Optical Monitoring of Water Side Permeation in Thin Film Encapsulation.

The stability of long-term microfabricated implants is hindered by the presence of multiple water diffusion paths within artificially patterned thin-film encapsulations. Side permeation, defined as infiltration of molecules through the lateral surface of the thin structure, becomes increasingly critical with the trend of developing high-density and miniaturized neural electrodes. However, current permeability measurement methods do not account for side permeation accurately nor quantitatively. Here, a novel optical, magnesium (Mg)-based method is proposed to quantify the side water transmission rate (SWTR) through thin film encapsulation and validate the approach using micrometric polyimide (PI) and polyimide-silicon carbide (PI-SiC) multilayers. Through computed digital grayscale images collected with corroding Mg film microcells coated with the thin encapsulation, side and surface WTRs are quantified. A 4.5-fold ratio between side and surface permeation is observed, highlighting the crucial role of the PI-PI interface in lateral diffusion. Universal guidelines for the design of flexible, hermetic neural interfaces are proposed. Increasing encapsulation's width (interelectrode spacing), creating stronger interfacial interactions, and integrating high-barrier interlayers such as SiC significantly enhance the lateral hermeticity.

Recycling of Bottle Grade PET: Influence of HDPE Contamination on the Microstructure and Mechanical Performance of 3D Printed Parts.

As part of a project that aims to provide people with disabilities with simple assistive devices in Colombia, the possibility of creating a PET filament that can be printed by Fused Deposition Modelling (FDM) from beverage bottle waste was investigated, with the aim to remain as simple as possible in terms of plastic collection, sorting, processing, and printing. Recycled PET filaments were thus produced by extrusion from collected PET bottles, with the potential addition of HDPE, which comes from caps and rings. The microstructure, mechanical performance, and printing quality of parts produced with these filaments were investigated in comparison to commercial PET virgin and recycled filaments. HDPE presence as an immiscible blend did not affect the ease of extrusion or the quality of the printing, which were all satisfactory. In some conditions, the addition of 5 wt% of HDPE to recycled PET had a toughening effect on otherwise brittle samples. This behavior was attributed to the presence of elongated HDPE inclusions resulting from shear forces induced by the layer-by-layer printing, provided that the interface temperature remained high between layer depositions. This confirms that the mechanical performance of recycled PET is very sensitive to the processing conditions, especially in the case of 3D printing. Nonetheless, this low-cost process that did not require sophisticated compatibilization schemes allowed for the printing of parts with mechanical properties comparable to those obtained with high purity, commercially recycled filaments, opening interesting perspectives for a low-cost PET recycling process.

Uniformly Dispersed Poly(lactic acid)-Grafted Lignin Nanoparticles Enhance Antioxidant Activity and UV-Barrier Properties of Poly(lactic acid) Packaging Films.

Poly(lactic acid) (PLA) represents one of the most widely used biodegradable polymers for food packaging applications. While this material provides many advantages, it is characterized by limited antioxidant and UV-barrier properties. Blending PLA with lignin is an attractive strategy to address these limitations. Lignin possesses antioxidant properties and absorbs UV-light and is a widely available low value byproduct of the paper and pulp industry. This study has explored the use of lignin nanoparticles to augment the properties of PLA-based films. A central challenge in the preparation of PLA-lignin nanoparticle blend films is to avoid nanoparticle aggregation, which could compromise optical properties as well as antioxidant activity, among others. To avoid nanoparticle aggregation in the PLA matrix, PLA-grafted lignin nanoparticles were prepared via organocatalyzed lactide ring-opening polymerization. In contrast to lignin and unmodified lignin nanoparticles, these PLA-grafted lignin nanoparticles could be uniformly dispersed in PLA for lignin contents up to 10 wt %. The addition of as little as the equivalent of 1 wt % of lignin of these nanoparticles effectively blocked transmission of 280 nm UV-light. At the same time, these blend films retained reasonable visible light transmittance. The optical properties of the PLA lignin blend films also benefited from the well-dispersed nature of the PLA-grafted nanoparticles, as evidenced by significantly higher visible light transmittance of blends of PLA and PLA-grafted nanoparticles, as compared to blends prepared from PLA with lignin or unmodified lignin nanoparticles. Finally, blending PLA with PLA-grafted lignin nanoparticles greatly augments the antioxidant activity of these films.

Sustainable polyesters via direct functionalization of lignocellulosic sugars.

The development of sustainable plastics from abundant renewable feedstocks has been limited by the complexity and efficiency of their production, as well as their lack of competitive material properties. Here we demonstrate the direct transformation of the hemicellulosic fraction of non-edible biomass into a tricyclic diester plastic precursor at 83% yield (95% from commercial xylose) during integrated plant fractionation with glyoxylic acid. Melt polycondensation of the resulting diester with a range of aliphatic diols led to amorphous polyesters (Mn = 30-60 kDa) with high glass transition temperatures (72-100 °C), tough mechanical properties (ultimate tensile strengths of 63-77 MPa, tensile moduli of 2,000-2,500 MPa and elongations at break of 50-80%) and strong gas barriers (oxygen transmission rates (100 µm) of 11-24 cc m-2 day-1 bar-1 and water vapour transmission rates (100 µm) of 25-36 g m-2 day-1) that could be processed by injection moulding, thermoforming, twin-screw extrusion and three-dimensional printing. Although standardized biodegradation studies still need to be performed, the inherently degradable nature of these materials facilitated their chemical recycling via methanolysis at 64 °C, and eventual depolymerization in room-temperature water.

Photoresponsive Movement in 3D Printed Cellulose Nanocomposites.

Photoresponsive soft liquid crystalline elastomers (LCEs) transform light's energy into dynamic shape changes and are considered promising candidates for production of soft robotic or muscle-like devices. 3D printing allows access to elaborated geometries as well as control of the photoactuated movements; however, this development is still in its infancy and only a limited choice of LCE is yet available. Herein, we propose to introduce biocompatible and sustainable cellulose nanocrystals (CNC) into an LCE in order to facilitate the printing process by direct ink writing (DIW) and to benefit from the anisotropic mechanical properties resulting from the extrusion-induced alignment of such nanoparticles. After a first printing step where the rheological influence of CNC allows the production of self-standing structures, a doping process introduces the azobenzene photoswitches in the composite, conferring photomechanical behaviors to the printed material. This approach results in soft composites, with an elastic modulus around 20-30 MPa, that present fully reversible photosoftening of 35% and photomechanical actuation occurring less than 3 s after illumination. The presence of CNC as reinforcement particles allows precise tailoring of mechanical properties, rendering such phototriggered materials suitable candidates for the production of actuators and 3D structures with particular and dynamic load cases.

Recent Advances in Encapsulation of Flexible Bioelectronic Implants: Materials, Technologies, and Characterization Methods.

Bioelectronic implantable systems (BIS) targeting biomedical and clinical research should combine long-term performance and biointegration in vivo. Here, recent advances in novel encapsulations to protect flexible versions of such systems from the surrounding biological environment are reviewed, focusing on material strategies and synthesis techniques. Considerable effort is put on thin-film encapsulation (TFE), and specifically organic-inorganic multilayer architectures as a flexible and conformal alternative to conventional rigid cans. TFE is in direct contact with the biological medium and thus must exhibit not only biocompatibility, inertness, and hermeticity but also mechanical robustness, conformability, and compatibility with the manufacturing of microfabricated devices. Quantitative characterization methods of the barrier and mechanical performance of the TFE are reviewed with a particular emphasis on water-vapor transmission rate through electrical, optical, or electrochemical principles. The integrability and functionalization of TFE into functional bioelectronic interfaces are also discussed. TFE represents a must-have component for the next-generation bioelectronic implants with diagnostic or therapeutic functions in human healthcare and precision medicine.

Extended Barrier Lifetime of Partially Cracked Organic/Inorganic Multilayers for Compliant Implantable Electronics.

Flexible and soft bioelectronics display conflicting demands on miniaturization, compliance, and reliability. Here, the authors investigate the design and performance of thin encapsulation multilayers against hermeticity and mechanical integrity. Partially cracked organic/inorganic multilayer coatings are demonstrated to display surprisingly year-long hermetic lifetime under demanding mechanical and environmental loading. The thin hermetic encapsulation is grown in a single process chamber as a continuous multilayer with dyads of atomic layer deposited (ALD) Al2 O3 -TiO2 and chemical vapor deposited Parylene C films with strong interlayer adhesion. Upon tensile loading, tortuous diffusion pathways defined along channel cracks in the ALD oxide films and through tough Parylene films efficiently postpone the hermeticity failure of the partially cracked coating. The authors assessed the coating performance against prolonged exposure to biomimetic physiological conditions using coated magnesium films, platinum interdigitated electrodes, and optoelectronic devices prepared on stretchable substrates. Designed extension of the lifetime preventing direct failures reduces from over 5 years yet tolerates the lifetime of 3 years even with the presence of critical damage, while others will directly fail less than two months at 37 °C. This strategy should accelerate progress on thin hermetic packaging for miniaturized and compliant implantable electronics.

Valorization of Byproducts of Hemp Multipurpose Crop: Short Non-Aligned Bast Fibers as a Source of Nanocellulose.

Nanocellulose was extracted from short bast fibers, from hemp (Cannabis sativa L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers. No bleaching was performed. The chemically pretreated fibers were then refined in a beater and treated with a cellulase enzyme, followed by mechanical defibrillation in an ultrafine friction grinder. The fibers were characterized by microscopy, infrared spectroscopy, thermogravimetric analysis and X-ray diffraction after each step of the process to understand the evolution of their morphology and composition. The obtained nanocellulose suspension was composed of short nanofibrils with widths of 5-12 nm, stacks of nanofibrils with widths of 20-200 nm, and some larger fibers. The crystallinity index was found to increase from 74% for the raw fibers to 80% for the nanocellulose. The nanocellulose retained a yellowish color, indicating the presence of some residual lignin. The properties of the nanopaper prepared with the hemp nanocellulose were similar to those of nanopapers prepared with wood pulp-derived rod-like nanofibrils.

Interface-Dominated Time-Dependent Behavior of Poled Poly(Vinylidene Fluoride-Trifluoroethylene)/Barium Titanate Composites.

Composites in which particles of ferroelectric ceramic phase are randomly dispersed in a polymeric matrix are of interest because of flexibility, conformability, and ease of processing. However, their piezoelectric properties are rather low, unless very high volume fractions of ceramics are used. This brings agglomeration and porosity issues due to the large mismatch between the surface energies of the ceramics and of the polymer. Particle surface modification is a common approach for better dispersion; however, it may bring other effects on the properties of the composites, which are usually concealed by the huge improvement in performance due to the more homogenous microstructure. In this work, we compared poly(vinylidene fluoride-trifluoroethylene)/barium titanate composites containing 15 vol.% and 60 vol.% of pristine ceramic particles or particles modified with an aminosilane or a fluorosilane. Similar morphology, with good particle dispersion and low porosity, was achieved for all composites, owing to an efficient dispersion method. The materials were poled with two different poling procedures, and the piezoelectric coefficient d33, the relative permittivity, and the poling degree of barium titanate were followed in time. We highlighted that, although similar d33 were obtained with all types of particles, the nature of the particles surface and the poling procedure were associated with different charge trapping and influenced the evolution of d33 with time.

Nitrogen-doped graphene stabilized copper nanoparticles for Huisgen [3+2] cycloaddition "click" chemistry.

Nitrogen-doped reduced graphene oxide (NRGO) stabilized copper nanoparticles are designed to assist Cu(i)-catalyzed Huisgen [3+2] cycloaddition "click" chemistry (CuAAC). This study demonstrates a robust route for the synthesis of vastly dispersed heterogeneous catalysts (NRGO/Cu2O), achieving CuAAC at low temperature without any external additive (oxidizing/reducing agent) with high stability and recyclability. Underlying mechanisms are analysed using DFT calculations, confirming the experimental results.

Organic-Inorganic Hybrid Planarization and Water Vapor Barrier Coatings on Cellulose Nanofibrils Substrates.

Cellulose nanofibrils (CNF) can be produced in the form of thin, transparent and flexible films. However, the permeability of such materials to oxygen and water vapor is very sensitive to moisture, which limits their potential for a variety of packaging and encapsulation applications. Diffusion barrier coatings were thus developed to reduce the access of water molecules to enzymatically pre-treated and carboxymethylated CNF substrates. The coatings were based on UV curable organic-inorganic hybrids with epoxy, tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethylenesilane (GPTS) precursors and additional vapor formed SiNx layers. A total of 14 monolayer and multilayer coatings with various thickness and hybrid composition were produced and analyzed. The water vapor transmission rate (WVTR) of the bilayer epoxy/CNF film was two times lower compared to that of uncoated CNF film. This was partly due to the water vapor permeability of the epoxy, a factor of two times lower than CNF. The epoxy coating improved the transparency of CNF, however it did not properly wet to the CNF surfaces and the interfacial adhesion was low. In contrast hybrid epoxy-silica coatings led to high adhesion levels owing to the formation of covalent interactions through condensation reactions with the OH-terminated CNF surface. The barrier and optical performance of hybrid coated CNF substrates was similar to that of CNF coated with pure epoxy. In addition, the hybrid coatings provided an excellent planarization effect, with roughness close to 1 nm, one to two orders of magnitude lower than that of the CNF substrates. The WVTR and oxygen transmission rate values of the hybrid coated CNF laminates were in the range 5-10 g/m2/day (at 38°C and 50% RH) and 3-6 cm3/m2/day/bar (at 23°C and 70% RH), respectively, which matches food and pharmaceutical packaging requirements. The permeability to water vapor of the hybrid coatings was moreover found to decrease with increasing the TEOS/GPTS ratio up to 30 wt% and then increase at higher ratio, and to be much lower for thinner coatings due to further UV-induced silanol condensation and faster evaporation of byproducts. The addition of a single 150 nm thick SiNx layer on the hybrid coated CNF improved its water vapor barrier performance by more than 680 times, with WVTR below the 0.02 g/m2/day detection limit.

A Facile in Situ and UV Printing Process for Bioinspired Self-Cleaning Surfaces.

A facile in situ and UV printing process was demonstrated to create self-cleaning synthetic replica of natural petals and leaves. The process relied on the spontaneous migration of a fluorinated acrylate surfactant (PFUA) within a low-shrinkage acrylated hyperbranched polymer (HBP) and its chemical immobilization at the polymer-air interface. Dilute concentrations of 1 wt. % PFUA saturated the polymer-air interface within 30 min, leading to a ten-fold increase of fluorine concentration at the surface compared with the initial bulk concentration and a water contact angle (WCA) of 108°. A 200 ms flash of UV light was used to chemically crosslink the PFUA at the HBP surface prior to UV printing with a polydimethylsiloxane (PDMS) negative template of red and yellow rose petals and lotus leaves. This flash immobilization hindered the reverse migration of PFUA within the bulk HBP upon contacting the PDMS template, and enabled to produce texturized surfaces with WCA well above 108°. The synthetic red rose petal was hydrophobic (WCA of 125°) and exhibited the adhesive petal effect. It was not superhydrophobic due to insufficient concentration of fluorine at its surface, a result of the very large increase of the surface of the printed texture. The synthetic yellow rose petal was quasi-superhydrophobic (WCA of 143°, roll-off angle of 10°) and its self-cleaning ability was not good also due to lack of fluorine. The synthetic lotus leaf did not accurately replicate the intricate nanotubular crystal structures of the plant. In spite of this, the fluorine concentration at the surface was high enough and the leaf was superhydrophobic (WCA of 151°, roll-off angle below 5°) and also featured self-cleaning properties.

Lab-on-a-chip for multiplexed biosensing of residual antibiotics in milk.

A multiplexed immunoassay-based antibiotic sensing device integrated in a lab-on-a-chip format is described. The approach is multidisciplinary and involves the convergent development of a multi-antibiotic competitive immunoassay based on sensitive wavelength interrogated optical sensor (WIOS) technology and a polymer-based self-contained microfluidic cartridge. Immunoassay solutions are pressure-driven through external and concerted actuation of a single syringe pump and multiposition valve. Moreover, the use of a novel photosensitive material in a 'one step' fabrication process allowed the rapid fabrication of microfluidic components and interconnection port simultaneously. Pre-filled microfluidic cartridges were used as binary response rapid tests for the simultaneous detection of three antibiotic families - sulfonamides, fluoroquinolones and tetracyclines - in raw milk. For test interpretation, any signal lower than the threshold value obtained for the corresponding Maximum Residue Limit (MRL) concentration (100 microg L(-1)) was considered negative for a given antibiotic. The reliability of the multiplexed detection system was assessed by way of a validation test carried out on a series of six blind milk samples. A test accuracy of 95% was calculated from this experiment. The whole immunoassay procedure is fast (less than 10 minutes) and easy to handle (automated actuation).