Decrease In Molar Mass Research Articles

A step to microplastic formation: Microcracking and associated surface transformations of recycled LDPE, LLDPE, HDPE, and PP plastics exposed to UV radiation

Plastics when exposed to UV radiation start to degrade via photooxidative aging including free radical formation, oxidation, chain scission and/or crosslinking reactions. These chemical changes can cause loss in mechanical strength, surface embrittlement, and eventually surface erosion. The eroded particles are microplastics (MPs), which have been identified as a potentially serious threat to the environment and its inhabitants. In general, photodegradation of virgin plastics has been studied extensively, but there is not much literature on the degradation of recycled plastics. The goal of the study was to investigate the changes caused by photodegradation in recycled plastics and assess the potential risks of MPs formation. And eventually, knowing the chemical and physical transformations occurring on the surface understand the mechanism behind surface microcracking, which is the first step of MPs formation. Pellets of five industrially recycled plastics (low-density polyethylene (rLDPE), linear low-density polyethylene (rLLDPE), high-density polyethylene (rHDPE), and two polypropylenes (rPP)) from different waste sources were analysed. UV irradiation was performed in an accelerated weathering chamber for milled (< 400 µm) plastic powder to ensure homogeneous changes throughout the sample. The properties were investigated by ATR-FTIR, HT-SEC, XPS and DSC. Formation of microcracks was studied on plastic pellets by SEM. The results showed that the degradation significantly differed between the recycled plastics, and the waste source was more important than the plastic type. rLDPE and one of the rPP samples showed a significant increase in carbonyl index as well as decrease in molar mass during the first 500 h of UV exposure. The other rPP and rHDPE samples showed first considerable signs of degradation only after 1000 h of UV exposure. Minor changes were observed for the rLLDPE sample during the whole test. The SEM revealed microcracking on the surface of all samples, which also had noticeable degradation identified by other methods. These recycled plastics can be considered the ones with the highest potential of MPs formation. From the chemical and physical transformations identified on the surface, the mechanism leading to microcracking, which is the first step in the formation of MPs, is proposed.

Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification.

This communication reports on vinyl polymers capable of selective and fast main-chain scission (MCS). The trick is the domino reaction in an alternating sequence of methyl 2-(trimethylsiloxymethyl)acrylate and 5,6-benzo-2-methylene-1,3-dioxepane, a cyclic ketene acetal for radical ring-opening polymerization. Removal of the trimethylsilyl group using Bu4N+·F- readily led to MCS via irreversible transesterification of the ester backbone, affording a five-membered lactone fragment. The molar mass decreased drastically within 5 min, and no side reactions were observed. Control experiments suggest that the formation of a five-membered ring via a domino reaction is critical for fast and selective MCS. The terpolymers with methyl methacrylate and styrene also exhibited a large decrease in molar mass within 5 min. In addition, MCS was also observed for the heterogeneous reaction system in acidic aqueous media; treatment of the binary copolymer in a 50 wt % acetic acid solution resulted in a significant decrease in molar mass after 30 min. These results suggest efficient construction of degradable sites using a binary monomer system corresponding to the pendant trigger and ester backbone. Because this molecular design using a binary monomer system provides selective and fast MCS for terpolymers containing other vinyl monomers, it can provide various degradable vinyl polymers.

Action of AA9 lytic polysaccharide monooxygenase enzymes on different cellulose allomorphs

Lytic polysaccharide monooxygenase (LPMO)-catalyzed oxidative processes play a major role in natural biomass conversion. Despite their oxidative cleavage at the surface of polysaccharides, understanding of their mode of action, and the impact of structural patterns of the cellulose fiber on LPMO activity is still not fully understood. In this work, we investigated the action of two different LPMOs from Podospora anserina on celluloses showing different structural patterns. For this purpose, we prepared cellulose II and cellulose III allomorphs from cellulose I cotton linters, as well as amorphous cellulose. LPMO action was monitored in terms of surface morphology, molar mass changes and monosaccharide profile. Both PaLPMO9E and PaLPMO9H were active on the different cellulose allomorphs (I, II and III), and on amorphous cellulose (PASC) whereas they displayed a different behavior, with a higher molar mass decrease observed for cellulose I. Overall, the pretreatment with LPMO enzymes clearly increased the accessibility of all types of cellulose, which was quantified by the higher carboxylate content after carboxymethylation reaction on LPMO-pretreated celluloses. This work gives more insight into the action of LPMOs as a tool for deconstructing lignocellulosic biomass to obtain new bio-based building blocks.

Development of reversibly photo-crosslinkable water-stable poly(2-ethyl-2-oxazoline) nanofibers via functionalization with cinnamoyl moieties

Poly(2-ethyl-2-oxazoline) (PEtOx) is a potent member of the versatile poly(2-oxazoline) polymer platform with its high hydrophilicity that could be beneficial in numerous biomedical applications, especially in the form of a nanofibrous membrane. However, its water-solubility limits its application in situations where a stable, nanofibrous morphology is required in aqueous environments. The present work offers a straightforward route towards water-stable PEtOx-based nanofibrous membranes, via post-polymerization functionalization with cinnamoyl moieties (PEtOx-Cin) and photo-crosslinking of the electrospun membranes. It is shown that a UVB treatment does not significantly affect the nanofibrous morphology, while successfully inducing the cinnamoyl dimerization process and hence the formation of a polymeric network, as evidenced by spectral analysis. The hereby crosslinked PEtOx-based nanofibers exhibit a prolonged water-stability (at least 45 days), while, interestingly, intermediate irradiation times yield the best results. Full disintegration of the photo-crosslinked nanofibers in aqueous media could be achieved by subsequent UVC exposure. This is not only due to decrosslinking of the cinnamoyl dimers, but was also found to be due to partial degradation of the polymeric backbone. The investigation of UVB/UVC exposure on pure PEtOx nanofibrous membranes confirmed the photo-degradation of the polymeric backbone by a significant decrease in molar mass as observed by size exclusion chromatography and supported by spectral analysis. The hereby proposed, straightforward route for reversible crosslinking of PEtOx-based nanofibrous membranes and their accessible disintegration will contribute to the promotion of these materials in biomedical applications where a water-stable, nanofibrous morphology combined with high hydrophilicity and easy removal is required.

Meniscal repair with additive manufacture of bioresorbable polymer: From physicochemical characterization to implantation of 3D printed poly (L-co-D, L lactide-co-trimethylene carbonate) with autologous stem cells in rabbits.

Three-dimensional (3D) structures are actually the state-of-the-art technique to create porous scaffolds for tissue engineering. Since regeneration in cartilage tissue is limited due to intrinsic cellular properties this study aims to develop and characterize three-dimensional porous scaffolds of poly (L-co-D, L lactide-co-trimethylene carbonate), PLDLA-TMC, obtained by 3D fiber deposition technique. The PLDLA-TMC terpolymer scaffolds (70:30), were obtained and characterized by scanning electron microscopy, gel permeation chromatography, differential scanning calorimetry, thermal gravimetric analysis, compression mechanical testing and study on in vitro degradation, which showed its amorphous characteristics, cylindrical geometry, and interconnected pores. The in vitro degradation study showed significant loss of mechanical properties compatible with a decrease in molar mass, accompanied by changes in morphology. The histocompatibility association of mesenchymal stem cells from rabbit's bone marrow, and PLDLA-TMC scaffolds, were evaluated in the meniscus regeneration, proving the potential of cell culture at in vivo tissue regeneration. Nine New Zealand rabbits underwent total medial meniscectomy, yielding three treatments: implantation of the seeded PLDLA-TMC scaffold, implantation of the unseeded PLDLA-TMC and negative control (defect without any implant). After 24weeks, the results revealed the presence of fibrocartilage in the animals treated with polymer. However, the regeneration obtained with the seeded PLDLA-TMC scaffolds with mesenchymal stem cells had become intimal to mature fibrocartilaginous tissue of normal meniscus both macroscopically and histologically. This study demonstrated the effectiveness of the PLDLA-TMC scaffold in meniscus regeneration and the potential of mesenchymal stem cells in tissue engineering, without the use of growth factors. It is concluded that bioresorbable polymers represent a promising alternative for tissue regeneration.

Evaluation of the in vivo chemical reactivity of a novel copolymer insulation on cardiac leads in a single-center study

BackgroundHuman in vivo data on the chemical stability of different transvenous lead materials, particularly OptimTM leads, are lacking. ObjectivesThe purpose of this study was to determine the chemical reactivity of insulation materials by analyzing the molar mass of extracted pacing and defibrillator leads MethodsWe collected extracted leads at Emory University Hospitals and sent the leads with thermoplastic outer insulation material for molar mass analysis, a material characteristic that informs biostability. Leads were separated based on the chemical identity of the outer insulation material, and the molar mass was measured by an independent party. The extent of chemical reaction was compared across leads having different materials: poly(ether)urethane 55D, poly(ether)urethane 80A, and Optim. ResultsA total of 70 leads were extracted. The subset of extracted leads having outer insulation materials composed of PEU or Optim were analyzed for molar mass, where implant times ranged from 0.12 to 16.26 years. The rate of chemical degradation was compared by plotting the extent of reaction [Mn(t = 0)/Mn(t)] as a function of implant time. The Optim molar mass decreased to 40% of its initial value at 10 years of implant. No change in the molar mass of the PEU insulations could be resolved over the same 10-year implant time. ConclusionBecause the molar mass of a polymer is directly related to its mechanical integrity, the observed decrease in molar mass of Optim likely translates into premature insulation defects and is consistent with the observed increased rate of electrical malfunction/noise in this subset of cardiac leads.

Synthesis, physicochemical and emulsifying properties of OSA-modified tamarind seed polysaccharides with different degrees of substitution

Octenyl succinic anhydride modified tamarind seed polysaccharides (OTSPs) with various degrees of substitution were first synthesized and characterized in this work. The structural, solid-state, solution and emulsifying properties of the OTSPs and the effect of the degree of substitution (DS) were investigated. The structural characterization confirmed the successful grafting of the OSA moiety into TSP and the chain extension of the OTSPs. The hydrophobicity of the modified polysaccharide molecules increased, the absolute value of the zeta potential increased, and the thermal stability decreased, which were positively or negatively correlated with the changes in DS. In contrast, the hydrolysis of polysaccharides in alkaline aqueous solution led to a decrease in molar mass and the rigidity of the molecules, which were not significantly related to DS. Particle size analysis showed that OTSPs tended to aggregate into relatively small agglomerates, which was confirmed by the results of morphological analysis. Most importantly, the instability indices of emulsions stabilized by TSP, arabic gum and OSA-starch were 0.521, 0.715, and 0.804, respectively, while for OTSPs this parameter was between 0.04 and 0.19 under the same conditions, indicating better physical stability of the OTSP-stabilized emulsions, especially for OTSP-30. Overall, OTSP has great potential as an emulsifier for oil-in-water emulsions, especially for emulsification and stabilization in food processing.

Enhancing the equilibrium solubility of salicylic acid in aqueous media by using polyethylene glycols 200, 400 and 600 as cosolvents: Correlation and dissolution thermodynamics

The solubility of salicylic acid in three mixtures of polyethylene glycol (PEG) with different molar masses of 200 to 600 g/mole were experimentally determined by a shake flask method at temperature range of (293.15 to 313.15) K under ambient pressure (≈85 kPa). The experimental results indicated that the solubility of salicylic acid enhanced by the introduction of PEGs to the water, and that could be explained with Hansen’s parameters and like-dissolves-like rule. Based on the results, PEG 600 had the best solubilization power, whereas PEG 200 displayed the lowest solubilization power, and generally the solubility decreased with decreasing molar mass of PEG and also decreasing temperature. Moreover, the equilibrium solid phase crystal of salicylic acid is characterized with X-ray powder diffraction analysis to identify no polymorphic transformation, solvate formation or crystal transition during the whole solvent crystallization process. A number of linear and nonlinear cosolvency models including the Jouyban-Acree based models along with the equations of van’t Hoff, the mixture response surface, the combined nearly ideal binary solvent/Redlich-Kister, λh and the modified Wilson-van’t Hoff were challenged to correlate/predict the solubility of salicylic acid in these mixtures. The computed values of the Jouyban-Acree based models presented a good agreement with the experiment data than the others, as a consequent of a low mean percentage deviation (MPD ≤ 15.7%). According to the enthalpy–entropy compensation analysis, there observed slope changes indicating that two mechanisms, enthalpy or entropy controlled the solubility increment depending on the PEG mass fraction in each solution.

Optimized Lytic Polysaccharide Monooxygenase Action Increases Fiber Accessibility and Fibrillation by Releasing Tension Stress in Cellulose Cotton Fibers.

Lytic polysaccharide monooxygenase (LPMO) enzymes have recently shaken up our knowledge of the enzymatic degradation of biopolymers and cellulose in particular. This unique class of metalloenzymes cleaves cellulose and other recalcitrant polysaccharides using an oxidative mechanism. Despite their potential in biomass saccharification and cellulose fibrillation, the detailed mode of action of LPMOs at the surface of cellulose fibers still remains poorly understood and highly challenging to investigate. In this study, we first determined the optimal parameters (temperature, pH, enzyme concentration, and pulp consistency) of LPMO action on the cellulose fibers by analyzing the changes in molar mass distribution of solubilized fibers using high performance size exclusion chromatography (HPSEC). Using an experimental design approach with a fungal LPMO from the AA9 family (PaLPMO9H) and cotton fibers, we revealed a maximum decrease in molar mass at 26.6 °C and pH 5.5, with 1.6% w/w enzyme loading in dilute cellulose dispersions (100 mg of cellulose at 0.5% w/v). These optimal conditions were used to further investigate the effect of PaLPMO9H on the cellulosic fiber structure. Direct visualization of the fiber surface by scanning electron microscopy (SEM) revealed that PaLPMO9H created cracks on the cellulose surface while it attacked tension regions that triggered the rearrangement of cellulose chains. Solid-state NMR indicated that PaLPMO9H increased the lateral fibril dimension and created novel accessible surfaces. This study confirms the LPMO-driven disruption of cellulose fibers and extends our knowledge of the mechanism underlying such modifications. We hypothesize that the oxidative cleavage at the surface of the fibers releases the tension stress with loosening of the fiber structure and peeling of the surface, thereby increasing the accessibility and facilitating fibrillation.

Depolymerised lignin oil: A promising building block towards thermoplasticity in polyurethanes

The use of lignin as building block in the preparation of lignin-based thermoplastics has been a great challenge for the scientific community. Indeed, both the heterogeneous branched structure and the high hydroxyl functionality of lignin favours crosslinking reactions leading to the formation of thermosetting chemical structures. Some attempts have been made to circumvent these limitations, although the approaches required labour-intensive and time-consuming modifications of lignin and used only a relatively low amount in the materials. To tackle this problem, the present work employs lignin hydrogenolysis oil (LHO) which contains a low hydroxyl functionality oligomeric fraction suitable for the synthesis of thermoplastic polyurethanes (TPUs) via a two-step polymerization process. A series of TPUs were synthesized to investigate the impact of lignin content as well as soft segment molar mass on the chemical and thermo-mechanical properties of the materials. The study demonstrates that the use of high lignin content (38–46 wt. %) and high molar mass of the polyol (polypropylene glycol, PPG, Mn=4 kg mol−1) enhanced the mechanical properties of the obtained TPUs compared to counterpart polymers synthesized with lower molar mass of PPG. Additionally, LHO-based TPUs were applied as hot-melt adhesives for wood and their bonding strengths were evaluated by single lap shear tests. The lap shear adhesiveness was found to increase with increasing LHO concentration and decreasing molar mass of PPG. The developed methodology could lead to the preparation of robust thermoplastic lignin-based polyurethanes with a wide range of desired properties.

UV accelerated aging of unidirectional flax composites: Comparative study between recycled and virgin polypropylene matrix

Previous studies on the photooxidation of natural fiber composites have focused on using short fibers and virgin matrices. In this work, unidirectional flax fiber composites with virgin and recycled polypropylene matrix were prepared by thermocompression to compare their accelerated aging. These composites were exposed to two accelerated xenon arc UV exposures where only the irradiance was modified. A multi-scale characterization was carried out to evaluate the consequences of the photooxidation on their mechanical and physicochemical properties with time. Results show that the photooxidation was limited to the surface. In addition, the photo-degradation of the surfaces of both composites was identified by the appearance of cracks, the variation of crystallinity, the decrease in weight average molar mass, and the appearance of new chemical products. These physicochemical variations are more evident with increasing irradiance. Despite these variations, the mechanical tensile properties of recycled matrix composites remain relatively indifferent to the two UV exposures compared to those with virgin polypropylene. It can be concluded that recycled polypropylene, if well selected, can replace virgin polypropylene in natural fiber composites for better mechanical resistance to photooxidation.

Effect of chemical ageing on fatigue life of short glass fiber-reinforced Polyamide 6,6

In this study, the effect of hydrolysis and oxidation on fatigue life of Polyamide 6,6 reinforced with 30 wt% glass fibers has been studied systematically for the first time. The chemical changes due to these two chemical processes were monitored, especially the molar mass decrease over ageing time, homogeneous throughout the sample for hydrolysis and localized in a near-surface layer for oxidized samples. In both cases the fatigue life was significantly decreased with ageing. For homogeneously aged samples, the maximal applied stress at a given number of cycles to failure was correlated to the decrease of the molar mass of the matrix using a Flory-based model. This leads to the definition of a critical molar mass around 13 kg/mol which can be linked to the molar mass between entanglements, suggesting that fatigue is governed by fracture occurring in the glassy amorphous phase. To explain the decrease in fatigue life for oxidized heterogeneous samples, we proposed that a brittle layer, smaller than the oxidized layer itself, is considered as not sustaining any stress. The existence of this brittle layer was confirmed by fracture surface analysis and found in good agreement with the values extracted from the analytical model proposed.

Hydrolytic degradation of biodegradable poly(butylene adipate-co-terephthalate) (PBAT) - Towards an understanding of microplastics fragmentation

The long-term behaviour of PBAT subjected to hydrolytic ageing is investigated in this paper. Samples were aged in water at several temperatures ranging from 80 to 100 °C for different durations. Changes in physico-chemical properties were investigated through NMR, GPC, DSC and X-Ray analyses and embrittlement was assessed by tensile tests. It is demonstrated that hydrolysis of PBAT occurs first on the ester group located between the terephthalate and adipate groups leading to a decrease in molar mass. For longer ageing durations, the ester situated within the adipate group undergoes hydrolysis. An increase in crystallinity ratio and a decrease in amorphous layer thickness was observed as consequences of the chain scission process. Finally, a clear change in mechanical behaviour is noted; for the early stages of ageing, the polymer exhibits a ductile behaviour while for longer ageing durations, the polymer is brittle due to a lack of chain entanglement. This transition takes place once the molar mass of PBAT falls below 11 kg/mol, i.e. when a critical molar mass M’c is reached.

Durability of the optical plastic polycarbonate under modulated blue LED irradiation at different duty cycles

In order to provide longer LED lifetimes, all LED-related components, including lenses and other optical components, need to be adapted to increasing radiation levels. Pulse width modulation (PWM) is an easy-to-implement method for driving and dimming LEDs and could be a cost-effective way to extend the lifetime of optical components installed in conjunction with the LED. In this study, polycarbonate (PC) samples were artificially aged with high-power blue LEDs using different driving modes in a newly developed test setup. The LEDs were pulse-width modulated in three different modes (50% duty cycle, 25% duty cycle, and continuous wave (CW)), while emitting the same optical power. Optical light microscopy, UV/vis spectroscopy, FTIR spectroscopy and gel permeation chromatography were performed to measure transmittance changes and general aging effects of the samples. The results indicate a substantial correlation of aging with the mode of exposure. It is found that the samples age most severely under CW irradiation, as both the decrease in transmission (at 295 nm wavelength, after 1500 h) and the sample temperature, and thus the degradation, are highest. FTIR spectroscopy showed the expected results for optical aging under LED irradiation, again the changes tended to be more pronounced for the samples irradiated without PWM. Gel permeation chromatography shows a decrease in the weight averaged molar mass, once more with the CW irradiated samples exhibiting the most significant decrease. However, optical light microscopy did not reveal any significant aging effects on the sample surface. Overall, modulation of the LED, and in particular a reduction of the duty cycle, has a positive effect on the durability of optical plastics at similar radiative energy loads. In order to explain the different aging behavior of the samples under the different driving modes, a model of the time-related temperature changes in the material during the heating phase at different duty cycles is proposed.

Effects of Thermal Aging on Molar Mass of Ultra-High Molar Mass Polyethylene Fibers.

Ultra-high molar mass polyethylene (UHMMPE) is commonly used for ballistic-resistant body armor applications due to the superior strength of the fibers fabricated from this material combined with its low density. However, polymeric materials are susceptible to thermally induced degradation during storage and use, which can reduce the high strength of these fibers, and, thus, negatively impact their ballistic resistance. The objective of this work is to advance the field of lightweight and soft UHMMPE inserts used in various types of ballistic resistant-body armor via elucidating the mechanisms of chemical degradation and evaluating this chemical degradation, as well as the corresponding physical changes, of the UHMMPE fibers upon thermal aging. This is the first comprehensive study on thermally aged UHMMPE fibers that measures their decrease in the average molar mass via high-temperature size exclusion chromatography (HT-SEC) analysis. The decrease in the molar mass was further supported by the presence of carbon-centered free radicals in the polyethylene that was detected using electron paramagnetic resonance (EPR) spectroscopy. These carbon-centered radicals result from a cascade of thermo-oxidative reactions that ultimately induce C–C ruptures along the backbone of the polymer. Changes in the crystalline morphology of the UHMMPE fibers were also observed through wide-angle X-ray diffraction (WAXS), showing an increase in the amorphous regions, which promotes oxygen diffusion into the material, specifically through these areas. This increase in the amorphous fraction of the highly oriented polyethylene fibers has a synergistic effect with the thermo-oxidative degradation processes and contributes significantly to the decrease in their molar mass.

Photostability of polylactide with respect to blue LED radiation at very high irradiance and ambient temperature

For an overall sustainable development of lighting systems, it is crucial to establish alternatives to fossil based optical plastics. One biodegradable plastic alternative, based exclusively on renewable raw materials and having outstanding optical properties, could be the bioplastic polylactide (PLA). In order to evaluate the stability of PLA under the influence of extreme levels of optical LED radiation (λmax = 450 nm, FWHM = 16.3 nm), aging experiments were carried out over a period of 5000 h (~ 7 months) using an innovative self-developed test setup. As a reference the widely used optical plastic polycarbonate (PC) was aged under the same conditions. The novel test setup allowed aging tests at low temperatures of 23.0 and 36.1 °C (below the crystallization temperature of PLA) with irradiances of 7.9 and 16.1 kW/m2, respectively. Photodegradation tests in which temperature can be varied virtually independent of radiant flux were performed. To the best of our knowledge this is a first in degradation experiments. By this, aging can be attributed to more radiation- or temperature-related phenomena. Before, during, and after aging, optical, mechanical and chromatographic methods were used to analyze the samples. PLA was found to be largely resistant to visible blue LED radiation under the selected aging conditions. Only an increase in surface hardness and stiffness, indicating embrittlement, was observed. In contrast, even at the low temperatures used in these experiments, PC shows a significant decrease in transmission in the short-wavelength range of up to 17.0% after prolonged aging. Moreover, known degradation products (by FTIR spectroscopy), a decrease in molar mass (5.1%) and a trend increase in Martens hardness and indentation modulus, were detected for all PC of samples.

Polycaryophyllene as a Promising Plasticizer for Ethylene Propylene Diene Monomer Elastomers

This work focused on the synthesis of polycaryophyllene (Pcar) with controlled molar mass through ring-opening metathesis polymerization of caryophyllene in the presence of styrene as a nonpolar chain transfer agent (CTA). The CTA easily allowed for tuning the molar mass of resulting Pcar from a molar mass of 2 × 104 g mol–1 in the absence of CTA to molar masses ranging between 9 × 102 g mol–1 and 6.5 × 103 depending on the molar ratio of monomer to CTA. As expected, the molar mass decrease affected the glass transition temperature (Tg) of styrene end-capped Pcar varying from −36 °C to a range between −40 and −65 °C. The Pcar with a low molar mass (Pcar@Sty#02) emerges as a promising biobased plasticizer candidate for the ethylene propylene diene monomer elastomer (EPDM) because it decreases EPDM Tg from −46 to −54 °C. The vulcanized plasticized EPDM with Pcar@Sty#02 showed improved flexibility compared to the one plasticized with the petroleum-based plasticizer or nonplasticized EPDM.

Nonlinear rheometry of entangled polymeric rings and ring-linear blends

We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of shear rate as well as molecular parameters (molar mass, blend composition and decreasing molar mass of linear component in blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends. For the latter, the size of the undershoot and respective strain appear to increase with shear rate. Universal scaling of strain at overshoot and fractional overshoot (ratio of maximum to steady-state shear stress growth coefficient) indicates subtle differences in the shear-rate dependence between rings and linear polymers or their blends. The shear thinning behaviour of pure rings yields a slope nearly identical to predictions (-4/7) of a recent shear slit model and molecular dynamics simulations. Data for the second normal stress difference are reported for rings and ring-linear blends. While N 2 is negative and its absolute value stays below that of N 1 , as for linear polymers, the ratio -N 2 /N 1 is unambiguously larger for rings compared to linear polymer solutions with the same number of entanglements (almost by factor of two), in agreement with recent non-equilibrium molecular dynamics simulations. Further, -N 2 exhibits slightly weaker shear rate dependence compared to N 1 at high rates, and the respective power-law exponents can be rationalized in view of the slit model (3/7) and simulations (0.6), although further work is needed to unravel the molecular original of the observed behaviour. The comparison of shear and elongational stress growth coefficients for blends reflects the effect of ring-linear threading which leads to significant viscosity enhancement in elongation. Along the same lines, the elongational stress is much larger than the first normal stress in shear, and their ratio is much larger for rings and ring-linear blends compared to linear polymers. This conforms the interlocking scenario of rings and their important role in mechanically reinforcing linear matrices.

Green and controlled synthesis of short diol oligomers from polyhydroxyalkanoate to develop fully biobased thermoplastics

Polyhydroxyalkanoates (PHAs) are a biodegradable and biobased family of bacterial polyesters with different architectures. Among them, the poly-3-hydroxybutyrate (PHB) is one of the most conventional and easily obtained by biotechnologies from different bioresources. However, this thermoplastic polyester known since more than 50 years presents until now only very limited applications due to a certain number of drawbacks such as poor mechanical properties, high degree of crystallinity, and low thermal stability. One major way to valorize this bacterial polyester could be to develop controlled building blocks for the synthesis of new generation of biobased polymers. In this way, short linear PHB diols oligomers (oligoPHB-diol) with controlled low molar masses have been successfully obtained from a new synthetic pathway using reactive solvents in a green way. Different transesterification reaction parameters were investigated to control the PHB molar mass decrease, such as the catalyst and reactive solvent contents, the temperature and the reactive solvent type. Obtained oligomers were then analyzed in detail and further incorporated into fully biobased thermoplastics. In this work, thermoplastic polyurethanes (TPU) were elaborated as an example of second-generation biobased thermoplastics. To obtain TPUs with high biobased content, a dimer fatty acid-based diisocyanate, the dimeryl diisocyanate, and another biobased diol, the isosorbide, were used. Two series of TPUs were prepared with (i) varying the isosorbide/oligoPHB-diol ratio, and (ii) different oligoPHB-diol molar mass. Materials were fully evaluated for their structural, thermal and mechanical properties, as well as their crystalline behavior. A large range of properties were obtained for these innovative thermoplastics which could open a large range of applications with a green and sustainable approach.

Diffusivities in Binary Mixtures of n-Hexane or 1-Hexanol with Dissolved CH4, Ne, Kr, R143a, SF6, or R236fa Close to Infinite Dilution

This work is a continuation of previous studies focusing on the influence of intermolecular interactions on the diffusive mass transport in mixtures consisting of liquids with dissolved gases by determining the Fick diffusion coefficient of the mixtures or self-diffusion coefficient of the gas solutes. Dynamic light scattering, Raman spectroscopy, and molecular dynamics simulations are applied to study the interplay between the liquid structure and diffusive mass transport in binary mixtures consisting of methane, neon, krypton, sulfur hexafluoride, and the two refrigerants R143a and R236fa dissolved in n-hexane or 1-hexanol. Experiments and simulations were performed at the macroscopic thermodynamic equilibrium close to infinite dilution of the solute at temperatures between 303 and 423 K. The obtained Fick diffusion coefficients increase with increasing temperature and are always smaller in mixtures based on 1-hexanol compared to those of n-hexane. For both solvents, a decreasing molar mass of the solutes leads to increasing Fick diffusion coefficients with the exception of methane and neon showing the opposite behavior. Next to a general discussion and comparison with the literature, the present diffusivity data are compared with values predicted by a semiempirical model, which was previously developed to predict mass diffusivities in binary mixtures consisting of n-alkanes or 1-alcohols with dissolved gases close to infinite dilution.