPDI. The elastomers synthesized from H12MDI and MDI both exhibited an intermediate YM, while the stiffest elastomer, i.e., that comprising the symmetric CHDI, had a YM three-times higher than that prepared with IPDI. The PSUs were subjected to load–unload cycles at 100% and 300% strain to study the influence of HS morphology on 10-cycle hysteresis behavior. At 100% strain, the first-cycle hysteresis values of the IPDI- and H12MDI-based elastomers first decreased to a minimum of approximately 9–10% at an HS content of 10% and increased again to 22–28% at an HS content of 20%. A similar, though less pronounced, trend was observed at 300% strain. First-cycle hysteresis among the PSU copolymers at 100% strain was lowest in the case of CHDI and highest in the IPDI-based elastomer. However, this effect was reversed at 300% strain, with CHDI displaying the highest hysteresis in the first cycle. In vitro cytotoxicity tests performed using HaCaT cells did not show any adverse effects, revealing their potential suitability for biomedical applications.
This article contains data on the synthesis and mechanical characterization of polysiloxane-based urea-elastomers (PSUs) and is related to the research article entitled “Influence of PDMS molecular weight on transparency and mechanical properties of soft polysiloxane-urea-elastomers for intraocular lens application” (Riehle et al., 2018) [1]. These elastomers were prepared by a two-step polyaddition using the aliphatic diisocyanate 4,4′-Methylenbis(cyclohexylisocyanate) (H12MDI), a siloxane-based chain extender 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (APTMDS) and amino-terminated polydimethylsiloxanes (PDMS) or polydimethyl-methyl-phenyl-siloxane-copolymers (PDMS-Me,Ph), respectively. (More details about the synthesis procedure and the reaction scheme can be found in the related research article (Riehle et al., 2018) [1]).
Amino-terminated polydimethylsiloxanes with varying molecular weights and PDMS-Me,Ph-copolymers were prepared prior by a base-catalyzed ring-chain equilibration of a cyclic siloxane and the endblocker APTMDS. This DiB article contains a procedure for the synthesis of the base catalyst tetramethylammonium-3-aminopropyl-dimethylsilanolate and a generic synthesis procedure for the preparation of a PDMS having a targeted number average molecular weight of 3000 g mol−1. Molecular weights and the amount of methyl-phenyl-siloxane within the polysiloxane-copolymers were determined by 1H NMR and 29Si NMR spectroscopy. The corresponding NMR spectra and data are described in this article.
Additionally, this DiB article contains processed data on in line and off line FTIR-ATR spectroscopy, which was used to follow the reaction progress of the polyaddition by showing the conversion of the diisocyanate. All relevant IR band assignments of a polydimethylsiloxane-urea spectrum are described in this article.
Finally, data on the tensile properties and the mechanical hysteresis-behaviour at 100% elongation of PDMS-based polyurea-elastomers are shown in dependence to the PDMS molecular weight.
Soft thermoplastic polysiloxane-urea-elastomers (PSUs) were prepared for the application as a biomaterial to replace the human natural lens after cataract surgery. PSUs were synthesized from amino-terminated polydimethylsiloxanes (PDMS), 4,4′-Methylenebis(cyclohexylisocyanate) (H12MDI) and 1,3–Bis(3-aminopropyl)-1,1,3,3–tetramethyldisiloxane (APTMDS) by a two-step polyaddition route. Such a material has to be highly transparent and must exhibit a low Young’s Modulus and excellent dimensional stability. Polydimethylsiloxanes in the range of 3000–33,000 g·mol−1 were therefore prepared by ring-chain-equilibration of octamethylcyclotetrasiloxane (D4) and APTMDS in order to study the influence of the soft segment molecular weight on the mechanical properties and the transparency of the PSU-elastomers. 2,4,6,8-Tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (D4Me,Ph) was co-polymerized with D4 in order to adjust the refractive index of the polydimethyl-methyl-phenyl-siloxane-copolymers to a value equivalent to a young human natural lens. Very elastic PSUs with Elongation at Break values higher than 700% were prepared. PSU-elastomers, synthesized from PDMS of molecular weights up to 18,000 g·mol−1, showed transmittance values of over 90% within the visible spectrum range. The soft segment refractive index was increased through the incorporation of 14 mol % of methyl-phenyl-siloxane from 1.4011 to 1.4346 (37 °C). Young’s Moduli of PSU-elastomers were around 1 MPa and lower at PDMS molecular weights up to 15,000 g·mol−1. 10-cycle hysteresis measurements were applied to evaluate the mechanical stability of the PSUs at repeated stress. Hysteresis values at 100% strain decreased from 32 to 2% (10th cycle) with increasing PDMS molecular weight. Furthermore, hysteresis at 5% strain was only detected in PSU-elastomers with low PDMS molecular weights. Finally, preliminary results of in vitro cytotoxicity tests on a PSU-elastomer showed no toxic effects on HaCaT-cells.
Block-copolyesters of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) were synthesized via reactive extrusion. The influence of processing parameters on the material properties on a molecular scale like degree of trans-esterification, block length, and degree of randomness were investigated. The varied process factors were extrusion temperature and rotational speed. The effects of process parameter variation were investigated by 1H-NMR-spectroscopy. The experimental results show a clear dependence of the molecular properties on the processing conditions. By using statistical experimental design (DoE), it was possible to prepare defined copolyesters from PET and PEN without addition of further chemicals. With a degree of randomness between 0.05 and 0.5, the presence of an actual copolyester was confirmed when appropriate extrusion conditions were applied. The reactive extrusion process was confirmed to be suitable to produce defined block-copolyesters in a predictable and reproducible way. It was possible to produce designed sequence lengths, which could be adjusted within a range of 11–136 repeating units in the case of PET and, in the case of PEN, of 2.5–26. The produced materials can be used as barrier materials or barrier coatings to protect substrates against molecular oxygen and water vapour, e.g., in organic photovoltaic applications or food packaging. The described method is a one-pot alternative method to the previously described chemical recycling pathway.
Comparative analysis of the R&D efficiency of 14 leading pharmaceutical companies for the years 1999–2018 shows that there is a close positive correlation between R&D spending and the two investigated R&D output parameters, approved NMEs and the cumulative impact factor of their publications. In other words, higher R&D investments (input) were associated with higher R&D output. Second, our analyses indicate that there are "economies of scale" (size) in pharmaceutical R&D.
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.
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.
Hybrid organic/inorganic nanocomposites combine the distinct properties of the organic polymer and the inorganic filler, resulting in overall improved system properties. Monodisperse porous hybrid beads consisting of tetraethylene pentamine functionalized poly(glycidyl methacrylateco-ethylene glycol dimethacrylate) particles and silica nanoparticles (SNPs) were synthesized under Stoeber sol-gel process conditions. A wide range of hybrid organic/silica nanocomposite materials with different material properties was generated. The effects of n(H2O)/n(TEOS) and c(NH3 ) on the hybrid bead properties particle size, SiO2 content, median pore size, specific surface area, pore volume and size of the SNPs were studied. Quantitative models with a high robustness and predictive power were established using a statistical and systematic approach based on response surface methodology. It was shown that the material properties depend in a complex way on the process factor settings and exhibit non-linear behaviors as well as partly synergistic interactions between the process factors. Thus, the silica content, median pore size, specific surface area, pore volume and size of the SNPs are non-linearly dependent on the water-to-precursor ratio. This is attributed to the effect of the water-to-precursor ratio on the hydrolysis and condensation rates of TEOS. A possible mechanism of SNP incorporation into the porous polymer network is discussed.
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.
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.
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.
The chemical synthesis of polysiloxanes from monomeric starting materials involves a series of hydrolysis, condensation and modification reactions with complex monomeric and oligomeric reaction mixtures. Real-time monitoring and precise process control of the synthesis process is of great importance to ensure reproducible intermediates and products and can readily be performed by optical spectroscopy. In chemical reactions involving rapid and simultaneous functional group transformations and complex reaction mixtures, however, the spectroscopic signals are often ambiguous due to overlapping bands, shifting peaks and changing baselines. The univariate analysis of individual absorbance signals is hence often only of limited use. In contrast, batch modelling based on the multivariate analysis of the time course of principal components (PCs) derived from the reaction spectra provides a more efficient tool for real time monitoring. In batch modelling, not only single absorbance bands are used but information over a broad range of wavelengths is extracted from the evolving spectral fingerprints and used for analysis. Thereby, process control can be based on numerous chemical and morphological changes taking place during synthesis. “Bad” (or abnormal) batches can quickly be distinguished from “normal” ones by comparing the respective reaction trajectories in real time. In this work, FTIR spectroscopy was combined with multivariate data analysis for the in-line process characterization and batch modelling of polysiloxane formation. The synthesis was conducted under different starting conditions using various reactant concentrations. The complex spectral information was evaluated using chemometrics (principal component analysis, PCA). Specific spectral features at different stages of the reaction were assigned to the corresponding reaction steps. Reaction trajectories were derived based on batch modelling using a wide range of wavelengths. Subsequently, complexity was reduced again to the most relevant absorbance signals in order to derive a concept for a low-cost process spectroscopic set-up which could be used for real-time process monitoring and reaction control.
Mass-customization is a megatrend that also affects the wood industry. To obtain individually designed laminates in batch size one efficient printing and processing technologies are required. Digital printing was envisaged as it does not depend on highly costly printing cylinders (as used in rotogravure printing) and allows rapid exchange of the printing designs. In the present work, two wellestablished digital printing approaches, the multi-pass and the single-pass technique, were investigated and evaluated for their applicability in decorating engineered wood and low-pressure melamine films. Three different possibilities of implementing digital printing in the decorative laminates manufacturing process were studied: (1) digital printing on coated chipboard and subsequently applying a lacquered top-coat or melamine overlay (designated as “direct printing”, since the LPM was the printing substrate), (2) digital printing on decorative paper which was subsequently impregnated before hot pressing (designated as “indirect printing, variant A”) and (3) digital printing on decorative paper with subsequent interlamination of the paper between impregnated under- and overlay paper layers during the pressing process (designated as “indirect printing, variant B”). Due to various advantages of the resulting cured melamine resin surfaces including a much better technological performance and flexibility in surface texture design, it was decided to industrially further pursue only the indirect digital printing process comprising interlamination and the direct printing process with a melamine overlay-finishing. Basis for the successful trials on production and laboratory scales were the identification of applicable inks (in terms of compatibility with melamine resin) and of appropriate printing paper quality (in terms of impregnation and imprinting ability). After selection and fine tuning of suitable materials, the next challenge to overcome was the initially insufficient bond strength between impregnated overlay and the ink layers which led to unsatisfactory quality of the print appearance and delamination effects. However, the optimization of the pressing program and the development of a modified impregnation procedure for the underlay and overlay papers allowed the successful implementation of digital printing in the production line of our industrial partner FunderMax.
Properties data of phenolic resins synthetized for the impregnation of saturating Kraft paper
(2018)
The quality of decorative laminates boards depends on the impregnation process of Kraft papers with a phenolic resin,which constitute the raw materials for the manufacture of the cores of such boards.In the laminates industries,the properties of resins are adapted via their syntheses,usually by mixing phenol and formaldehyde in a batch,where additives,temperature and stirring parameters can be controlled. Therefore, many possibilities of preparation and phenolic resins exist, that leads to different combinations of physico chemical properties. In this article, the properties data of eight phenolic resins synthetized with different parameters of pH and reaction times at 60 °C and 90 °C are presented: the losses of pH after synthesis and the dynamic viscosities measured after synthesis and one the solid content is adjusted to 45%w/w in methanol. Data aquired by Differential Scanning Calorimetry (DSC) of the resins and Inverse Gas Chromatography (IGC) of cured solids are given as well.
High quality decorative laminate panels typically consist of two major types of components: the surface layers comprising décor and overlay papers that are impregnated with melamine-based resins, and the core which is made of stacks of kraft papers impregnated with phenolic (PF) resin. The PF-impregnated layers impart superior hydrolytic stability, mechanical strength and fire-resistance to the composite. The manufacturing involves the complex interplay between resin, paper and impregnation/drying processes. Changes in the input variables cause significant alterations in the process characteristics and adaptations of the used materials and specific process conditions may, in turn, be required. This review summarizes the main variables influencing both processability and technological properties of phenolic resin impregnated papers and laminates produced therefrom. It is aimed at presenting the main influences from the involved components (resin and paper), how these may be controlled during the respective process steps (resin preparation and paper production), how they influence the impregnation and lamination conditions, how they affect specific aspects of paper and laminate performance, and how they interact with each other
(synergies).
Impact of phenolic resin preparation on its properties and its penetration behavior in Kraft paper
(2018)
The core of decorative laminates is generally made of stacked Kraft paper sheets impregnated with a phenolic resin. As the impregnation process in industry is relatively fast, new methods need to be developed to characterize it for different paper-resin systems. Several phenolic resins were synthesized with the same Phenol:Formaldehyde ratio of 1:1.8 and characterized by Fourier Transform Infrared Spectrometry (FTIR) as well as Size-Exclusion Chromatography (SEC). In addition, their viscosities and surface tensions when diluted in methanol to 45% of solid content were measured. The capacity of each resin to penetrate a Kraft paper sheet was characterized using a new method, which measures the conductivities induced by the liquid resin crossing the paper substrate. With this method, crossing times could be measured with a good accuracy. Surprisingly, the results showed that the penetration time of the resin samples is not correlated to the viscosity values, but rather to the surface tension characteristics and the chemical characteristics of paper. Furthermore, some resins had a higher swelling effect on the fibers that delayed the crossing of the liquid through the paper.
Here, the effects of substituting portions of fossil-based phenol in phenol formaldehyde resin by renewable lignin from two different sources are investigated using a factorial screening experimental design. Among the resins consumed by the wood-based industry, phenolics are one of the most important types used for impregnation, coating or gluing purposes. They are prepared by condensing phenol with formaldehyde (PF). One major use of PF is as matrix polymer for decorative laminates in exterior cladding and wet-room applications. Important requirements for such PFs are favorable flow properties (low viscosity), rapid curing behavior (high reactivity) and sufficient self-adhesion capacity (high residual curing potential). Partially substituting phenol in PF with bio-based phenolic co-reagents like lignin modifies the physicochemical properties of the resulting resin. In this study, phenol-formaldehyde formulations were synthesized where either 30% or 50% (in weight) of the phenol monomer were substituted by either sodium lignosulfonate or Kraft lignin. The effect of modifying the lignin material by phenolation before incorporation into the resin synthesis was also investigated. The resins so obtained were characterized by Fourier Transform Infra-Red (FTIR) spectroscopy, Size Exclusion Chromatography (SEC), Differential Scanning Calorimetry (DSC), rheology, and measurements of contact angle and surface tension using the Wilhelmy plate method and drop shape analysis.
Impregnated paper-based decorative laminates prepared from lignin-substituted phenolic resins
(2020)
High Pressure Laminates (HPL) panels consist of stacks of self-gluing paper sheets soaked with phenol-formaldehyde (PF) resins. An important requirement for such PFs is that they must rapidly penetrate and saturate the paper pores. Partially substituting phenol with bio-based phenolic chemicals like lignin changes the physico-chemical properties of the resin and affects its ability to penetrate the paper. In this study, PF formulations containing different proportions of lignosulfonate and kraft lignin were used to prepare paper-based laminates. The penetration of a Kraft paper sheet was characterized by a recently introduced, new device measuring the conductivity between both sides of the paper sheet after a drop of resin was placed on the surface and allowed to penetrate the sheet. The main target value measured was the time required for a specific resin to completely penetrate the defined paper sample (“penetration time”). This penetration time generally depends on the molecular weight distribution, the flow behavior and the polarity of the resin which in turn are dependent on the manufacturing conditions of the resin. In the present study, the influences of the three process factors: (1) type of lignin material used for substitution, (2) lignin modification by phenolation and (3) degree of phenol substitution on the penetration times of various lignin-phenolic hybrid impregnation resins were studied using a complete twolevel three-factorial experimental design. Thin laminates made with the resins diluted in methanol were mechanically tested in terms of tensile and flexural strains, and their cross-sections were studied by light microscopy.
This article provides a general overview of the most promising candidates of bio based materials and deals with the most important issues when it comes to their incorporation into PF resins. Due to their abundance on Earth, much knowledge of lignin-based materials has already been gained and uses of lignin in PF resins have been studied for many decades. Other natural polyphenols that are less frequently considered for impregnation are covered as well, as they do also possess some potential for PF substitution.
Allyls
(2022)
This chapter addresses the importance and usage of the commercially low-volume thermoset plastics group known as allyls. The three significant subelements of this group are poly(diallylphthalates), poly(diallylisophthalates), and poly(allyldiglycol carbonate). Chemistry, processing, and properties are also described. Allyl polymers are synthesized by radical polymerizations of allyl monomers that usually do not produce high-molecular-mass macromolecules. Therefore only a few specific monomers can produce thermosetting materials. Diallyldiglycolcarbonate (CR-39) and diallylphthalates are the most significant examples that have considerably improved our everyday life.
Allyls
(2014)
This chapter addresses the importance and usage of the commercially low volume thermoset plastics group known as allyls. The three significant sub-elements of this group are poly(diallylphthalates), poly(diallylisophthalates), and poly(allyldiglycol carbonate). Chemistry, processing, and properties are also described. Allyl polymers are synthesized by radical polymerizations of allyl monomers that usually do not produce high-molecular-mass macromolecules. Therefore, only a few specific monomers can produce thermosetting materials. Diallyldiglycolcarbonate (CR-39) and diallylphthalates are the most significant examples that have considerably improved our everyday life.
Thermoplastic polymers like ethylene-octene copolymer (EOC) may be grafted with silanes via reactive extrusion to enable subsequent crosslinking for advanced biomaterials manufacture. However, this reactive extrusion process is difficult to control and it is still challenging to reproducibly arrive at well-defined products. Moreover, high grafting degrees require a considerable excess of grafting reagent. A large proportion of the silane passes through the process without reacting and needs to be removed at great expense by subsequent purification. This results in unnecessarily high consumption of chemicals and a rather resource-inefficient process. It is thus desired to be able to define desired grafting degrees with optimum grafting efficiency by means of suitable process control. In this study, the continuous grafting of vinyltrimethoxysilane (VTMS) on ethylene-octene copolymer (EOC) via reactive extrusion was investigated. Successful grafting was verified and quantified by 1H-NMR spectroscopy. The effects of five process parameters and their synergistic interactions on grafting degree and grafting efficiency were determined using a face-centered experimental design (FCD). Response surface methodology (RSM) was applied to derive a causal process model and define process windows yielding arbitrary grafting degrees between <2 and >5% at a minimum waste of grafting agent. It was found that the reactive extrusion process was strongly influenced by several second-order interaction effects making this process difficult to control. Grafting efficiencies between 75 and 80% can be realized as long as grafting degrees <2% are admitted.
We present the modification of ethylene-propylene rubber (EPM) with vinyltetra-methydisiloxane (VTMDS) via reactive extrusion to create a new silicone-based material with the potential for high-performance applications in the automotive, industrial and biomedical sectors. The radical-initiated modification is achieved with a peroxide catalyst starting the grafting reaction. The preparation process of the VTMDS-grafted EPM was systematically investigated using process analytical technology (in-line Raman spectroscopy) and the statistical design of experiments (DoE). By applying an orthogonal factorial array based on a face-centered central composite experimental design, the identification, quantification and mathematical modeling of the effects of the process factors on the grafting result were undertaken. Based on response surface models, process windows were defined that yield high grafting degrees and good grafting efficiency in terms of grafting agent utilization. To control the grafting process in terms of grafting degree and grafting efficiency, the chemical changes taking place during the modification procedure in the extruder were observed in real-time using a spectroscopic in-line Raman probe which was directly inserted into the extruder. Successful grafting of the EPM was validated in the final product by 1H-NMR and FTIR spectroscopy.
Structural and functional thermosetting composite materials are exposed to different kinds of stress which can damage the polymer matrix, thus impairing the intended properties. Therefore, self-healing materials have attracted the attention of many research groups over the last decades in order to provide satisfactory material properties and outstanding product durability. The present article provides a critical overview of promising self-healing strategies for crosslinked thermoset polymers. It is organized in two parts: an overview about the different approaches to self-healing is given in the first part, whereas the second part focuses on the specific chemistries of the main strategies to achieve self-healing through crosslinking. It is attempted to provide a comprehensive discussion of different approaches which are described in the scientific literature. By comparison of the advantages and disadvantages, the authors wish to provide helpful insights on the assessment of the potential to transfer the extensive present knowledge about self-healing materials and methods to surface varnishing thermoset coatings.
Homogeneous and monodispersed furan functionalised melamine-formaldehyde particles were produced. As a precursor, 2-chloro-1,3,5-triazine-2,4-diamine (Mel) was selectively substituted with 2-aminomethyl furan (Fu) units in a convenient one step reaction. The pure reaction product Fu-Mel, which was used without further purification, was reacted with formaldehyde by conventional sol-gel condensation in aqueous medium to yield chemically homogenous, spherically shaped and monodispersed particles. The particles were analysed using ATR-FT-IR, Raman, 1H and 13C NMR spectroscopy, TGA, SEM and DSC measurements. The reactivity of the furan groups located at the particle surface was studied by performing a thermoreversible Diels-Alder cycloaddition reaction with bis-maleimide coupling agents. The formed networks showed thermoreversible behaviour, which was characterised by dynamic IR and DSC measurements.
The data presented in this article characterize the thermomechanical and microhardness properties of a novel melamine-formaldehyde resin (MF) intended for the use as a self-healing surface coating. The investigated MF resin is able to undergo reversible crosslinking via Diels Alder reactive groups. The microhardness data were obtained from nanoindentation measurements performed on solid resin film samples at different stages of the self-healing cycle. Thermomechanical analysis was performed under dynamic load conditions. The data provide supplemental material to the manuscript published by Urdl et al. 2020 (https://doi.org/10.1016/j.eurpolymj.2020.109601) on the self-healing performance of this resin, where a more thorough discussion on the preparation, the properties of this coating material and its application in impregnated paper-based decorative laminates can be found.
The self-healing effect of melamine-based surfaces, triggered by temperature, was investigated. The temperature triggered reversible healing chemistry, on which the self-healing effect is based, was the Diels-Alder (DA) reaction between furan and malemeide groups. Melamine-furan containing building blocks were connected by multi-functional maleimide crosslinker via a Diels-Alder (DA) reaction to giva a DA adduct. The DA adduct was then reacted with formaldehyde to form a network by conventional condensation reaction of melamine amino groups with formaldehyde. The obtained resin was characterised and used for the impregnation of paper. Impregnated papers and neat resin werde used to perform scratch-healing tests and mechanical analysis of the novel coating system.
The data present in this article affords insides in the characterization of a newly described bi-functional furan-melamine monomer, which is used for the production of monodisperse, furan-functionalized melamine formaldehyde particles. In the related research article Urdl et al., 2019 data interpretations can be found. The furan functionalization of particles is necessary to perform reversible Diels-Alder reactions with maleimide (BMI) crosslinker to form thermoreversible network systems. To understand the reaction conditions of Diels Alder (DA) reaction with a Fu-Mel monomer and a maleimide crosslinker, model DA reaction were performed and evaluated using dynamic FT-IR measurements. During retro Diels-Alder (rDA) reactions of the monomer system, it was found out that some side reaction occurred at elevated temperatures. The data of evaluating the side reaction is described in one part of this manuscript. Additional high resolution SEM images of Fu Mel particles are shown and thermoreversible particle networks with BMI2 are shown. The data of different Fu-Mel particle networks with maleimide crosslinker are presented. Therefore, the used maleimide crosslinker with different spacer lengths were synthesized and the resulting networks were analyzed by ATR-FT-IR, SEM and DSC.
Functionalised particles are highly requested in materials research, as they can be used as vital components in many advanced applications such as smart materials, functional coatings, drug carrier systems or adsorption materials. In this study, furan-functionalised melamine-formaldehyde (MF) particles were successfully prepared for the first time using an organic sol-gel process. Commercially available 2-Aminomethylfuran (AMF) and 2-Aminomethyl-5-methylfuran (AMMF) were used as modifying agents. In the isolated polymer particles, a melamine (M) to modifying agent ratio of M:AMF mol/mol 2.04:1 and M:AMMF ratio of mol/mol 1.25:1 was used. The obtained particles were isolated in various centrifugation and re-dispersion cycles and analysed using ATR-FT-IR, Raman and solid state 13C NMR spectroscopy, TGA, SEM and DSC measurements. Upon functionalisation the size of the MF particles increased (MF 1.59 µm, 27% CV (coefficient of variation); MF-AMF 2.56 µm, 25% CV; MF-AMMF 2.20 µm, 35% CV). DSC measurements showed that another type of exothermic residual reactivity besides condensation-based curing takes place with the furan-modified particles that is not related to the liberation of volatile compounds. The newly obtained particles are able to undergo Diels-Alder reactions with maleimide groups. The characteristic IR and Raman absorbance bands of the reaction products after the particles were reacted with 4,4′-Diphenylmethanebismaleimide reagent confirm the formation of a Diels-Alder adduct.
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.
Metalworking fluids (MWFs) are widely used to cool and lubricate metal workpieces during processing to reduce heat and friction. Extending a MWF’s service life is of importance from both economical and ecological points of view. Knowledge about the effects of processing conditions on the aging behavior and reliable analytical procedures are required to properly characterize the aging phenomena. While so far no quantitative estimations of ageing effects on MWFs have been described in the literature other than univariate ones based on single parameter measurements, in the present study we present a simple spectroscopy-based set-up for the simultaneous monitoring of three quality parameters of MWF and a mathematical model relating them to the most influential process factors relevant during use. For this purpose, the effects of MWF concentration, pH and nitrite concentration on the droplet size during aging were investigated by means of a response surface modelling approach. Systematically varied model MWF fluids were characterized using simultaneous measurements of absorption coefficients µa and effective scattering coefficients µ’s. Droplet size was determined via dynamic light scattering (DLS) measurements. Droplet size showed non-linear dependence on MWF concentration and pH, but the nitrite concentration had no significant effect. pH and MWF concentration showed a strong synergistic effect, which indicates that MWF aging is a rather complex process. The observed effects were similar for the DLS and the µ’s values, which shows the comparability of the methodologies. The correlations of the methods were R2c = 0.928 and R2P = 0.927, as calculated by a partial least squares regression (PLS-R) model. Furthermore, using µa, it was possible to generate a predictive PLS-R model for MWF concentration (R2c = 0.890, R2P = 0.924). Simultaneous determination of the pH based on the µ’s is possible with good accuracy (R²c = 0.803, R²P = 0.732). With prior knowledge of the MWF concentration using the µa-PLS-R model, the predictive capability of the µ’s-PLS-R model for pH was refined (10 wt%: R²c = 0.998, R²p = 0.997). This highlights the relevance of the combined measurement of µa and µ’s. Recognizing the synergistic nature of the effects of MWF concentration and pH on the droplet size is an important prerequisite for extending the service life of an MWF in the metalworking industry. The presented method can be applied as an in-process analytical tool that allows one to compensate for ageing effects during use of the MWF by taking appropriate corrective measures, such as pH correction or adjustment of concentration.
Natural wood colors occur within a wide range from almost white (e.g., white poplar), various yellowish, reddish, and brownish hues to almost black (e.g., ebony). The intrinsic color of wood is basically defined by its chemical composition. However, other factors such as specific anatomical formations or physical properties further affect the optical impression. Starting with the chemical composition of wood and anatomical basics, wood color and its modifications are discussed in this chapter. The classic method of coloring or re-coloring wood-based material surfaces is the application of a coating containing appropriate dyes or pigments. Different concepts for wood coating and coloration are presented. Another method used dyes for coloration of the wood structure. As alternative techniques, physical methods, for example, drying, steaming, ammoniation, bleaching, enzyme treatment, as well as treatment with electromagnetic irradiation (e.g., UV), are explained in this chapter.
The isothermal curing of melamine resin is investigated by in-line infrared spectroscopy at different temperatures. The infrared spectra are decomposed into time courses of characteristic spectral patterns using Multivariate Curve Resolution (MCR). It was found that depending on the applied curing temperature, melamine films with different spectral fingerprints and correspondingly different chemical network structures are formed. The network structures of fully cured resin films are specific for the applied curing temperatures used and cannot simply be compensated by changes in the curing time. For industrial curing processes, this means that cure temperature is the main system determining factor at constant M:F ratio. However, different MF resin networks can be specifically obtained from one and the same melamine resin by suitable selection of the curing time and temperatures profiles to design resin functionality. The spectral fingerprints after short curing time as well as after long curing time reflect the fundamental differences in the thermoset networks that can be obtained with industrial short-cycle and multi-daylight presses.
Here, we study resin cure and network formation of solid melamine formaldehyde pre-polymer over a large temperature range viadynamic temperature curing profiles. Real-time infrared spectroscopy is used to analyze the chemical changes during network formation and network hardening. By applying chemometrics (multivariate curve resolution,MCR), the essential chemical functionalities that constitute the network at a given stage of curing are mathematically extracted and tracked over time. The three spectral components identified by MCR were methylol-rich, ether linkages-rich and methylene linkages-rich resin entities. Based on dynamic changes of their characteristic spectral patterns in dependence of temperature, curing is divided into five phases: (I) stationary phase with free methylols as main chemical feature, (II) formation of flexible network cross-linked by ether linkages, (III) formation of rigid, ether-cross-linked network, (IV) further hardening via transformation of methylols and ethers into methylene-cross-linkages, and (V) network consolidation via transformation of ether into methylene bridges. The presented spectroscopic/chemometric approach can be used as methodological basis for the functionality design of MF-based surface films at the stage of laminate pressing, i.e., for tailoring the technological property profile of cured MF films using a causal understanding of the underlying chemistry based on molecular markers and spectroscopic fingerprints.
During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.
Melamine–formaldehyde (MF) resins are widely used as adhesives and finishing materials in the wood industry. During resin cure, either methylene ether or methylene bridges are formed, leading to the formation of a three‐dimensional resin network. Not only the curing degree, but also the chemical species present in the cured resin determine the quality of the final product. Analytical methods allowing a detailed investigation of network formation are of great benefit to manufacturers. In the present work, resin cure of an MF precondensate is studied at different temperatures (100–200 °C) without considering the initial pH as a factor. Isoconversional kinetic analysis based on exothermal curing enthalpies enables calculation of the crosslinking degree at a given time/temperature regime. A semiquantitative determination of the chemical groups present is performed based on solid‐state nuclear magnetic resonance data. Fourier transform infrared spectroscopy has shown to be a fast and reliable analytical tool with high sensitivity toward functional groups and with great potential for at‐line process control.
Hardboards (HBs) (wet-process high-density fibreboards) were made in an industrial trial using a binder system consisting of cationic mimosa tannin and laccase or just cationic tannin without any thermosetting adhesive. The boards displayed superior mechanical strength compared to reference boards made with phenol–formaldehyde, easily exceeding the European standards for general-purpose HBs. The thickness swell of most of the boards was slightly greater than the standards would allow, so some optimisation is required in this area. The improved board properties appear to be mainly associated with ionic interactions involving quaternary amino groups in cationic tannin and negatively charged wood fibres rather than to cross-linking of fibres via laccase-assisted formation and coupling of radicals in tannin and fibre lignin.
Powder coating of engineered wood panels such as medium density fibreboards (MDF) is gaining industrial interest due to ecological and economic advantages of powder coating technology. For transferring powder coating technology to temperature-sensitive substrates like MDF, a thorough understanding of the melting, flowing and curing behaviour of the used low-bake resins is required. In the present study, thermo-analysis in combination with iso-conversional kinetic data analysis as well as rheometry is applied to characterise the properties of an epoxy-based powder coating. Neat resin and cured powder coating films are examined in order to define an ideal production window within which the resin is preferably applied and processed to yield satisfactory surface performance on the one hand and without exposing the carrier MDF too high a temperature load on the other hand to prevent the panel from deteriorating in mechanical strength. In order to produce powder coated films of high surface gloss – a feature that has not yet successfully been realized on MDF with powder coatings – a new curing technology, in-mould surface finishing, has been applied.
Here, we report the mechanical and water sorption properties of a green composite based on Typha latifolia fibres. The composite was prepared either completely binder-less or bonded with 10% (w/w) of a bio-based resin which was a mixture of an epoxidized linseed oil and a tall-oil based polyamide. The flexural modulus of elasticity, the flexural strength and the water absorption of hot pressed Typha panels were measured and the influence of pressing time and panel density on these properties was investigated. The cure kinetics of the biobased resin was analyzed by differential scanning calorimetry (DSC) in combination with the iso-conversional kinetic analysis method of Vyazovkin to derive the curing conditions required for achieving completely cured resin. For the binderless Typha panels the best technological properties were achieved for panels with high density. By adding 10% of the binder resin the flexural strength and especially the water absorption were improved significantly.