Control of curing rate and exothermicity during processing of thermosetting composite materials is essential in order to minimize the formation of internal stresses leading to mechanical and ...dimensional defects in the samples, especially in thick composite samples. It was recently proposed that sequential heat release, an approach based on the kinetic control of the curing sequence of dual‐curing thermosets, would enable a step‐wise release of the reaction heat and therefore a better control of conversion and temperature profiles during the crosslinking stage. In this article, it is shown experimental proof of this concept obtained by means of an instrumented mold that can be used for the processing of small samples with and without carbon fiber reinforcement. Safe processing scenarios have been defined by numerical simulation using a simplified two‐dimensional heat transfer model and validated experimentally.
Off‐stoichiometric thiol‐epoxy dual‐curing systems make it possible to process composites in well‐defined curing stages. A temperature overshoot in the first stage is observed, corresponding to the activation of the first reaction (thiol‐epoxy addition), leading to a stable and uniform intermediate material, ungelled or barely crosslinked. The second reaction (epoxy homopolymerization) is activated in a second stage upon heating, producing a crosslinking process with little or no temperature and conversion gradients, therefore enhancing the quality of processed parts.
In this work, the effect of the addition of boron nitride (BN) fillers in a thiol-cycloaliphatic epoxy formulation has been investigated. Calorimetric studies put into evidence that the kinetics of ...the curing has been scarcely affected and that the addition of particles does not affect the final structure of the network. Rheologic studies have shown the increase in the viscoelastic properties on adding the filler and allow the percolation threshold to be calculated, which was found to be 35.5%. The use of BN agglomerates of bigger size increases notably the viscosity of the formulation. Glass transition temperatures are not affected by the filler added, but Young's modulus and hardness have been notably enhanced. Thermal conductivity of the composites prepared shows a linear increase with the proportion of BN particle sheets added, reaching a maximum of 0.97 W/K·m. The addition of 80 μm agglomerates, allowed to increase this value until 1.75 W/K·m.
The main objective of this work was to further analyze the optimization of the production factors of
L. fiberboards obtained without adhesives. The production of boards derived from
L. without added ...adhesives and with high mechanical performance has already been demonstrated. This present study explored a modification in the production process through a final curing thermal treatment (final heat treatment, FHT). Since pressing time is an influential factor in the production cost, it is expected that curing allows a reduction of this time. This study compared the results obtained by three panel-production alternatives: long pressing time (tp) without curing and long and short tp with FHT. Of the two factors analyzed, pressing pressure (Pp) was the most important production factor in both the modulus of elasticity (MOE) and modulus of rupture (MOR), while curing was the most important factor for the internal bond (IB). The study shows that a FHT facilitates the distribution of lignin and a possible improvement in the quantity and quality of bonds between lignin and cellulosic fibers. As a consequence, it improves the IB, produces boards with more homogeneous physical and mechanical properties and thereby makes them more hydrophobic. The curing thermal treatment allows high performance panels to be obtained in a manner which is more ecological, quicker, and cheaper.
This study presents an unexplored method to produce formaldehyde-free MDF. Steam exploded
L. (STEX-AD) and untreated wood fibers (WF) were mixed at different mixing rates (0/100, 50/50, and 100/0, ...respectively) and two series of boards were manufactured, with 4 wt% of pMDI, based on dry fibers, and self-bonded. The mechanical and physical performance of the boards was analyzed as a function of the adhesive content and the density. The mechanical performance and dimensional stability were determined by following European standards. The material formulation and the density of the boards had a significant effect on both mechanical and physical properties. The boards made solely of STEX-AD were comparable to those made with pMDI, while the panels made of WF without adhesive were those that performed the worst. The STEX-AD showed the ability to reduce the TS for both pMDI-bonded and self-bonded boards, although leading to a high WA and a higher short-term absorption for the latter. The results presented show the feasibility of using STEX-AD in the manufacturing of self-bonded MDF and the improvement of dimensional stability. Nonetheless, further studies are needed especially to address the enhancement of the internal bond (IB).
This paper explores the possibility of producing all-lignocellulosic fiberboards from
L. as a source of lignocellulosic fibers with no synthetic binders. This raw material was steam exploded with a ...thermomechanical aqueous vapor process in a batch reactor. The
raw material and its obtained pulp were characterized in terms of chemical composition and the results were compared to other lignocellulosic materials. The chemical composition of steam exploded
fibers showed high cellulose and a moderate lignin content suggesting it was a good raw material for fiberboard production. The all-lignocellulosic fiberboards were produced on laboratory scale; using the steam exploded
by means of a wet process. The effects of pressing pressure on physical and mechanical properties were evaluated and the conditions that optimize the responses were found. The analyzed properties were density (d); water absorption (WA); thickness swelling (TS); modulus of elasticity (MOE); modulus of rupture (MOR); and internal bond strength (IB). The tested levels of the pressing pressure range from 0.35 to 15 MPa. The optimum IB; MOE; MOR; WA and TS were 1.28 MPa, 7439 MPa, 40.4 MPa, 17.6% and 13.3%, respectively. The obtained fiberboards were of very good quality and more than satisfy the requirements of the relevant standard specifications.
The pure trifunctional glycidyl monomer from phloroglucinol (3EPO-Ph) was synthesized and used as feedstock in the preparation of novel bio-based thermosets by thiol-epoxy curing. The monomer was ...crosslinked with different commercially available thiols: tetrafunctional thiol (PETMP), trifunctional thiol (TTMP) and an aromatic dithiol (TBBT) as curing agents in the presence of a base. As catalyst, two different commercial catalysts: LC-80 and 4-(
,
-dimethylamino) pyridine (DMAP) and a synthetic catalyst, imidazolium tetraphenylborate (base generator, BG) were employed. The curing of the reactive mixtures was studied by using DSC and the obtained materials by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The results revealed that only the formulations catalyzed by BG showed a latent character. Already prepared thermosetting materials showed excellent thermal, thermomechanical and mechanical properties, with a high transparency. In addition to that, when compared with the diglycidyl ether of bisphenol A (DGEBA)/PETMP material, the thermosets prepared from the triglycidyl derivative of phloroglucinol have better final characteristics and therefore this derivative can be considered as a partial or total renewable substitute of DGEBA in technological applications.
Analysis of the cell operation at the metabolic level requires collecting data of different types and to determine their confidence level. In addition, the acquired information has to be combined in ...order to obtain a consistent operational view. In the case of Pichia pastoris, information of its biomass composition at macromolecular and elemental level is scarce particularly when different environmental conditions, such as oxygen availability or, genetic backgrounds (e.g. recombinant protein production vs. non production conditions) are compared.
P. pastoris cells growing in carbon-limited chemostat cultures under different oxygenation conditions (% O2 in the bioreactor inlet gas: 21%, 11% and 8%, corresponding to normoxic, oxygen-limiting and hypoxic conditions, respectively), as well as under recombinant protein (antibody fragment, Fab) producing and non-producing conditions, were analyzed from different points of view. On the one hand, the macromolecular and elemental composition of the biomass was measured using different techniques at the different experimental conditions and proper reconciliation techniques were applied for gross error detection of the measured substrates and products conversion rates. On the other hand, fermentation data was analyzed applying elemental mass balances. This allowed detecting a previously missed by-product secreted under hypoxic conditions, identified as arabinitol (aka. arabitol). After identification of this C5 sugar alcohol as a fermentation by-product, the mass balances of the fermentation experiments were validated.
After application of a range of analytical and statistical techniques, a consistent view of growth parameters and compositional data of P. pastoris cells growing under different oxygenation conditions was obtained. The obtained data provides a first view of the effects of oxygen limitation on the physiology of this microorganism, while recombinant Fab production seems to have little or no impact at this level of analysis. Furthermore, the results will be highly useful in other complementary quantitative studies of P. pastoris physiology, such as metabolic flux analysis.
New thermosets from a triglycidyl eugenol derivative (3EPOEU) as a renewable epoxy monomer were obtained by an epoxy-amine curing process. A commercially-available Jeffamine
and isophorone diamine, ...both obtained from renewable resources, were used as crosslinking agents, and the materials obtained were compared with those obtained from a standard diglycidylether of bisphenol A (DGEBA). The evolution of the curing process was studied by differential scanning calorimetry and the materials obtained were characterized by means of calorimetry, thermogravimetry, thermodynamomechanical analysis, stress-strain tests and microindentation. 3EPOEU formulations were slightly less reactive, and the thermosets obtained showed higher
s than those prepared from DGEBA, since they had higher crosslinking density than formulations with DGEBA because of the more compact structure and higher functionality of the eugenol derivative. 3EPOEU thermosets showed good thermal stability and mechanical properties. The results obtained in this study allow us to conclude that the triglycidyl derivative of eugenol, 3EPOEU, is a safe and environmentally friendly alternative to DGEBA.
Novel composite coatings prepared from 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECC) and different ceramic fillers have been prepared to improve the thermal dissipation of ...electronic devices. As latent cationic initiator, a benzylanilinium salt with triethanolamine has been used, which leads to a polyether matrix. Different proportions of Al₂O₃, AlN and SiC as fillers were added to the reactive formulation. The effect of the fillers selected and their proportions on the evolution of the curing was studied by calorimetry and rheometry. The thermal conductivity, thermal stability, thermal expansion coefficient and thermomechanical and mechanical properties of the composites were evaluated. An improvement of 820% in thermal conductivity in reference to the neat material was reached with a 75 wt % of AlN, whereas glass transition temperatures higher than 200 °C were determined in all the composites.
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