Search results for: isothermal calorimetry

Authors: Serdar Yaman, Hanzade Haykiri-Acma

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Biomass is a CO₂-neutral fuel that is renewable and sustainable along with having very huge global potential. Efficient use of biomass in power generation and production of biomass-based biofuels can mitigate the greenhouse gasses (GHG) and reduce dependency on fossil fuels. There are also other beneficial effects of biomass energy use such as employment creation and pollutant reduction. However, most of the biomass materials are not capable of competing with fossil fuels in terms of energy content. High moisture content and high volatile matter yields of biomass make it low calorific fuel, and it is very significant concern over fossil fuels. Besides, the density of biomass is generally low, and it brings difficulty in transportation and storage. These negative aspects of biomass can be overcome by thermal pretreatments that upgrade the fuel property of biomass. That is, torrefaction is such a thermal process in which biomass is heated up to 300ºC under non-oxidizing conditions to avoid burning of the material. The treated biomass is called as biochar that has considerably lower contents of moisture, volatile matter, and oxygen compared to the parent biomass. Accordingly, carbon content and the calorific value of biochar increase to the level which is comparable with that of coal. Moreover, hydrophilic nature of untreated biomass that leads decay in the structure is mostly eliminated, and the surface properties of biochar turn into hydrophobic character upon torrefaction. In order to investigate the effectiveness of torrefaction process on biomass properties, several biomass species such as olive milling residue (OMR), Rhododendron (small shrubby tree with bell-shaped flowers), and ash tree (timber tree) were chosen. The fuel properties of these biomasses were analyzed through proximate and ultimate analyses as well as higher heating value (HHV) determination. For this, samples were first chopped and ground to a particle size lower than 250 µm. Then, samples were subjected to torrefaction in a horizontal tube furnace by heating from ambient up to temperatures of 200, 250, and 300ºC at a heating rate of 10ºC/min. The biochars obtained from this process were also tested by the methods applied to the parent biomass species. Improvement in the fuel properties was interpreted. That is, increasing torrefaction temperature led to regular increases in the HHV in OMR, and the highest HHV (6065 kcal/kg) was gained at 300ºC. Whereas, torrefaction at 250ºC was seen optimum for Rhododendron and ash tree since torrefaction at 300ºC had a detrimental effect on HHV. On the other hand, the increase in carbon contents and reduction in oxygen contents were determined. Burning characteristics of the biochars were also studied using thermal analysis technique. For this purpose, TA Instruments SDT Q600 model thermal analyzer was used and the thermogravimetric analysis (TGA), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), and differential thermal analysis (DTA) curves were compared and interpreted. It was concluded that torrefaction is an efficient method to upgrade the fuel properties of biomass and the biochars from which have superior characteristics compared to the parent biomasses.

Keywords: biochar, biomass, fuel upgrade, torrefaction

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Authors: Leslie Raphael de M. Ferraz, Salvana Priscylla M. Costa, Tarcyla de A. Gomes, Giovanna Christinne R. M. Schver, Cristóvão R. da Silva, Magaly Andreza M. de Lyra, Danilo Augusto F. Fontes, Larissa A. Rolim, Amanda Carla Q. M. Vieira, Miracy M. de Albuquerque, Pedro J. Rolim-Neto

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Efavirenz (EFV) is a drug used as first-line treatment of AIDS. However, it has poor aqueous solubility and wettability, presenting problems in the gastrointestinal tract absorption and bioavailability. One of the most promising strategies to improve the solubility is the use of solid dispersions (SD). Therefore, this study aimed to characterize SD EFZ with the polymers: PVP-K30, PVPVA 64 and SOLUPLUS in order to find an optimal formulation to compose a future pharmaceutical product for AIDS therapy. Initially, Physical Mixtures (PM) and SD with the polymers were obtained containing 10, 20, 50 and 80% of drug (w/w) by the solvent method. The best formulation obtained between the SD was selected by in vitro dissolution test. Finally, the drug-carrier system chosen, in all ratios obtained, were analyzed by the following techniques: Differential Scanning Calorimetry (DSC), polarization microscopy, Scanning Electron Microscopy (SEM) and spectrophotometry of absorption in the region of infrared (IR). From the dissolution profiles of EFV, PM and SD, the values of area Under The Curve (AUC) were calculated. The data showed that the AUC of all PM is greater than the isolated EFV, this result is derived from the hydrophilic properties of the polymers thus favoring a decrease in surface tension between the drug and the dissolution medium. In adittion, this ensures an increasing of wettability of the drug. In parallel, it was found that SD whom had higher AUC values, were those who have the greatest amount of polymer (with only 10% drug). As the amount of drug increases, it was noticed that these results either decrease or are statistically similar. The AUC values of the SD using the three different polymers, followed this decreasing order: SD PVPVA 64-EFV 10% > SD PVP-K30-EFV 10% > SD Soluplus®-EFV 10%. The DSC curves of SD’s did not show the characteristic endothermic event of drug melt process, suggesting that the EFV was converted to its amorphous state. The analysis of polarized light microscopy showed significant birefringence of the PM’s, but this was not observed in films of SD’s, thus suggesting the conversion of the drug from the crystalline to the amorphous state. In electron micrographs of all PM, independently of the percentage of the drug, the crystal structure of EFV was clearly detectable. Moreover, electron micrographs of the SD with the two polymers in different ratios investigated, we observed the presence of particles with irregular size and morphology, also occurring an extensive change in the appearance of the polymer, not being possible to differentiate the two components. IR spectra of PM corresponds to the overlapping of polymer and EFV bands indicating thereby that there is no interaction between them, unlike the spectra of all SD that showed complete disappearance of the band related to the axial deformation of the NH group of EFV. Therefore, this study was able to obtain a suitable formulation to overcome the solubility limitations of the EFV, since SD PVPVA 64-EFZ 10% was chosen as the best system in delay crystallization of the prototype, reaching higher levels of super saturation.

Keywords: characterization, dissolution, Efavirenz, solid dispersions

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Authors: Matar Celine, Gaucel Sebastien, Gontard Nathalie, Guilbert Stephane, Guillard Valerie

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To increase the very short shelf life of fresh fruits and vegetable, Modified Atmosphere Packaging (MAP) allows an optimal atmosphere composition to be maintained around the product and thus prevent its decay. This technology relies on the modification of internal packaging atmosphere due to equilibrium between production/consumption of gases by the respiring product and gas permeation through the packaging material. While, to the best of our knowledge, benefit of MAP for fresh fruits and vegetable has been widely demonstrated in the literature, its effect on shelf life increase has never been quantified and formalized in a clear and simple manner leading difficult to anticipate its economic and environmental benefit, notably through the decrease of food losses. Mathematical modelling of mass transfers in the food/packaging system is the basis for a better design and dimensioning of the food packaging system. But up to now, existing models did not permit to estimate food quality nor shelf life gain reached by using MAP. However, shelf life prediction is an indispensable prerequisite for quantifying the effect of MAP on food losses reduction. The objective of this work is to propose an innovative approach to predict shelf life of MAP food product and then to link it to a reduction of food losses and wastes. In this purpose, a ‘Virtual MAP modeling tool’ was developed by coupling a new predictive deterioration model (based on visual surface prediction of deterioration encompassing colour, texture and spoilage development) with models of the literature for respiration and permeation. A major input of this modelling tool is the maximal percentage of deterioration (MAD) which was assessed from dedicated consumers’ studies. Strawberries of the variety Charlotte were selected as the model food for its high perishability, high respiration rate; 50-100 ml CO₂/h/kg produced at 20°C, allowing it to be a good representative of challenging post-harvest storage. A value of 13% was determined as a limit of acceptability for the consumers, permitting to define products’ shelf life. The ‘Virtual MAP modeling tool’ was validated in isothermal conditions (5, 10 and 20°C) and in dynamic temperature conditions mimicking commercial post-harvest storage of strawberries. RMSE values were systematically lower than 3% for respectively, O₂, CO₂ and deterioration profiles as a function of time confirming the goodness of model fitting. For the investigated temperature profile, a shelf life gain of 0.33 days was obtained in MAP compared to the conventional storage situation (no MAP condition). Shelf life gain of more than 1 day could be obtained for optimized post-harvest conditions as numerically investigated. Such shelf life gain permitted to anticipate a significant reduction of food losses at the distribution and consumer steps. This food losses' reduction as a function of shelf life gain has been quantified using a dedicated mathematical equation that has been developed for this purpose.

Keywords: food losses and wastes, modified atmosphere packaging, mathematical modeling, shelf life prediction

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Authors: J. Roberto Lopez, Hened Saade, Graciela Morales, Javier Enriquez, Raul G. Lopez

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Implementation of systems based on nanostructures for drug delivery applications have taken relevance in recent studies focused on biomedical applications. Although there are several nanostructures as drugs carriers, the use of polymeric nanoparticles (PNP) has been widely studied for this purpose, however, the main issue for these nanostructures is the size control below 50 nm with a narrow distribution size, due to they must go through different physiological barriers and avoid to be filtered by kidneys (< 10 nm) or the spleen (> 100 nm). Thus, considering these and other factors, it can be mentioned that drug-loaded nanostructures with sizes varying between 10 and 50 nm are preferred in the development and study of PNP/drugs systems. In this sense, the Semicontinuous Heterophase Polymerization (SHP) offers the possibility to obtain PNP in the desired size range. Considering the above explained, methacrylic copolymer nanoparticles were obtained under SHP. The reactions were carried out in a jacketed glass reactor with the required quantities of water, ammonium persulfate as initiator, sodium dodecyl sulfate/sodium dioctyl sulfosuccinate as surfactants, methyl methacrylate and methacrylic acid as monomers with molar ratio of 2/1, respectively. The monomer solution was dosed dropwise during reaction at 70 °C with a mechanical stirring of 650 rpm. Nanoparticles of poly(methyl methacrylate-co-methacrylic acid) were loaded with acetylsalicylic acid (ASA, aspirin) by a chemical adsorption technique. The purified latex was put in contact with a solution of ASA in dichloromethane (DCM) at 0.1, 0.2, 0.4 or 0.6 wt-%, at 35°C during 12 hours. According to the boiling point of DCM, as well as DCM and water densities, the loading process is completed when the whole DCM is evaporated. The hydrodynamic diameter was measured after polymerization by quasi-elastic light scattering and transmission electron microscopy, before and after loading procedures with ASA. The quantitative and qualitative analyses of PNP loaded with ASA were measured by infrared spectroscopy, differential scattering calorimetry and thermogravimetric analysis. Also, the molar mass distributions of polymers were determined in a gel permeation chromatograph apparatus. The load capacity and efficiency were determined by gravimetric analysis. The hydrodynamic diameter results for methacrylic PNP without ASA showed a narrow distribution with an average particle size around 10 nm and a composition methyl methacrylate/methacrylic acid molar ratio equal to 2/1, same composition of Eudragit S100, which is a commercial compound widely used as excipient. Moreover, the latex was stabilized in a relative high solids content (around 11 %), a monomer conversion almost 95 % and a number molecular weight around 400 Kg/mol. The average particle size in the PNP/aspirin systems fluctuated between 18 and 24 nm depending on the initial percentage of aspirin in the loading process, being the drug content as high as 24 % with an efficiency loading of 36 %. These average sizes results have not been reported in the literature, thus, the methacrylic nanoparticles here reported are capable to be loaded with a considerable amount of ASA and be used as a drug carrier.

Keywords: aspirin, biocompatibility, biodegradable, Eudragit S100, methacrylic nanoparticles

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Authors: S. Cichosz, A. Masek

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A new cellulose hybrid modification approach, which is undoubtedly a scientific novelty, is introduced. The study reports the properties of cellulose (Arbocel UFC100 – Ultra Fine Cellulose) and characterizes cellulose filled polymer composites based on an ethylene-norbornene copolymer (TOPAS Elastomer E-140). Moreover, the approach of physicochemical two-stage cellulose treatment is introduced: solvent exchange (to ethanol or hexane) and further chemical modification with maleic anhydride (MA). Furthermore, the impact of the drying process on cellulose properties was investigated. Suitable measurements were carried out to characterize cellulose fibers: spectroscopic investigation (Fourier Transform Infrared Spektrofotometer-FTIR, Near InfraRed spectroscopy-NIR), thermal analysis (Differential scanning calorimetry, Thermal gravimetric analysis ) and Karl Fischer titration. It should be emphasized that for all UFC100 treatments carried out, a decrease in moisture content was evidenced. FT-IR reveals a drop in absorption band intensity at 3334 cm-1, the peak is associated with both –OH moieties and water. Similar results were obtained with Karl Fischer titration. Based on the results obtained, it may be claimed that the employment of ethanol contributes greatly to the lowering of cellulose water absorption ability (decrease of moisture content to approximately 1.65%). Additionally, regarding polymer composite properties, crucial data has been obtained from the mechanical and thermal analysis. The highest material performance was noted in the case of the composite sample that contained cellulose modified with MA after a solvent exchange with ethanol. This specimen exhibited sufficient tensile strength, which is almost the same as that of the neat polymer matrix – in the region of 40 MPa. Moreover, both the Payne effect and filler efficiency factor, calculated based on dynamic mechanical analysis (DMA), reveal the possibility of the filler having a reinforcing nature. What is also interesting is that, according to the Payne effect results, fibers dried before the further chemical modification are assumed to allow more regular filler structure development in the polymer matrix (Payne effect maximum at 1.60 MPa), compared with those not dried (Payne effect in the range 0.84-1.26 MPa). Furthermore, taking into consideration the data gathered from DSC and TGA, higher thermal stability is obtained in case of the materials filled with fibers that were dried before the carried out treatments (degradation activation energy in the region of 195 kJ/mol) in comparison with the polymer composite samples filled with unmodified cellulose (degradation activation energy of approximately 180 kJ/mol). To author’s best knowledge this work results in the introduction of a novel, new filler hybrid treatment approach. Moreover, valuable data regarding the properties of composites filled with cellulose fibers of various moisture contents have been provided. It should be emphasized that plant fiber-based polymer bio-materials described in this research might contribute significantly to polymer waste minimization because they are more readily degraded.

Keywords: cellulose fibers, solvent exchange, moisture content, ethylene-norbornene copolymer

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Authors: Aurica P. Chiriac, Vera Balan, Mihai Asandulesa, Elena Butnaru, Nita Tudorachi, Elena Stoleru, Loredana E. Nita, Iordana Neamtu, Alina Diaconu, Liliana Mititelu-Tartau

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The interest for studying ‘smart’ materials is entirely justified and in this context were realized investigations on poly(2-hydroxyethylmethacrylate-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5) undecane), which is a macromolecular compound with sensibility at pH and temperature, gel formation capacity, binding properties, amphilicity, good oxidative and thermal stability. Physico-chemical characteristics in terms of the molecular weight, temperature-sensitive abilities and thermal stability, as well rheological, dielectric and spectroscopic properties were evaluated in correlation with further coupling capabilities. Differential scanning calorimetry investigation indicated Tg at 36.6 °C and a melting point at Tm=72.8°C, for the studied copolymer, and up to 200oC two exothermic processes (at 99.7°C and 148.8°C) were registered with losing weight of about 4 %, respective 19.27%, which indicate just processes of thermal decomposition (and not phenomena of thermal transition) owing to scission of the functional groups and breakage of the macromolecular chains. At the same time, the rheological studies (rotational tests) confirmed the non-Newtonian shear-thinning fluid behavior of the copolymer solution. The dielectric properties of the copolymer have been evaluated in order to investigate the relaxation processes and two relaxation processes under Tg value were registered and attributed to localized motions of polar groups from side chain macromolecules, or parts of them, without disturbing the main chains. According to literature and confirmed as well by our investigations, β-relaxation is assigned with the rotation of the ester side group and the γ-relaxation corresponds to the rotation of hydroxy- methyl side groups. The fluorescence spectroscopy confirmed the copolymer structure, the spiroacetal moiety getting an axial conformation, more stable, with lower energy, able for specific interactions with molecules from environment, phenomena underlined by different shapes of the emission spectra of the copolymer. Also, the copolymer was used as template for indomethacin incorporation as model drug, and the biocompatible character of the complex was confirmed. The release behavior of the bioactive compound was dependent by the copolymer matrix composition, the increasing of 3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5) undecane comonomer amount attenuating the drug release. At the same time, the in vivo studies did not show significant differences of leucocyte formula elements, GOT, GPT and LDH levels, nor immune parameters (OC, PC, and BC) between control mice group and groups treated just with copolymer samples, with or without drug, data attesting the biocompatibility of the polymer samples. The investigation of the physico-chemical characteristics of poly(2-hydrxyethyl methacrylate-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5) undecane) in terms of temperature-sensitive abilities, rheological and dielectrical properties, are bringing useful information for further specific use of this polymeric compound.

Keywords: bioapplications, dielectric and spectroscopic properties, dual sensitivity at pH and temperature, smart materials

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Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz

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There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.

Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling

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Authors: Giulia Fredi, Andrea Dorigato, Luca Fambri, Alessandro Pegoretti

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Thermal energy storage (TES) is the storage of heat for later use, thus filling the gap between energy request and supply. The most widely used materials for TES are the organic solid-liquid phase change materials (PCMs), such as paraffin. These materials store/release a high amount of latent heat thanks to their high specific melting enthalpy, operate in a narrow temperature range and have a tunable working temperature. However, they suffer from a low thermal conductivity and need to be confined to prevent leakage. These two issues can be tackled by confining PCMs with carbon nanotubes (CNTs). TES applications include the buildings industry, solar thermal energy collection and thermal management of electronics. In most cases, TES systems are an additional component to be added to the main structure, but if weight and volume savings are key issues, it would be advantageous to embed the TES functionality directly in the structure. Such multifunctional materials could be employed in the automotive industry, where the diffusion of lightweight structures could complicate the thermal management of the cockpit environment or of other temperature sensitive components. This work aims to produce epoxy/carbon structural laminates containing CNT-stabilized paraffin. CNTs were added to molten paraffin in a fraction of 10 wt%, as this was the minimum amount at which no leakage was detected above the melting temperature (45°C). The paraffin/CNT blend was cryogenically milled to obtain particles with an average size of 50 µm. They were added in various percentages (20, 30 and 40 wt%) to an epoxy/hardener formulation, which was used as a matrix to produce laminates through a wet layup technique, by stacking five plies of a plain carbon fiber fabric. The samples were characterized microstructurally, thermally and mechanically. Differential scanning calorimetry (DSC) tests showed that the paraffin kept its ability to melt and crystallize also in the laminates, and the melting enthalpy was almost proportional to the paraffin weight fraction. These thermal properties were retained after fifty heating/cooling cycles. Laser flash analysis showed that the thermal conductivity through the thickness increased with an increase of the PCM, due to the presence of CNTs. The ability of the developed laminates to contribute to the thermal management was also assessed by monitoring their cooling rates through a thermal camera. Three-point bending tests showed that the flexural modulus was only slightly impaired by the presence of the paraffin/CNT particles, while a more sensible decrease of the stress and strain at break and the interlaminar shear strength was detected. Optical and scanning electron microscope images revealed that these could be attributed to the preferential location of the PCM in the interlaminar region. These results demonstrated the feasibility of multifunctional structural TES composites and highlighted that the PCM size and distribution affect the mechanical properties. In this perspective, this group is working on the encapsulation of paraffin in a sol-gel derived organosilica shell. Submicron spheres have been produced, and the current activity focuses on the optimization of the synthesis parameters to increase the emulsion efficiency.

Keywords: carbon fibers, carbon nanotubes, lightweight materials, multifunctional composites, thermal energy storage

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Authors: Nikola Toshikj, Michel Ramonda, Sylvain Catrouillet, Jean-Jacques Robin, Sebastien Blanquer

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Biodegradable and biocompatible block copolymers have risen as the golden materials in both medical and environmental applications. Moreover, if their architecture is of controlled manner, higher applications can be foreseen. In the meantime, organocatalytic ROP has been promoted as more rapid and immaculate route, compared to the traditional organometallic catalysis, towards efficient synthesis of block copolymer architectures. Therefore, herein we report novel organocatalytic pathway with guanidine molecules (TBD) for supported synthesis of trimethylene carbonate initiated by poly(caprolactone) as pre-polymer. Pristine PTMC-b-PCL-b-PTMC block copolymer structure, without any residual products and clear desired block proportions, was achieved under 1.5 hours at room temperature and verified by NMR spectroscopies and size-exclusion chromatography. Besides, when elaborating block copolymer films, further stability and amelioration of mechanical properties can be achieved via additional reticulation step of precedently methacrylated block copolymers. Subsequently, stimulated by the insufficient studies on the phase-separation/crystallinity relationship in these semi-crystalline block copolymer systems, their intrinsic thermal and morphology properties were investigated by differential scanning calorimetry and atomic force microscopy. Firstly, by DSC measurements, the block copolymers with χABN values superior to 20 presented two distinct glass transition temperatures, close to the ones of the respecting homopolymers, demonstrating an initial indication of a phase-separated system. In the interim, the existence of the crystalline phase was supported by the presence of melting temperature. As expected, the crystallinity driven phase-separated morphology predominated in the AFM analysis of the block copolymers. Neither crosslinking at melted state, hence creation of a dense polymer network, disturbed the crystallinity phenomena. However, the later revealed as sensible to rapid liquid nitrogen quenching directly from the melted state. Therefore, AFM analysis of liquid nitrogen quenched and crosslinked block copolymer films demonstrated a thermodynamically driven phase-separation clearly predominating over the originally crystalline one. These AFM films remained stable with their morphology unchanged even after 4 months at room temperature. However, as demonstrated by DSC analysis once rising the temperature above the melting temperature of the PCL block, neither the crosslinking nor the liquid nitrogen quenching shattered the semi-crystalline network, while the access to thermodynamical phase-separated structures was possible for temperatures under the poly (caprolactone) melting point. Precisely this coexistence of dual crosslinked/crystalline networks in the same copolymer structure allowed us to establish, for the first time, the shape-memory properties in such materials, as verified by thermomechanical analysis. Moreover, the response temperature to the material original shape depended on the block copolymer emplacement, hence PTMC or PCL as end-block. Therefore, it has been possible to reach a block copolymer with transition temperature around 40°C thus opening potential real-life medical applications. In conclusion, the initial study of phase-separation/crystallinity relationship in PTMC-b-PCL-b-PTMC block copolymers lead to the discovery of novel shape memory materials with superior properties, widely demanded in modern-life applications.

Keywords: biodegradable block copolymers, organocatalytic ROP, self-assembly, shape-memory

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Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

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Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

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Authors: Michael Sigruener, Dirk Muscat, Nicole Struebbe

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Fiber reinforcement is a state of the art to enhance mechanical properties in plastics. For concrete and civil engineering, steel reinforcements are commonly used. Steel reinforcements show disadvantages in their chemical resistance and weight, whereas polymer fibers' major problems are in fiber-matrix adhesion and mechanical properties. In spite of these facts, longevity and easy handling, as well as chemical resistance motivate researches to develop a polymeric material for fiber reinforced concrete. Adhesion and interfacial mechanism in fiber-polymer-composites are already studied thoroughly. For polymer fibers used as concrete reinforcement, the bonding behavior still requires a deeper investigation. Therefore, several differing polymers (e.g., polypropylene (PP), polyamide 6 (PA6) and polyetheretherketone (PEEK)) were spun into fibers via single screw extrusion and monoaxial stretching. Fibers then were embedded in a concrete matrix, and Single-Fiber-Pull-Out-Tests (SFPT) were conducted to investigate bonding characteristics and microstructural interface of the composite. Differences in maximum pull-out-force, displacement and slope of the linear part of force vs displacement-function, which depicts the adhesion strength and the ductility of the interfacial bond were studied. In SFPT fiber, debonding is an inhomogeneous process, where the combination of interfacial bonding and friction mechanisms add up to a resulting value. Therefore, correlations between polymeric properties and pull-out-mechanisms have to be emphasized. To investigate these correlations, all fibers were introduced to a series of analysis such as differential scanning calorimetry (DSC), contact angle measurement, surface roughness and hardness analysis, tensile testing and scanning electron microscope (SEM). Of each polymer, smooth and abraded fibers were tested, first to simulate the abrasion and damage caused by a concrete mixing process and secondly to estimate the influence of mechanical anchoring of rough surfaces. In general, abraded fibers showed a significant increase in maximum pull-out-force due to better mechanical anchoring. Friction processes therefore play a major role to increase the maximum pull-out-force. The polymer hardness affects the tribological behavior and polymers with high hardness lead to lower surface roughness verified by SEM and surface roughness measurements. This concludes into a decreased maximum pull-out-force for hard polymers. High surface energy polymers show better interfacial bonding strength in general, which coincides with the conducted SFPT investigation. Polymers such as PEEK or PA6 show higher bonding strength in smooth and roughened fibers, revealed through high pull-out-force and concrete particles bonded on the fiber surface pictured via SEM analysis. The surface energy divides into dispersive and polar part, at which the slope is correlating with the polar part. Only polar polymers increase their SFPT-function slope due to better wetting abilities when showing a higher bonding area through rough surfaces. Hence, the maximum force and the bonding strength of an embedded fiber is a function of polarity, hardness, and consequently surface roughness. Other properties such as crystallinity or tensile strength do not affect bonding behavior. Through the conducted analysis, it is now feasible to understand and resolve different effects in pull-out-behavior step-by-step based on the polymer properties itself. This investigation developed a roadmap on how to engineer high adhering polymeric materials for fiber reinforcement of concrete.

Keywords: fiber-matrix interface, polymeric fibers, fiber reinforced concrete, single fiber pull-out test

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Authors: Piotr K. Szewczyk, Arkadiusz Gradys, Sungkyun Kim, Luana Persano, Mateusz M. Marzec, Oleksander Kryshtal, Andrzej Bernasik, Sohini Kar-Narayan, Pawel Sajkiewicz, Urszula Stachewicz

Abstract:

Piezoelectric polymers have received great attention in smart textiles, wearables, and flexible electronics. Their potential applications range from devices that could operate without traditional power sources, through self-powering sensors, up to implantable biosensors. Semi-crystalline PVDF is often proposed as the main candidate for industrial-scale applications as it exhibits exceptional energy harvesting efficiency compared to other polymers combined with high mechanical strength and thermal stability. Plenty of approaches have been proposed for obtaining PVDF rich in the desired β-phase with electric polling, thermal annealing, and mechanical stretching being the most prevalent. Electrospinning is a highly tunable technique that provides a one-step process of obtaining highly piezoelectric PVDF fibers without the need for post-treatment. In this study, voltage polarity and relative humidity influence on electrospun PVDF, fibers were investigated with the main focus on piezoelectric β-phase contents and piezoelectric performance. Morphology and internal structure of fibers were investigated using scanning (SEM) and transmission electron microscopy techniques (TEM). Fourier Transform Infrared Spectroscopy (FITR), wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) were used to characterize the phase composition of electrospun PVDF. Additionally, surface chemistry was verified with X-ray photoelectron spectroscopy (XPS). Piezoelectric performance of individual electrospun PVDF fibers was measured using piezoresponse force microscopy (PFM), and the power output from meshes was analyzed via custom-built equipment. To prepare the solution for electrospinning, PVDF pellets were dissolved in dimethylacetamide and acetone solution in a 1:1 ratio to achieve a 24% solution. Fibers were electrospun with a constant voltage of +/-15kV applied to the stainless steel nozzle with the inner diameter of 0.8mm. The flow rate was kept constant at 6mlh⁻¹. The electrospinning of PVDF was performed at T = 25°C and relative humidity of 30 and 60% for PVDF30+/- and PVDF60+/- samples respectively in the environmental chamber. The SEM and TEM analysis of fibers produced at a lower relative humidity of 30% (PVDF30+/-) showed a smooth surface in opposition to fibers obtained at 60% relative humidity (PVDF60+/-), which had wrinkled surface and additionally internal voids. XPS results confirmed lower fluorine content at the surface of PVDF- fibers obtained by electrospinning with negative voltage polarity comparing to the PVDF+ obtained with positive voltage polarity. Changes in surface composition measured with XPS were found to influence the piezoelectric performance of obtained fibers what was further confirmed by PFM as well as by custom-built fiber-based piezoelectric generator. For PVDF60+/- samples humidity led to an increase of β-phase contents in PVDF fibers as confirmed by FTIR, WAXS, and DSC measurements, which showed almost two times higher concentrations of β-phase. A combination of negative voltage polarity with high relative humidity led to fibers with the highest β-phase contents and the best piezoelectric performance of all investigated samples. This study outlines the possibility to produce electrospun PVDF fibers with tunable piezoelectric performance in a one-step electrospinning process by controlling relative humidity and voltage polarity conditions. Acknowledgment: This research was conducted within the funding from m the Sonata Bis 5 project granted by National Science Centre, No 2015/18/E/ST5/00230, and supported by the infrastructure at International Centre of Electron Microscopy for Materials Science (IC-EM) at AGH University of Science and Technology. The PFM measurements were supported by an STSM Grant from COST Action CA17107.

Keywords: crystallinity, electrospinning, PVDF, voltage polarity

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