Search results for: Sebastien Nouveau

Authors: Allaire Eric, Hauet Pascal, Floresco Jean, Beley Sebastien, Sussman Helene, Virag Ronald

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Background: Caverno-venous leakage (CVL) is devastating, although barely known disease, the first cause of major physical impairment in men under 25, and responsible for 50% of resistances to phosphodiesterase 5-inhibitors (PDE5-I), affecting 30 to 40% of users in this medication class. In this condition, too early blood drainage from corpora cavernosa prevents penile rigidity and penetration during sexual intercourse. The role of conservative surgery in this disease remains controversial. Aim: Assess complications and results of combined open surgery and embolization for CVL. Method: Between June 2016 and September 2021, 133 consecutive patients underwent surgery in our institution for CVL, causing severe erectile dysfunction (ED) resistance to oral medical treatment. Procedures combined vein embolization and ligation with microsurgical techniques. We performed a pre-and post-operative clinical (Erection Harness Scale: EHS) hemodynamic evaluation by duplex sonography in all patients. Before surgery, the CVL network was visualized by computed tomography cavernography. Penile EMG was performed in case of diabetes or suspected other neurological conditions. All patients were optimized for hormonal status—data we prospectively recorded. Results: Clinical signs suggesting CVL were ED since age lower than 25, loss of erection when changing position, penile rigidity varying according to the position. Main complications were minor pulmonary embolism in 2 patients, one after airline travel, one with Factor V Leiden heterozygote mutation, one infection and three hematomas requiring reoperation, one decreased gland sensitivity lasting for more than one year. Mean pre-operative pharmacologic EHS was 2.37+/-0.64, mean pharmacologic post-operative EHS was 3.21+/-0.60, p<0.0001 (paired t-test). The mean EHS variation was 0.87+/-0.74. After surgery, 81.5% of patients had a pharmacologic EHS equal to or over 3, allowing for intercourse with penetration. Three patients (2.2%) experienced lower post-operative EHS. The main cause of failure was leakage from the deep dorsal aspect of the corpus cavernosa. In a 14 months follow-up, 83.2% of patients had a clinical EHS equal to or over 3, allowing for sexual intercourse with penetration, one-third of them without any medication. 5 patients had a penile implant after unsuccessful conservative surgery. Conclusion: Open surgery combined with embolization for CVL is an efficient approach to CVL causing severe erectile dysfunction.

Keywords: erectile dysfunction, cavernovenous leakage, surgery, embolization, treatment, result, complications, penile duplex sonography

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Authors: Gautier Girard, Marion Martiny, Sebastien Mercier, Mohamad Jrad, Mohamed-Slim Bahi, Laurent Bodin, Francois Lechleiter, David Nevo, Sophie Dareys

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Reliability of electronic devices has always been of highest interest for Aero-MIL and space applications. In any electronic device, Printed Circuit Board (PCB), providing interconnection between components, is a key for reliability. During the last decades, PCB technologies evolved to sustain and/or fulfill increased original equipment manufacturers requirements and specifications, higher densities and better performances, faster time to market and longer lifetime, newer material and mixed buildups. From the very beginning of the PCB industry up to recently, qualification, experiments and trials, and errors were the most popular methods to assess system (PCB) reliability. Nowadays OEM, PCB manufacturers and scientists are working together in a close relationship in order to develop predictive models for PCB reliability and lifetime. To achieve that goal, it is fundamental to characterize precisely base materials (laminates, electrolytic copper, …), in order to understand failure mechanisms and simulate PCB aging under environmental constraints by means of finite element method for example. The laminates are woven composites and have thus an orthotropic behaviour. The in-plane properties can be measured by combining classical uniaxial testing and digital image correlation. Nevertheless, the out-of-plane properties cannot be evaluated due to the thickness of the laminate (a few hundred of microns). It has to be noted that the knowledge of the out-of-plane properties is fundamental to investigate the lifetime of high density printed circuit boards. A homogenization method combining analytical and numerical approaches has been developed in order to obtain the complete elastic orthotropic behaviour of a woven composite from its precise 3D internal structure and its experimentally measured in-plane elastic properties. Since the mechanical properties of the resin surrounding the fibres are unknown, an inverse method is proposed to estimate it. The methodology has been applied to one laminate used in hyperfrequency spatial applications in order to get its elastic orthotropic behaviour at different temperatures in the range [-55°C; +125°C]. Next; numerical simulations of a plated through hole in a double sided PCB are performed. Results show the major importance of the out-of-plane properties and the temperature dependency of these properties on the lifetime of a printed circuit board. Acknowledgements—The support of the French ANR agency through the Labcom program ANR-14-LAB7-0003-01, support of CNES, Thales Alenia Space and Cimulec is acknowledged.

Keywords: homogenization, orthotropic behaviour, printed circuit board, woven composites

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Authors: Bastien Sanglard, Lou Magnat, Ligia Barna, Julian Carrey, Sébastien Lachaize

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Cooking is a primary need for humans, several techniques being used around the globe based on different sources of energy: electricity, solid fuel (wood, coal...), fuel or liquefied petroleum gas. However, all of them leads to direct or indirect greenhouse gas emissions and sometimes health damage in household. Therefore, the solar concentrated power represent a great option to lower the damages because of a cleaner using phase. Nevertheless, the construction phase of the solar cooker still requires primary energy and materials, which leads to environmental impacts. The aims of this work is to analyse the ecological impacts of a commercialaluminium parabola and to compare it with other means of cooking, taking the boiling of 2 litres of water three times a day during 40 years as the functional unit. Life cycle assessment was performed using the software Umberto and the EcoInvent database. Calculations were realized over more than 13 criteria using two methods: the international panel on climate change method and the ReCiPe method. For the reflector itself, different aluminium provenances were compared, as well as the use of recycled aluminium. For the structure, aluminium was compared to iron (primary and recycled) and wood. Results show that climate impacts of the studied parabola was 0.0353 kgCO2eq/kWh when built with Chinese aluminium and can be reduced by 4 using aluminium from Canada. Assessment also showed that using 32% of recycled aluminium would reduce the impact by 1.33 and 1.43 compared to the use of primary Canadian aluminium and primary Chinese aluminium, respectively. The exclusive use of recycled aluminium lower the impact by 17. Besides, the use of iron (recycled or primary) or wood for the structure supporting the reflector significantly lowers the impact. The impact categories of the ReCiPe method show that the parabola made from Chinese aluminium has the heaviest impact - except for metal resource depletion - compared to aluminium from Canada, recycled aluminium or iron. Impact of solar cooking was then compared to gas stove and induction. The gas stove model was a cast iron tripod that supports the cooking pot, and the induction plate was as well a single spot plate. Results show the parabolic solar cooker has the lowest ecological impact over the 13 criteria of the ReCiPe method and over the global warming potential compared to the two other technologies. The climate impact of gas cooking is 0.628kgCO2/kWh when used with natural gas and 0.723 kgCO2/kWh when used with a bottle of gas. In each case, the main part of emissions came from gas burning. Induction cooking has a global warming potential of 0.12 kgCO2eq/kWh with the electricity mix of France, 96.3% of the impact being due to electricity production. Therefore, the electricity mix is a key factor for this impact: for instance, with the electricity mix of Germany and Poland, impacts are 0.81kgCO2eq/kWh and 1.39 kgCO2eq/kWh, respectively. Therefore, the parabolic solar cooker has a real ecological advantages compared to both gas stove and induction plate.

Keywords: life cycle assessement, solar concentration, cooking, sustainability

Procedia PDF Downloads 134

Authors: Elizaveta Korzhova, Sebastien Deon, Patrick Fievet, Dmitry Lopatin, Oleg Baranov

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Filtration with nanoporous ultrafiltration membranes is an attractive option to remove ionic pollutants from contaminated effluents. Unfortunately, commercial membranes are not necessarily suitable for specific applications, and their modification by polymer deposition is a fruitful way to adapt their performances accordingly. Many methods are usually used for surface modification, but a novel technique based on electrospray is proposed here. Various quantities of polymers were deposited on a commercial membrane, and the impact of the deposit is investigated on filtration performances and discussed in terms of charge and hydrophobicity. The electrospray deposition is a technique which has not been used for membrane modification up to now. It consists of spraying small drops of polymer solution under a high voltage between the needle containing the solution and the metallic support on which membrane is stuck. The advantage of this process lies in the small quantities of polymer that can be coated on the membrane surface compared with immersion technique. In this study, various quantities (from 2 to 40 μL/cm²) of solutions containing two charged polymers (13 mmol/L of monomer unit), namely polyethyleneimine (PEI) and polystyrene sulfonate (PSS), were sprayed on a negatively charged polyethersulfone membrane (PLEIADE, Orelis Environment). The efficacy of the polymer deposition was then investigated by estimating ion rejection, permeation flux, zeta-potential and contact angle before and after the polymer deposition. Firstly, contact angle (θ) measurements show that the surface hydrophilicity is notably improved by coating both PEI and PSS. Moreover, it was highlighted that the contact angle decreases monotonously with the amount of sprayed solution. Additionally, hydrophilicity enhancement was proved to be better with PSS (from 62 to 35°) than PEI (from 62 to 53°). Values of zeta-potential (ζ were estimated by measuring the streaming current generated by a pressure difference on both sides of a channel made by clamping two membranes. The ζ-values demonstrate that the deposits of PSS (negative at pH=5.5) allow an increase of the negative membrane charge, whereas the deposits of PEI (positive) lead to a positive surface charge. Zeta-potentials measurements also emphasize that the sprayed quantity has little impact on the membrane charge, except for very low quantities (2 μL/m²). The cross-flow filtration of salt solutions containing mono and divalent ions demonstrate that polymer deposition allows a strong enhancement of ion rejection. For instance, it is shown that rejection of a salt containing a divalent cation can be increased from 1 to 20 % and even to 35% by deposing 2 and 4 μL/cm² of PEI solution, respectively. This observation is coherent with the reversal of the membrane charge induced by PEI deposition. Similarly, the increase of negative charge induced by PSS deposition leads to an increase of NaCl rejection from 5 to 45 % due to electrostatic repulsion of the Cl- ion by the negative surface charge. Finally, a notable fall in the permeation flux due to the polymer layer coated at the surface was observed and the best polymer concentration in the sprayed solution remains to be determined to optimize performances.

Keywords: ultrafiltration, electrospray deposition, ion rejection, permeation flux, zeta-potential, hydrophobicity

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Authors: Boukary Lam, Sebastien Deon, Patrick Fievet, Nadia Crini, Gregorio Crini

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Treatment of heavy metal-contaminated industrial wastewater has become a major challenge over the last decades. Conventional processes for the treatment of metal-containing effluents do not always simultaneously satisfy both legislative and economic criteria. In this context, coupling of processes can then be a promising alternative to the conventional approaches used by industry. The polymer-assisted ultrafiltration (PAUF) process is one of these coupling processes. Its principle is based on a sequence of steps with reaction (e.g., complexation) between metal ions and a polymer and a step involving the rejection of the formed species by means of a UF membrane. Unlike free ions, which can cross the UF membrane due to their small size, the polymer/ion species, the size of which is larger than pore size, are rejected. The PAUF process was deeply investigated herein in the case of removal of nickel ions by adding chitosan and carboxymethyl cellulose (CMC). Experiments were conducted with synthetic solutions containing 1 to 100 ppm of nickel ions with or without the presence of NaCl (0.05 to 0.2 M), and an industrial discharge water (containing several metal ions) with and without polymer. Chitosan with a molecular weight of 1.8×105 g mol⁻¹ and a degree of acetylation close to 15% was used. CMC with a degree of substitution of 0.7 and a molecular weight of 9×105 g mol⁻¹ was employed. Filtration experiments were performed under cross-flow conditions with a filtration cell equipped with a polyamide thin film composite flat-sheet membrane (3.5 kDa). Without the step of polymer addition, it was found that nickel rejection decreases from 80 to 0% with increasing metal ion concentration and salt concentration. This behavior agrees qualitatively with the Donnan exclusion principle: the increase in the electrolyte concentration screens the electrostatic interaction between ions and the membrane fixed the charge, which decreases their rejection. It was shown that addition of a sufficient amount of polymer (greater than 10⁻² M of monomer unit) can offset this decrease and allow good metal removal. However, the permeation flux was found to be somewhat reduced due to the increase in osmotic pressure and viscosity. It was also highlighted that the increase in pH (from 3 to 9) has a strong influence on removal performances: the higher pH value, the better removal performance. The two polymers have shown similar performance enhancement at natural pH. However, chitosan has proved more efficient in slightly basic conditions (above its pKa) whereas CMC has demonstrated very weak rejection performances when pH is below its pKa. In terms of metal rejection, chitosan is thus probably the better option for basic or strongly acid (pH < 4) conditions. Nevertheless, CMC should probably be preferred to chitosan in natural conditions (5 < pH < 8) since its impact on the permeation flux is less significant. Finally, ultrafiltration of an industrial discharge water has shown that the increase in metal ion rejection induced by the polymer addition is very low due to the competing phenomenon between the various ions present in the complex mixture.

Keywords: carboxymethyl cellulose, chitosan, heavy metals, nickel ion, polymer-assisted ultrafiltration

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Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

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Authors: Abdelkhalek Bouchikhi, Elyes Benmokhtar, Sebastien Saletzki

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The aeronautical field is experiencing issues with RF spectrum congestion due to the constant increase in the number of flights, aircrafts and telecom systems on board. In addition, these systems are bulky in size, weight and energy consumption. The cognitive radio helps particularly solving the spectrum congestion issue by its capacity to detect idle frequency channels then, allowing an opportunistic exploitation of the RF spectrum. The present work aims to propose a new use case for aeronautical spectrum sharing and to study the performances of three different detection techniques: energy detector, matched filter and cyclostationary detector within the aeronautical use case. The spectrum in the proposed cognitive radio is allocated dynamically where each cognitive radio follows a cognitive cycle. The spectrum sensing is a crucial step. The goal of the sensing is gathering data about the surrounding environment. Cognitive radio can use different sensors: antennas, cameras, accelerometer, thermometer, etc. In IEEE 802.22 standard, for example, a primary user (PU) has always the priority to communicate. When a frequency channel witch used by the primary user is idle, the secondary user (SU) is allowed to transmit in this channel. The Distance Measuring Equipment (DME) is composed of a UHF transmitter/receiver (interrogator) in the aircraft and a UHF receiver/transmitter on the ground. While the future cognitive radio will be used jointly to alleviate the spectrum congestion issue in the aeronautical field. LDACS, for example, is a good candidate; it provides two isolated data-links: ground-to-air and air-to-ground data-links. The first contribution of the present work is a strategy allowing sharing the L-band. The adopted spectrum sharing strategy is as follow: the DME will play the role of PU which is the licensed user and the LDACS1 systems will be the SUs. The SUs could use the L-band channels opportunely as long as they do not causing harmful interference signals which affect the QoS of the DME system. Although the spectrum sensing is a key step, it helps detecting holes by determining whether the primary signal is present or not in a given frequency channel. A missing detection on primary user presence creates interference between PU and SU and will affect seriously the QoS of the legacy radio. In this study, first brief definitions, concepts and the state of the art of cognitive radio will be presented. Then, a study of three communication channel detection algorithms in a cognitive radio context is carried out. The study is made from the point of view of functions, material requirements and signal detection capability in the aeronautical field. Then, we presented a modeling of the detection problem by three different methods (energy, adapted filter, and cyclostationary) as well as an algorithmic description of these detectors is done. Then, we study and compare the performance of the algorithms. Simulations were carried out using MATLAB software. We analyzed the results based on ROCs curves for SNR between -10dB and 20dB. The three detectors have been tested with a synthetics and real world signals.

Keywords: aeronautic, communication, navigation, surveillance systems, cognitive radio, spectrum sensing, software defined radio

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Authors: Yohann R. J. Thomas, Sébastien Solan

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Conventional battery technology includes the assembly of electrode/separator/electrode by standard techniques such as stacking or winding, depending on the format size. In that type of batteries, coating or pasting techniques are only used for the electrode process. The processes are suited for large scale production of batteries and perfectly adapted to plenty of application requirements. Nevertheless, as the demand for both easier and cost-efficient production modes, flexible, custom-shaped and efficient small sized batteries is rising. Thin-film, printable batteries are one of the key areas for printed electronics. In the frame of European BASMATI project, we are investigating the feasibility of a new design of lithium-ion battery: interdigitated planar core design. Polymer substrate is used to produce bendable and flexible rechargeable accumulators. Direct fully printed batteries lead to interconnect the accumulator with other electronic functions for example organic solar cells (harvesting function), printed sensors (autonomous sensors) or RFID (communication function) on a common substrate to produce fully integrated, thin and flexible new devices. To fulfill those specifications, a high resolution printing process have been selected: Aerosol jet printing. In order to fit with this process parameters, we worked on nanomaterials formulation for current collectors and electrodes. In addition, an advanced printed polymer-electrolyte is developed to be implemented directly in the printing process in order to avoid the liquid electrolyte filling step and to improve safety and flexibility. Results: Three different current collectors has been studied and printed successfully. An ink of commercial copper nanoparticles has been formulated and printed, then a flash sintering was applied to the interdigitated design. A gold ink was also printed, the resulting material was partially self-sintered and did not require any high temperature post treatment. Finally, carbon nanotubes were also printed with a high resolution and well defined patterns. Different electrode materials were formulated and printed according to the interdigitated design. For cathodes, NMC and LFP were efficaciously printed. For anodes, LTO and graphite have shown to be good candidates for the fully printed battery. The electrochemical performances of those materials have been evaluated in a standard coin cell with lithium-metal counter electrode and the results are similar with those of a traditional ink formulation and process. A jellified plastic crystal solid state electrolyte has been developed and showed comparable performances to classical liquid carbonate electrolytes with two different materials. In our future developments, focus will be put on several tasks. In a first place, we will synthesize and formulate new specific nano-materials based on metal-oxyde. Then a fully printed device will be produced and its electrochemical performance will be evaluated.

Keywords: high resolution digital printing, lithium-ion battery, nanomaterials, solid-state electrolytes

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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: 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

Procedia PDF Downloads 104