Thermomechanical Properties of Virgin and Recycled Polypropylene-High-Density Polyethylene Blends.

This paper provides evidence and discusses the variability in the thermomechanical behaviour of virgin and recycled polypropylene/high-density polyethylene blends without the addition of other components, which is sparse in the literature. Understanding the performance variability in recycled polymer blends is of critical importance in order to facilitate the re-entering of recycled materials to the consumer market and, thus, contribute towards a circular economy. This is an area that requires further research due to the inhomogeneity of recycled materials. Therefore, the thermal and mechanical properties of virgin and recycled polypropylene/high-density polyethylene blends were investigated systematically. Differential scanning calorimetry concludes that both the recycled and virgin blends are immiscible. Generally, recycled blends have lower overall crystallinity and melting temperatures compared with virgin blends while, remarkably, their crystallisation temperatures are compared favourably. Dynamical mechanical analysis showed little variation in the storage modulus of recycled and virgin blends. However, the alpha and beta relaxation temperatures are lower in recycled blends due to structural deterioration. Deterioration in the thermal and mechanical properties of recycled blends is thought to be caused by the presence of contaminants and structural degradation during reprocessing, resulting in shorter polymeric chains and the formation of imperfect crystallites. The tensile properties of recycled blends are also affected by the recycling process. The Young's modulus and yield strength of the recycled blends are inferior to those of virgin blends due to the deterioration during the recycling process. However, the elongation at break of the recycled blends is higher compared with the virgin blends, possibly due to the plasticity effect of the low-molecular-weight chain fragments.

Atomic Force Microscopy of Phytosterol Based Edible Oleogels.

This work reviews the use of atomic force microscopy (AFM) as a tool to investigate oleogels of edible triglyceride oils. Specific attention is given to those oleogels based on phytosterols and their esters, a class of material the authors have studied extensively. This work consists of a summary of the role of AFM in imaging edible oleogels, including the processing and preparation steps required to obtain high-quality AFM images of them. Finally, there is a comparison between AFM and other techniques that may be used to obtain structural information from oleogel samples. The aim of this review is to provide a useful introduction and summary of the technique for researchers in the fields of gels and food sciences looking to perform AFM measurements on edible oleogels.

A vertical additive-lathe printing system for the fabrication of tubular constructs using gelatin methacryloyl hydrogel.

Reproducing both the mechanical and biological performance of native blood vessels remains an ongoing challenge in vascular tissue engineering. Additive-lathe printing offers an attractive method of fabricating long tubular constructs as a potential vascular graft for the treatment of cardiovascular diseases. Printing hydrogels onto rotating horizontal mandrels often leads to sagging, resulting in poor and variable mechanical properties. In this study, an additive-lathe printing system with a vertical mandrel to fabricate tubular constructs is presented. Various concentrations of gelatin methacryloyl (gelMA) hydrogel were used to print grafts on the rotating mandrel in a helical pattern. The printing parameters were selected to achieve the bonding of consecutive gelMA filaments to improve the quality of the printed graft. The hydrogel filaments were fused properly under the action of gravity on the vertical mandrel. Thus, the vertical additive-lathe printing system was used to print uniform wall thickness grafts, eliminating the hydrogel sagging problem. Tensile testing performed in both circumferential and longitudinal direction revealed that the anisotropic properties of printed gelMA constructs were similar to those observed in the native blood vessels. In addition, no leakage was detected through the walls of the gelMA grafts during burst pressure measurement. Therefore, the current printing setup could be utilized to print vascular grafts for the treatment of cardiovascular diseases.

Semicrystalline Polymer Micro/Nanostructures Formed by Droplet Evaporation of Aqueous Poly(ethylene oxide) Solutions: Effect of Solution Concentration.

Deposits formed after evaporation of sessile droplets, containing aqueous solutions of poly(ethylene oxide), on hydrophilic glass substrates were studied experimentally and mathematically as a function of the initial solution concentration. The macrostructure and micro/nanostructures of deposits were studied using stereo microscopy and atomic force microscopy. A model, based on thin-film lubrication theory, was developed to evaluate the deposit macrostructure by estimating the droplet final height. Moreover, the model was extended to evaluate the micro/nanostructure of deposits by estimating the rate of supersaturation development in connection with the driving force of crystallization. Previous studies had only described the macrostructure of poly(ethylene oxide) deposits formed after droplet evaporation, whereas the focus of our study was the deposit micro/nanostructures. Our atomic force microscopy study showed that regions close to the deposit periphery were composed of predominantly semicrystalline micro/nanostructures in the form of out-of-plane lamellae, which require a high driving force of crystallization. However, deposit central areas presented semicrystalline micro/nanostructures in the form of in-plane terraces and spirals, which require a lower driving force of crystallization. Increasing the initial concentration of solutions led to an increase in the lengths and thicknesses of the out-of-plane lamellae at the deposits' periphery and enhanced the tendency to form spirals in the central areas. Our numerical study suggested that the rate of supersaturation development and thus the driving force of crystallization increased from the center toward the periphery of droplets, and the supersaturation rate was lower for solutions with higher initial concentrations at each radius. Therefore, periphery areas of droplets with lower initial concentrations were suitable for the formation of micro/nanostructures which require higher driving forces, whereas central areas of droplets with higher initial concentration were desirable for the formation of micro/nanostructures which require lower driving forces. These numerical results were in good qualitative agreement with the experimental findings.

Exploring how changes to the steroidal core alter oleogelation capability in sterol: γ-oryzanol blends.

Oleogels based on sterols such as ß-sitosterol blended with the sterol ester γ-oryzanol are a very interesting class of systems, but there are aspects of their formation and structure that remain elusive. It has previously been shown that a methyl group on the C30 position of the sterol-ester plays an important role in gelation. This work explored the effect that having C30 methyl groups on both the sterol and the sterol-ester had on the gelation process and subsequent gel structure. Lanosterol and saponified γ-oryzanol (which was synthesized as part of this study) were identified as materials of interest, as both feature a methyl group on the C30 position of their steroidal cores. It was observed that both sterols formed gels when blended with γ-oryzanol, and also that lanosterol gelled sunflower oil without the addition of γ-oryzanol. All of these gels were significantly weaker than that formed by ß-sitosterol blended with γ-oryzanol. To explore why, molecular docking simulations along with AFM and SAXS were used to examine these gels on a broad range of length scales. The results suggest that saponified γ-oryzanol-γ-oryzanol gels have a very similar structure to that of ß-sitosterol-γ-oryzanol gels. Lanosterol-γ-oryzanol gels and pure lanosterol gel, however, form with a totally different structure facilitated by the head-to-tail stacking motif exhibited by lanosterol. These results give further evidence that relatively slight changes to the molecular structure of gelators can result in significant differences in subsequent gel properties.

Fabrication of a Wearable Flexible Sweat pH Sensor Based on SERS-Active Au/TPU Electrospun Nanofibers.

Development of wearable sensing platforms is essential for the advancement of continuous health monitoring and point-of-care testing. Eccrine sweat pH is an analyte that can be noninvasively measured and used to diagnose and aid in monitoring a wide range of physiological conditions. Surface-enhanced Raman scattering (SERS) offers a rapid, optical technique for fingerprinting of biomarkers present in sweat. In this paper, a mechanically flexible, nanofibrous, SERS-active substrate was fabricated by a combination of electrospinning of thermoplastic polyurethane (TPU) and Au sputter coating. This substrate was then investigated for suitability toward wearable sweat pH sensing after functionalization with two commonly used pH-responsive molecules, 4-mercaptobenzoic acid (4-MBA), and 4-mercaptopyridine (4-MPy). The developed SERS pH sensor was found to have good resolution (0.14 pH units for 4-MBA; 0.51 pH units for 4-MPy), with only 1 µL of sweat required for a measurement, and displayed no statistically significant difference in performance after 35 days (p = 0.361). Additionally, the Au/TPU nanofibrous SERS pH sensors showed fast sweat-absorbing ability as well as good repeatability and reversibility. The proposed methodology offers a facile route for the fabrication of SERS substrates which could also be used to measure a wide range of health biomarkers beyond sweat pH.

One Surface Treatment, Multiple Possibilities: Broadening the Use-Potential of Para-Aramid Fibers with Mechanical Adhesion.

Aramid fibers are high-strength and high-modulus technical fibers used in protective clothing, such as bulletproof vests and helmets, as well as in industrial applications, such as tires and brake pads. However, their full potential is not currently utilized due to adhesion problems to matrix materials. In this paper, we study how the introduction of mechanical adhesion between aramid fibers and matrix material the affects adhesion properties of the fiber in both thermoplastic and thermoset matrix. A microwave-induced surface modification method is used to create nanostructures to the fiber surface and a high throughput microbond method is used to determine changes in interfacial shear strength with an epoxy (EP) and a polypropylene (PP) matrix. Additionally, Fourier transform infrared spectroscopy, atomic force microscopy, and scanning electron microscopy were used to evaluate the surface morphology of the fibers and differences in failure mechanism at the fiber-matrix interface. We were able to increase interfacial shear strength (IFSS) by 82 and 358%, in EP and PP matrix, respectively, due to increased surface roughness and mechanical adhesion. Also, aging studies were conducted to confirm that no changes in the adhesion properties would occur over time.

PDMS-ZnO Piezoelectric Nanocomposites for Pressure Sensors.

The addition of piezoelectric zinc oxide (ZnO) fillers into a flexible polymer matrix has emerged as potential piezocomposite materials that can be used for applications such as energy harvesters and pressure sensors. A simple approach for the fabrication of PDMS-ZnO piezoelectric nanocomposites based on two ZnO fillers: nanoparticles (NP) and nanoflowers (NF) is presented in this paper. The effect of the ZnO fillers' geometry and size on the thermal, mechanical and piezoelectric properties is discussed. The sensors were fabricated in a sandwich-like structure using aluminium (Al) thin films as top and bottom electrodes. Piezocomposites at a concentration of 10% w/w showed good flexibility, generating a piezoelectric response under compression force. The NF piezocomposites showed the highest piezoelectric response compared to the NP piezocomposites due to their geometric connectivity. The piezoelectric compound NF generated 4.2 V while the NP generated 1.86 V under around 36 kPa pressure. The data also show that the generated voltage increases with increasing applied force regardless of the type of filler.

Dispersive and filter loss performance of calcium carbonate nanoparticles in water for drilling fluid applications.

Adding nanoparticles in a drilling fluid can aid in the sealing of the nanopores in the borehole wall rock and the mud cake; in this way, the filtrate loss of the drilling fluid can be reduced and the borehole wall is stabilized. In this work, the spectrophotometric method was used to study the effect of dispersants on calcium carbonate nanoparticles. The best dispersion effect was achieved at cetyltrimethyl ammonium bromide (CTAB) concentration of 4 wt%, dispersing time of 45 min, pH value of 8 and stirring speed of 900 rpm. The structure analysis showed that the adsorption layer was formed on the surface of calcium carbonate nanoparticles after CTAB modification, and no new crystalline compounds appeared. Under these optimized dispersing conditions, aggregation was prevented as manifested by the dramatically decreased average particle size of calcium carbonate nanoparticles while the surface hydrophilicity and Zeta potential of calcium carbonate nanoparticles both increased. Furthermore, we showed that a drilling fluid incorporating such well dispersed calcium carbonate nanoparticles exhibit decreased filter loss and thus better performance in sealing compared to the calcium carbonate nanoparticles without dispersants.

A modified 3D printer as a hybrid bioprinting-electrospinning system for use in vascular tissue engineering applications.

There is a high demand for small diameter vascular grafts having mechanical and biological properties similar to that of living tissues. Tissue-engineered vascular grafts using current methods have often failed due to the mismatch of mechanical properties between the implanted graft and living tissues. To address this limitation, a hybrid bioprinting-electrospinning system is developed for vascular tissue engineering applications. The setup is capable of producing layered structure from electrospun fibres and cell-laden hydrogel. A Creality3D Ender 3D printer has been modified into a hybrid setup having one bioprinting head and two electrospinning heads. Fortus 250mc and Flashforge Creator Pro 3D printers were used to print parts using acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA) polymers. An Arduino mega 2560 and a Ramps 1.4 controller board were selected to control the functions of the hybrid bioprinting setup. The setup was tested successfully to print a tubular construct around a rotating needle.

Design and development of a nozzle-free electrospinning device for the high-throughput production of biomaterial nanofibers.

This technical note provides a step-by-step guide for the design and construction of a temperature-controlled nozzle-free electrospinning device. The equipment uses a rotating mandrel partially immersed within a polymer solution to produce fibers in an upward motion by inducing the formation of multiple Taylor cones and subsequently multi-jetting out of an electrified open surface. Free-surface electrospinning can overcome limitations and drawbacks associated with single and multi-nozzle spinneret configurations, such as low yield, limited production capacity, nonuniform electric field distribution, and clogging. Most importantly, this lab-scaled high-throughput device can provide an alternative economical route for needleless electrospinning research, in contrast to the high costs associated with industrially available upscaling equipment. Among the device's technical specifications, a key feature is a cryo-collector mandrel, capable of collecting fibers in sub-zero temperatures, which can induce ultra-porous nanostructures, wider pores, and subsequent in-depth penetration of cells. A multi-channel gas chamber allows the conditioning of the atmosphere, temperature, and airflow, while the chamber's design averts user exposure to the high-voltage components. All the Computer-Aided Design (CAD) files and point-by-point assembly instructions, along with a list of the materials used, are provided.

Recent advancements in the bioprinting of vascular grafts.

Recent advancements in the bioinks and three-dimensional (3D) bioprinting methods used to fabricate vascular constructs are summarized herein. Critical biomechanical properties required to fabricate an ideal vascular graft are highlighted, as well as various testing methods have been outlined to evaluate the bio-fabricated grafts as per the Food and Drug Administration (FDA) and International Organization for Standardization (ISO) guidelines. Occlusive artery disease and cardiovascular disease are the major causes of death globally. These diseases are caused by the blockage in the arteries, which results in a decreased blood flow to the tissues of major organs in the body, such as the heart. Bypass surgery is often performed using a vascular graft to re-route the blood flow. Autologous grafts represent a gold standard for such bypass surgeries; however, these grafts may be unavailable due to the previous harvesting or possess a poor quality. Synthetic grafts serve well for medium to large-sized vessels, but they fail when used to replace small-diameter vessels, generally smaller than 6 mm. Various tissue engineering approaches have been used to address the urgent need for vascular graft that can withstand hemodynamic blood pressure and has the ability to grow and remodel. Among these approaches, 3D bioprinting offers an attractive solution to construct patient-specific vessel grafts with layered biomimetic structures.

In Vitro Drug Release, Permeability, and Structural Test of Ciprofloxacin-Loaded Nanofibers.

Nanofibers of the poorly water-soluble antibiotic ciprofloxacin (CIP) were fabricated in the form of an amorphous solid dispersion by using poly(vinyl pyrrolidone) as a polymer matrix, by the low-cost electrospinning method. The solubility of the nanofibers as well as their in vitro diffusion were remarkably higher than those of the CIP powder or the physical mixture of the two components. The fiber size and morphology were optimized, and it was found that the addition of the CIP to the electrospinning solution decreased the nanofiber diameter, leading to an increased specific surface area. Structural characterization confirmed the interactions between the drug and the polymer and the amorphous state of CIP inside the nanofibers. Since the solubility of CIP is pH-dependent, the in vitro solubility and dissolution studies were executed at different pH levels. The nanofiber sample with the finest morphology demonstrated a significant increase in solubility both in water and pH 7.4 buffer. Single medium and two-stage biorelevant dissolution studies were performed, and the release mechanism was described by mathematical models. Besides, in vitro diffusion from pH 6.8 to pH 7.4 notably increased when compared with the pure drug and physical mixture. Ciprofloxacin-loaded poly(vinyl pyrrolidone) (PVP) nanofibers can be considered as fast-dissolving formulations with improved physicochemical properties.

High-throughput production of silk fibroin-based electrospun fibers as biomaterial for skin tissue engineering applications.

In this work, a nozzle-free electrospinning device was built to obtain high-throughput production of silk fibroin-based biocompatible composite fibers with tunable wettability. Synthetic biomaterials tend to present suboptimal cell growth and proliferation, with many studies linking this phenomenon to the hydrophobicity of such surfaces. In this study, electrospun mats consisting of Poly(caprolactone) blended with variant forms of Poly(glycerol sebacate) (PGS) and regenerated silk fibroin were fabricated. The main aim of this work was the development of fiber mats with tunable hydrophobicity/hydrophilicity properties depending on the esterification degree and concentration of PGS. A variation of the conventional protocol used for the extraction of silk fibroin from Bombyx mori cocoons was employed, achieving significantly increased yields of the protein, in a third of the time required via the conventional extraction protocol. By altering the surface properties of the electrospun membranes, the trinary composite biomaterial presented good in vitro fibroblast attachment behavior and optimal growth, indicating the potential of such constructs towards the development of an artificial skin-like platform that can aid wound healing and skin regeneration.

Low-cost FDM 3D-printed modular electrospray/electrospinning setup for biomedical applications.

Here, we report on the inexpensive fabrication of an electrospray/electrospinning setup by fused deposition modelling (FDM) 3D printing and provide the files and parameters needed to print this versatile device. Both electrospray and electrospinning technologies are widely used for pharmaceutical, healthcare and bioengineering applications. The setup was designed to be modular, thus its parts can be exchanged easily. The design provides a safe setup, ensuring that the users are not exposed to the high voltage parts of the setup. PLA, PVA, and a thermoplastic elastomer filament were used for the 3D printing. The filament cost was $100 USD and the rig was printed in 6 days. An Ultimaker 3 FDM 3D printer was used with dual print heads, and the PVA was used as a water-soluble support structure. The end part of the setup had several gas channels, allowing a uniform gas flowing against the direction of the nanoparticles/nanofibers, enhancing the drying process by enhancing the evaporation rate. The setup was tested in both electrospray and electrospinning modes successfully. Both the .sldprt and .stl files are provided for free download.

Thin Polymer Film Force Spectroscopy: Single Chain Pull-out and Desorption.

Atomic force microscopy (AFM) was utilized to investigate the force associated with chain pull-out and single chain desorption of poly(styrene-co-butadiene) random copolymer thin films on mica, silicon, and graphite substrates. Chain pull-out events were common and produced a force of 20-25 pN. The polymer desorption force was strongest on the graphite substrate and weakest on the mica, which agreed with the calculated work of adhesion for each system and the substrate hydrophobicity. Furthermore, it was demonstrated that there was a systematic order to when each of these phenomena occurred during the tip retraction from the surface, which provided information about the structure of the thin films.

On the Effect of Substrate Viscoelasticity on the Evaporation Kinetics and Deposition Patterns of Nanosuspension Drops.

This study investigates the evaporation of sessile pure water and nanosuspension drops on viscoelastic polydimethylsiloxane (PDMS) films. We varied the viscoelasticity of the PDMS films by controlling the curing ratio and categorized them into three types: stiff (10:1, 20:1, 40:1), soft (60:1, 80:1), and very soft (100:1, 120:1, 140:1, 160:1). On stiff surfaces, pure water drops initially evaporate in a constant contact radius (CCR) mode, followed by a constant contact angle mode, and finally in a mixed mode of evaporation. Nanosuspension drops follow the same trend as water drops but with a difference toward the end of their lifetimes, when a short second CCR mode is observed. Complete evaporation of nanosuspension drops on stiff substrates leads to particle deposition patterns similar to a coffee ring with cracks and deposition tails. On soft surfaces, the initial spreading is followed by a pseudo-CCR mode. Complete evaporation of nanosuspension drops on soft substrates leads to deposits in the form of a uniform ring with a sharp ox-horn profile. Unexpectedly, the initial spreading is followed by a mixed mode on very soft substrates, on which wetting ridges (WRs) pulled up by the vertical component of surface tension are clearly observed in the vicinity of the contact line (CL). As the evaporation proceeds, the decreasing contact angle breaks the force balance in the horizontal direction at the CL and gives rise to a net horizontal force, which causes the CL to recede, transferring the horizontal force to the WR. Because of the viscoelastic nature of the very soft substrate, this horizontal force acting on the WR cannot be completely countered by the bulk of the substrate underneath. As a result, the WR moves horizontally in a viscous-flow way, which also enables the CL to be continuously anchored to the ridge and to recede relative to the bulk of the substrate. Consequently, a mixed mode of evaporation occurs. Complete evaporation of nanosuspension drops on very soft substrates leads to finger-like deposits.

Probing phospholipid microbubbles by atomic force microscopy to quantify bubble mechanics and nanostructural shell properties.

Microbubbles (MBs), which are used as ultrasonic contrast agents, have distinct acoustic signatures which enable them to significantly enhance visualisation of the vasculature. Research is progressing to develop MBs which act as drug/gene delivery vehicles for site-specific therapeutics. In order to manufacture effective theranostic vehicles, it is imperative to understand the mechanical and nanostructural properties of these agents; this will enrich the understanding of how the structural, biophysical and chemical properties of these bubbles impact their functionality. We produced microfluidic phospholipid-based MBs due to their favourable properties, such as biocompatibility and echogenicity, as well as the ability to modify the shell for targeting applications. We have drawn upon atomic force microscopy to conduct force spectroscopy and tapping-mode imaging investigations. We have, for the first time to our knowledge, been able to accurately quantify the thickness and lipid configuration of phospholipid-shelled MBs - showing a trilayer as opposed to the conventional monolayer structure. Furthermore, we have measured MB stiffness and employed different mechanical theories to quantify the Young's modulus. We show that the Reissner theory is inappropriate for mechanical characterisation of phospholipid MBs, however, the Hertz model does offer biologically relevant comparisons. Analysis using the Alexander-de Gennes polymer brush theory has allowed us to provide new information regarding how the thickness of the polyethylene glycol brushes, end-grafted to our phospholipid microbubbles, changes with diameter.

Molecular Interactions behind the Self-Assembly and Microstructure of Mixed Sterol Organogels.

In this work, we have employed docking and atomistic molecular dynamics (MD) simulations supported by complementary experiments using atomic force microscopy, rheology, and spectroscopy to investigate the self-assembled structure of ß-sitosterol and γ-oryzanol molecules into cylindrical tubules in a nonaqueous solvent. Docking models of several phytosterols, including sitosterol, with oryzanol and other sterol esters demonstrate that for systems to form tubules, the phytosterol sterane group must be stacked in a wedge shape with the ester sterane group and a hydrogen bond must form between the hydroxyl group of the phytosterol and the carbonyl group of the ester. MD of the self-assembled structure were initiated with the molecules in a roughly cylindrical configuration, as suggested from previous experimental studies, and the configurations were found to be stable during 50 ns simulations. We performed MD simulations of two tubules in proximity to better understand the aggregation of these fibrils and how the fibrils interact in order to stick together. We found that an interfibril network of noncovalent bonds, in particular van der Waals and π-π contacts, which is formed between the ferulic acid groups of oryzanol through the hydroxyl, methoxy, and aromatic groups, is responsible for the surface-to-surface interactions between fibrils; an observation supported by molecular spectroscopy. We believe that these interactions are of primary importance in creating a strong organogel network.

Bacteria as living patchy colloids: Phenotypic heterogeneity in surface adhesion.

Understanding and controlling the surface adhesion of pathogenic bacteria is of urgent biomedical importance. However, many aspects of this process remain unclear (for example, microscopic details of the initial adhesion and possible variations between individual cells). Using a new high-throughput method, we identify and follow many single cells within a clonal population of Escherichia coli near a glass surface. We find strong phenotypic heterogeneities: A fraction of the cells remain in the free (planktonic) state, whereas others adhere with an adhesion strength that itself exhibits phenotypic heterogeneity. We explain our observations using a patchy colloid model; cells bind with localized, adhesive patches, and the strength of adhesion is determined by the number of patches: Nonadherers have no patches, weak adherers bind with a single patch only, and strong adherers bind via a single or multiple patches. We discuss possible implications of our results for controlling bacterial adhesion in biomedical and other applications.