Hair-Reinforced Elastomer Matrix Composites: Formulation, Mechanical Testing, and Advanced Microstructural Characterization.

Epoxy matrix composites reinforced with high-performance fibers, such as carbon, Kevlar, and glass, exhibit excellent specific stiffness and strength in many mechanical applications. However, these composites are disappointingly non-recyclable and are usually disposed of in landfill sites, with no realistic prospect for biodegradation in a reasonable time. In contrast, moldable composites with carbonized elastomeric matrices developed in the last decades possess attractive mechanical properties in final net-shape products and can also be incinerated or recycled. Many carbon and inorganic fillers have recently been evaluated to adjust the properties of carbonized elastomeric composites. Renewable organic fillers, such as human or animal hair, offer an attractive fibrous material with substantial potential for reinforcing composites with elastomeric matrices. Samples of unidirectional fiber composites (with hair volume fractions up to 7%) and quasi-isotropic short fiber composites (with hair volume fractions up to 20%) of human hair-reinforced nitrile butadiene rubbers (HH-NBRs) were produced in the peroxide-cured and carbonized states. The samples were characterized using scanning electron microscopy (SEM), Raman spectroscopy, and photoacoustic microscopy. Mechanical tests were performed under tension using a miniature universal testing machine. The expected effect of fiber reinforcement on the overall mechanical performance was demonstrated for both cured and carbonized composites. Considerable enhancement of the elastic modulus (up to ten times), ultimate tensile strength (up to three times), and damage tolerance was achieved. The evidence of satisfactory interfacial bonding between hair and rubber was confirmed via SEM imaging of fracture surfaces. The suitability of photoacoustic microscopy was assessed for 3D reconstructions of the fiber sub-system's spatial distribution and non-destructive testing.

Hydrogel-Inducing Graphene-Oxide-Derived Core-Shell Fiber Composite for Antibacterial Wound Dressing.

The study reveals the polymer-crosslinker interactions and functionality of hydrophilic nanofibers for antibacterial wound coatings. Coaxial electrospinning leverages a drug encapsulation protocol for a core-shell fiber composite with a core derived from polyvinyl alcohol and polyethylene glycol with amorphous silica (PVA-PEG-SiO2), and a shell originating from polyvinyl alcohol and graphene oxide (PVA-GO). Crosslinking with GO and SiO2 initiates the hydrogel transition for the fiber composite upon contact with moisture, which aims to optimize the drug release. The effect of hydrogel-inducing additives on the drug kinetics is evaluated in the case of chlorhexidine digluconate (CHX) encapsulation in the core of core-shell fiber composite PVA-PEG-SiO2-1x-CHX@PVA-GO. The release rate is assessed with the zero, first-order, Higuchi, and Korsmeyer-Peppas kinetic models, where the inclusion of crosslinking silica provides a longer degradation and release rate. CHX medicated core-shell composite provides sustainable antibacterial activity against Staphylococcus aureus.

Revealing the static and dynamic nanomechanical properties of diatom frustules-Nature's glass lace.

Diatoms are single cell microalgae enclosed in silica exoskeletons (frustules) that provide inspiration for advanced hybrid nanostructure designs mimicking multi-scale porosity to achieve outstanding mechanical and optical properties. Interrogating the structure and properties of diatoms down to nanometer scale leads to breakthrough advances reported here in the nanomechanical characterization of Coscinodiscus oculus-iridis diatom pure silica frustules, as well as of air-dried and wet cells with organic content. Static and dynamic mode Atomic Force Microscopy (AFM) and in-SEM nanoindentation revealed the peculiarities of diatom response with separate contributions from material nanoscale behavior and membrane deformation of the entire valve. Significant differences in the nanomechanical properties of the different frustule layers were observed. Furthermore, the deformation response depends strongly on silica hydration and on the support from the internal organic content. The cyclic loading revealed that the average compliance of the silica frustule is 0.019 m/N and increases with increasing number of cycles. The structure-mechanical properties relationship has a direct impact on the vibrational properties of the frustule as a complex micrometer-sized mechanical system. Lessons from Nature's nanostructuring of diatoms open up pathways to new generations of nano- and microdevices for electronic, electromechanical, photonic, liquid, energy storage, and other applications.

An In Vivo Rat Study of Bioresorbable Mg-2Zn-2Ga Alloy Implants.

In the present study, pins made from the novel Mg-2Zn-2Ga alloy were installed within the femoral bones of six Wistar rats. The level of bioresorption was assessed after 1, 3, and 6 months by radiography, histology, SEM, and EDX. Significant bioresorption was evident after 3 months, and complete dissolution of the pins occurred at 6 months after the installation. No pronounced gas cavities could be found at the pin installation sites throughout the postoperative period. The animals' blood parameters showed no signs of inflammation or toxication. These findings are sufficiently encouraging to motivate further research to broaden the experimental coverage to increase the number of observed animals and to conduct tests involving other, larger animals.

Analysis of Stress Relaxation in Bulk and Porous Ultra-High Molecular Weight Polyethylene (UHMWPE).

The reported study was devoted to the investigation of viscoelastic behavior for solid and porous ultra-high molecular weight polyethylene (UHMWPE) under compression. The obtained experimental stress curves were interpreted using a two-term Prony series to represent the superposition of two coexisting activation processes corresponding to long molecular (~160 s) and short structural (~20 s) time scales, respectively, leading to good statistical correlation with the observations. In the case of porous polymer, the internal strain redistribution during relaxation was quantified using digital image correlation (DIC) analysis. The strongly inhomogeneous deformation of the porous polymer was found not to affect the relaxation times. To illustrate the possibility of generalizing the results to three dimensions, X-ray tomography was used to examine the porous structure relaxation at the macro- and micro-scale levels. DIC analysis revealed positive correlation between the applied force and relative density. The apparent stiffness variation for UHMWPE foams with mixed open and closed cells was described using a newly proposed three-term expression. Furthermore, in situ tensile loading and X-ray scattering study was applied for isotropic solid UHMWPE specimens to investigate the evolution of internal structure and orientation during drawing and stress relaxation in another loading mode.

Fracture Toughness of Moldable Low-Temperature Carbonized Elastomer-Based Composites Filled with Shungite and Short Carbon Fibers.

This work evaluated the fracture toughness of the low-temperature carbonized elastomer-based composites filled with shungite and short carbon fibers. The effects of the carbonization temperature and filler content on the critical stress intensity factor (K1c) were examined. The K1c parameter was obtained using three-point bending tests for specimens with different l/b ratio (notch depth to sample thickness) ranging from 0.2 to 0.4. Reliable detection of the initiation and propagation of cracks was achieved using an acoustic sensor was attached to the samples during the bending test. The critical stress intensity factor was found to decrease linearly with increasing carbonization temperature. As the temperature increased from 280 to 380 °C, the K1c parameter was drastically reduced from about 5 to 1 MPa·m1/2 and was associated with intense outgassing during the carbonization step that resulted in sample porosity. The carbon fiber addition led to some incremental toughening; however, it reduced the statistical dispersion of the K1c values.

FIB-DIC Residual Stress Evaluation in Shot Peened VT6 Alloy Validated by X-ray Diffraction and Laser Speckle Interferometry.

Ga-ion micro-ring-core FIB-DIC evaluation of residual stresses in shot peened VT6 (Ti-6Al-4V) alloy was carried out and cross-validated against other non-destructive and semi-destructive residual stresses evaluation techniques, namely, the conventional sin2ψ X-ray diffraction and mechanical hole drilling. The Korsunsky FIB-DIC method of Ga-ion beam micro-ring-core milling within FIB-SEM with Digital Image Correlation (DIC) deformation analysis delivered spatial resolution down to a few micrometers, while the mechanical drilling of circular holes of ~2 mm diameter with laser speckle interferometry monitoring of strains gave a rough spatial resolution of a few millimeters. Good agreement was also found with the X-ray diffraction estimates of residual stress variation profiles as a function of depth. These results demonstrate that FIB-DIC provides rich information down to the micron scale, it also allows reliable estimation of macro-scale residual stresses.

A SERS platform based on diatomite modified by gold nanoparticles using a combination of layer-by-layer assembly and a freezing-induced loading method.

Siliceous diatom frustules represent an up-and-coming platform for a range of bio-assisted nanofabrication processes able to overcome the complexity and high cost of current engineering technology solutions in terms of negligibly small power consumption and environmentally friendly processing combined with unique highly porous structures and properties. Herein, the modification of diatomite - a soft, loose, and fine-grained siliceous sedimentary rock composed of the remains of fossilized diatoms - with gold nanoparticles using layer-by-layer technology in combination with a freezing-induced loading approach is demonstrated. The obtained composite structures are characterized by dynamic light scattering, extinction spectroscopy, scanning (SEM) and transmission electron microscopy (TEM), and photoacoustic imaging techniques, and tested as a platform for surface-enhanced Raman scattering (SERS) using Rhodamine 6G. SEM, TEM, and energy dispersive X-ray spectroscopy (EDX) confirmed a dense coating of gold nanoparticles with an average size of 19 nm on the surface of the diatomite and within the pores. The photoacoustic signal excited at a wavelength of 532 nm increases with increasing loading cycles of up to three polyelectrolyte-gold nanoparticle bilayers. The hybrid materials based on diatomite modified with gold nanoparticles can be used as SERS substrates, but also as biosensors, catalysts, and platforms for advanced bioimaging.

Effect of Graphene Oxide and Nanosilica Modifications on Electrospun Core-Shell PVA-PEG-SiO2@PVA-GO Fiber Mats.

Electrospinning is a well-established method for the fabrication of polymer biomaterials, including those with core-shell nanofibers. The variability of structures presents a great range of opportunities in tissue engineering and drug delivery by incorporating biologically active molecules such as drugs, proteins, and growth factors and subsequent control of their release into the target microenvironment to achieve therapeutic effect. The object of study is non-woven core-shell PVA-PEG-SiO2@PVA-GO fiber mats assembled by the technology of coaxial electrospinning. The task of the core-shell fiber development was set to regulate the degradation process under external factors. The dual structure was modified with silica nanoparticles and graphene oxide to ensure the fiber integrity and stability. The influence of the nano additives and crosslinking conditions for the composite was investigated as a function of fiber diameter, hydrolysis, and mechanical properties. Tensile mechanical tests and water degradation tests were used to reveal the fracture and dissolution behavior of the fiber mats and bundles. The obtained fibers were visualized by confocal fluorescence microscopy to confirm the continuous core-shell structure and encapsulation feasibility for biologically active components, selectively in the fiber core and shell. The results provide a firm basis to draw the conclusion that electrospun core-shell fiber mats have tremendous potential for biomedical applications as drug carriers, photocatalysts, and wound dressings.

On the Structural Peculiarities of Self-Reinforced Composite Materials Based on UHMWPE Fibers.

The structure of self-reinforced composites (SRCs) based on ultra-high molecular weight polyethylene (UHMWPE) was studied by means of Wide-Angle X-ray Scattering (WAXS), X-ray tomography, Raman spectroscopy, Scanning Electron Microscopy (SEM) and in situ tensile testing in combination with advanced processing tools to determine the correlation between the processing conditions, on one hand, and the molecular structure and mechanical properties, on the other. SRCs were fabricated by hot compaction of UHMWPE fibers at different pressure and temperature combinations without addition of polymer matrix or softener. It was found by WAXS that higher compaction temperatures led to more extensive melting of fibers with the corresponding reduction of the Herman's factor reflecting the degree of molecular orientation, while the increase of hot compaction pressure suppressed the melting of fibers within SRCs at a given temperature. X-ray tomography proved the absence of porosity while polarized light Raman spectroscopy measurements for both longitudinal and perpendicular fiber orientations showed qualitatively the anisotropy of SRC samples. SEM revealed that the matrix was formed by interlayers of molten polymer entrapped between fibers in SRCs. Moreover, in situ tensile tests demonstrated the increase of Young's modulus and tensile strength with increasing temperature.

The Analysis of Micro-Scale Deformation and Fracture of Carbonized Elastomer-Based Composites by In Situ SEM.

Carbonized elastomer-based composites (CECs) possess a number of attractive features in terms of thermomechanical and electromechanical performance, durability in aggressive media and facile net-shape formability, but their relatively low ductility and strength limit their suitability for structural engineering applications. Prospective applications such as structural elements of micro-electro-mechanical systems MEMS can be envisaged since smaller principal dimensions reduce the susceptibility of components to residual stress accumulation during carbonization and to brittle fracture in general. We report the results of in situ in-SEM study of microdeformation and fracture behavior of CECs based on nitrile butadiene rubber (NBR) elastomeric matrices filled with carbon and silicon carbide. Nanostructured carbon composite materials were manufactured via compounding of elastomeric substance with carbon and SiC fillers using mixing rolling mill, vulcanization, and low-temperature carbonization. Double-edge notched tensile (DENT) specimens of vulcanized and carbonized elastomeric composites were subjected to in situ tensile testing in the chamber of the scanning electron microscope (SEM) Tescan Vega 3 using a Deben microtest 1 kN tensile stage. The series of acquired SEM images were analyzed by means of digital image correlation (DIC) using Ncorr open-source software to map the spatial distribution of strain. These maps were correlated with finite element modeling (FEM) simulations to refine the values of elastic moduli. Moreover, the elastic moduli were derived from unloading curve nanoindentation hardness measurements carried out using a NanoScan-4D tester and interpreted using the Oliver-Pharr method. Carbonization causes a significant increase of elastic moduli from 0.86 ± 0.07 GPa to 14.12 ± 1.20 GPa for the composite with graphite and carbon black fillers. Nanoindentation measurements yield somewhat lower values, namely, 0.25 ± 0.02 GPa and 9.83 ± 1.10 GPa before and after carbonization, respectively. The analysis of fractography images suggests that crack initiation, growth and propagation may occur both at the notch stress concentrator or relatively far from the notch. Possible causes of such response are discussed, namely, (1) residual stresses introduced by processing; (2) shape and size of fillers; and (3) the emanation and accumulation of gases in composites during carbonization.

On the diatomite-based nanostructure-preserving material synthesis for energy applications.

The present article overviews the current state-of-the-art and future prospects for the use of diatomaceous earth (DE) in the continuously expanding sector of energy science and technology. An eco-friendly direct source of silica and the production of silicon, diatomaceous earth possesses a desirable nano- to micro-structure that offers inherent advantages for optimum performance in existing and new applications in electrochemistry, catalysis, optoelectronics, and biomedical engineering. Silica, silicon and silicon-based materials have proven useful for energy harvesting and storage applications. However, they often encounter setbacks to their commercialization due to the limited capability for the production of materials possessing fascinating microstructures to deliver optimum performance. Despite many current research trends focusing on the means to create the required nano- to micro-structures, the high cost and complex, potentially environmentally harmful chemical synthesis techniques remain a considerable challenge. The present review examines the advances made using diatomaceous earth as a source of silica, silicon-based materials and templates for energy related applications. The main synthesis routes aimed at preserving the highly desirable naturally formed neat nanostructure of diatomaceous earth are assessed in this review that culminates with the discussion of recently developed pathways to achieving the best properties. The trend analysis establishes a clear roadmap for diatomaceous earth as a source material of choice for current and future energy applications.

Multi-Scale Digital Image Correlation Analysis of In Situ Deformation of Open-Cell Porous Ultra-High Molecular Weight Polyethylene Foam.

Porous ultra-high molecular weight polyethylene (UHMWPE) is a high-performance bioinert polymer used in cranio-facial reconstructive surgery in procedures where relatively low mechanical stresses arise. As an alternative to much stiffer and more costly polyether-ether-ketone (PEEK) polymer, UHMWPE is finding further wide applications in hierarchically structured hybrids for advanced implants mimicking cartilage, cortical and trabecular bone tissues within a single component. The mechanical behaviour of open-cell UHMWPE sponges obtained through sacrificial desalination of hot compression-moulded UHMWPE-NaCl powder mixtures shows a complex dependence on the fabrication parameters and microstructural features. In particular, similarly to other porous media, it displays significant inhomogeneity of strain that readily localises within deformation bands that govern the overall response. In this article, we report advances in the development of accurate experimental techniques for operando studies of the structure-performance relationship applied to the porous UHMWPE medium with pore sizes of about 250 µm that are most well-suited for live cell proliferation and fast vascularization of implants. Samples of UHMWPE sponges were subjected to in situ compression using a micromechanical testing device within Scanning Electron Microscope (SEM) chamber, allowing the acquisition of high-resolution image sequences for Digital Image Correlation (DIC) analysis. Special masking and image processing algorithms were developed and applied to reveal the evolution of pore size and aspect ratio. Key structural evolution and deformation localisation phenomena were identified at both macro- and micro-structural levels in the elastic and plastic regimes. The motion of pore walls was quantitatively described, and the presence and influence of strain localisation zones were revealed and analysed using DIC technique.

Fast Mass-Production of Medical Safety Shields under COVID-19 Quarantine: Optimizing the Use of University Fabrication Facilities and Volunteer Labor.

COVID-19 pandemic provoked a number of restrictive measures, such as the closure or severe restriction of border transit for international trading traffic, quarantines and self-isolation. This caused a series of interrelated consequences that not only prevent or slow down the spread of disease, but also impact the medical systems' capability to treat the patients and help their recovery. In particular, steeply growing demand for medical safety goods cannot be satisfied by regular suppliers due to the shortage of raw materials originating from other countries or remotely located national sources, under conditions of quarantined manpower. The current context inevitably brings back memories (and records!) of the situation 80 years ago, when WWII necessitated major effort directed at the rapid build-up of low-cost mass production to satisfy all aspects of war-time need. In the present short report we document a successful case of fast mass-production of light transparent medical safety face shields (thousands per day) realized in Skolkovo Institute of Science and Technology (Skoltech) at Fablab and Machine Shop Shared Facility (Skoltech FabLab). The demand for safety face shields by tens of hospitals in Moscow and other cities rapidly ramped up due to the need to protect medical staff during patient collection and transportation to hospitals, and within both the infected ("red") and uninfected ("green") zones. Materials selection for sterilizable transparent materials was conducted based on the analysis of merit indices, namely, minimal weight at given stiffness and minimal cost at given stiffness. Due to the need for permanent wear, design was motivated by low weight and comfortable head fixation, along with high production efficiency. The selection of minimal tooling in University fabrication workshops and the use of distributed volunteer labor are discussed.

Photoacoustic and fluorescence lifetime imaging of diatoms.

Photoacoustic and fluorescent methods are used intensely in biology and medicine. These approaches can also be used to investigate unicellular diatom algae that are extremely important for Earth's ecology. They are enveloped within silica frustules (exoskeletons), which can be used in drug delivery systems. Here, we report for the first time the successful application of photoacoustic (PA) and fluorescent visualization of diatoms. Chlorophyll a and c and fucoxanthin were found likely to be responsible for the photoacoustic effect in diatoms. The PA signal was obtained from gel drops containing diatoms and was found to increase with the diatom concentration. The fluorescence lifetime of the diatom chromophores ranged from 0.5 to 2 ns. The dynamic light scattering, absorbance, and SEM characterization techniques were also applied. The results were considered in combination to elucidate the nature of the photoacoustic signal. Possible biotechnological applications are proposed for the remote photoacoustic monitoring of algae.

In Situ Formation of Nanoporous Silicon on a Silicon Wafer via the Magnesiothermic Reduction Reaction (MRR) of Diatomaceous Earth.

Successful direct route production of silicon nanostructures from diatomaceous earth (DE) on a single crystalline silicon wafer via the magnesiothermic reduction reaction is reported. The formed porous coating of 6 µm overall thickness contains silicon as the majority phase along with minor traces of Mg, as evident from SEM-EDS and the Focused Ion Beam (FIB) analysis. Raman peaks of silicon at 519 cm-1 and 925 cm-1 were found in both the film and wafer substrate, and significant intensity variation was observed, consistent with the SEM observation of the directly formed silicon nanoflake layer. Microstructural analysis of the flakes reveals the presence of pores and cavities partially retained from the precursor diatomite powder. A considerable reduction in surface reflectivity was observed for the silicon nanoflakes, from 45% for silicon wafer to below 15%. The results open possibilities for producing nanostructured silicon with a vast range of functionalities.

Development of biomimetic in vitro fatigue assessment for UHMWPE implant materials.

An important research goal in the field of biomaterials lies in the progressive amendment of in vivo tests with suitable in vitro experiments. Such approaches are gaining more significance nowadays because of an increasing demand on life sciences and the ethical issues bound to the sacrifice of animals for the sake of scientific research. Another advantage of transferring the experiments to the in vitro field is the possibility of accurately control the boundary conditions and experimental parameters in order to reduce the need of validation tests involving animals. With the aim to reduce the amount of needed in vivo studies for this cause, a short-time in vitro test procedure using instrumented load increase tests with superimposed environmental loading has been developed at TUD to assess the mechanical long-term durability of ultra-high molecular weight polyethylene (UHMWPE) under fatigue loading in a biological environment.