Identifying the Molecular Origins of Green BN-TADF Material Degradation and Device Stability via in†situ Raman Spectroscopy.

There is little investigation into the impact of molecular conformation on device efficiency and degradation of boron-nitrogen thermally activated delayed fluorescence emitters (BN-TADF). Herein, three highly-efficient green BN-TADF emitters have been designed to unveil the impact of peripheral phenyl groups on device efficiencies and lifetimes. Compared to BN-PhOH with the lowest EQEmax of 19 %, BN-PhOCH3 and BN-PhN(CH3 )2 have achieved strongly enhanced EQEmax of 25.6 % and 24.1 %, respectively. Importantly, the device lifetimes (LT50 ) are dramatically improved from 1.7 h of BN-PhOH to 4.4 h of BN-PhOCH3 and 7.7 h of BN-PhN(CH3 )2 without encapsulation. According to in situ Raman spectroscopy and simulations, BN-PhN(CH3 )2 of less conformation change after aging exhibits the best photostability. It is proposed that the torsion angle change between the BN core and the peripheral phenyl group results in BN-TADF degradation. This knowledge means precisely tuning peripheral groups of BN-TADF can achieve both higher device efficiencies and longer lifetimes.

Nonlinear Guided Wave Tomography for Detection and Evaluation of Early-Life Material Degradation in Plates.

In this paper, the possibility of using nonlinear ultrasonic guided waves for early-life material degradation in metal plates is investigated through both computational modeling and study. The analysis of the second harmonics of Lamb waves in a free boundary aluminum plate, and the internal resonance conditions between the Lamb wave primary modes and the second harmonics are investigated. Subsequently, Murnaghan's hyperelastic model is implemented in a finite element (FE) analysis to study the response of aluminum plates subjected to a 60 kHz Hanning-windowed tone burst. Different stages of material degradation are reflected as the changes in the third order elastic constants (TOECs) of the Murnaghan's model. The reconstructed degradations match the actual ones well across various degrees of degradation. The effects of several relevant factors on the accuracy of reconstructions are also discussed.

Tailoring Pyro-and Orthophosphate Species to Enhance Stem Cell Adhesion to Phosphate Glasses.

Phosphate-based glasses (PBGs) offer significant therapeutic potential due to their bioactivity, controllable compositions, and degradation rates. Several PBGs have already demonstrated their ability to support direct cell growth and in vivo cytocompatibility for bone repair applications. This study investigated development of PBG formulations with pyro- and orthophosphate species within the glass system (40 - x)P2O5·(16 + x)CaO·20Na2O·24MgO (x = 0, 5, 10 mol%) and their effect on stem cell adhesion properties. Substitution of phosphate for calcium revealed a gradual transition within the glass structure from Q2 to Q0 phosphate species. Human mesenchymal stem cells were cultured directly onto discs made from three PBG compositions. Analysis of cells seeded onto the discs revealed that PBG with higher concentration of pyro- and orthophosphate content (61% Q1 and 39% Q0) supported a 4.3-fold increase in adhered cells compared to glasses with metaphosphate connectivity (49% Q2 and 51% Q1). This study highlights that tuning the composition of PBGs to possess pyro- and orthophosphate species only, enables the possibility to control cell adhesion performance. PBGs with superior cell adhesion profiles represent ideal candidates for biomedical applications, where cell recruitment and support for tissue ingrowth are of critical importance for orthopaedic interventions.

A Gradient-Field Pulsed Eddy Current Probe for Evaluation of Hidden Material Degradation in Conductive Structures Based on Lift-Off Invariance.

Coated conductive structures are widely adopted in such engineering fields as aerospace, nuclear energy, etc. The hostile and corrosive environment leaves in-service coated conductive structures vulnerable to Hidden Material Degradation (HMD) occurring under the protection coating. It is highly demanded that HMD can be non-intrusively assessed using non-destructive evaluation techniques. In light of the advantages of Gradient-field Pulsed Eddy Current technique (GPEC) over other non-destructive evaluation methods in corrosion evaluation, in this paper the GPEC probe for quantitative evaluation of HMD is intensively investigated. Closed-form expressions of GPEC responses to HMD are formulated via analytical modeling. The Lift-off Invariance (LOI) in GPEC signals, which makes the HMD evaluation immune to the variation in thickness of the protection coating, is introduced and analyzed through simulations involving HMD with variable depths and conductivities. A fast inverse method employing magnitude and time of the LOI point in GPEC signals for simultaneously evaluating the conductivity and thickness of HMD region is proposed, and subsequently verified by finite element modeling and experiments. It has been found from the results that along with the proposed inverse method the GPEC probe is applicable to evaluation of HMD in coated conductive structures without much loss in accuracy.

Identification of a novel carbohydrate esterase from Bjerkandera adusta: structural and function predictions through bioinformatics analysis and molecular modeling.

A new gene from Bjerkandera adusta strain UAMH 8258 encoding a carbohydrate esterase (designated as BacesI) was isolated and expressed in Pichia pastoris. The gene had an open reading frame of 1410 bp encoding a polypeptide of 470 amino acid residues, the first 18 serving as a secretion signal peptide. Homology and phylogenetic analyses showed that BaCesI belongs to carbohydrate esterases family 4. Three-dimensional modeling of the protein and normal mode analysis revealed a breathing mode of the active site that could be relevant for esterase activity. Furthermore, the overall negative electrostatic potential of this enzyme suggests that it degrades neutral substrates and will not act on negative substrates such as peptidoglycan or p-nitrophenol derivatives. The enzyme shows a specific activity of 1.118 U mg(-1) protein on 2-naphthyl acetate. No activity was detected on p-nitrophenol derivatives as proposed from the electrostatic potential data. The deacetylation activity of the recombinant BaCesI was confirmed by measuring the release of acetic acid from several substrates, including oat xylan, shrimp shell chitin, N-acetylglucosamine, and natural substrates such as sugar cane bagasse and grass. This makes the protein very interesting for the biofuels production industry from lignocellulosic materials and for the production of chitosan from chitin.

Challenges and Future Recommendations for Lightning Strike Damage Assessments of Composites: Laboratory Testing and Predictive Modeling.

Lightning strike events pose significant challenges to the structural integrity and performance of composite materials, particularly in aerospace, wind turbine blade, and infrastructure applications. Through a meticulous examination of the state-of-the-art methodologies of laboratory testing and damage predictive modeling, this review elucidates the role of simulated lightning strike tests in providing inputs required for damage modeling and experimental data for model validations. In addition, this review provides a holistic understanding of what is there, what are current issues, and what is still missing in both lightning strike testing and modeling to enable a robust and high-fidelity predictive capability, and challenges and future recommendations are also presented. The insights gleaned from this review are poised to catalyze advancements in the safety, reliability, and durability of composite materials under lightning strike conditions, as well as to facilitate the development of innovative lightning damage mitigation strategies.

Meta-structure enhanced second harmonic S0 waves for material microstructural changes monitoring.

Cumulative second harmonic Lamb waves in nonlinear media feature increasing amplitudes with propagation distance, conducive to the monitoring of material microstructural changes in structures. The phenomenon can be readily generated by zero-order symmetric (S0) mode waves in the low-frequency range. However, in a practical piezoelectric-transducer-activated system, both S0 and A0 (zero-order antisymmetric) mode Lamb waves are inevitably excited, while only the former is responsible for cumulative effects. The generation efficiency of the cumulative second harmonics is then affected by the presence of the A0 waves. To tackle the problem, this study develops a metamaterial structure, referred to as a meta-structure, to tactically enhance the cumulative second harmonic S0 Lamb waves by converting the A0 mode components into S0 mode waves. Topology optimization is conducted to design the meta-structure, which is surface-mounted onto the structure under inspection, to achieve high-efficiency A0-to-S0 wave mode conversion. Through tuning the parameters and constraints of the optimization, the designed single-sided meta-structure breaks the structural symmetry in the thickness direction, while facilitating its practical implementation. Typical scenarios with different meta-structure materials are discussed. Numerical simulations demonstrate that the strain amplitudes of the fundamental S0 mode waves can be increased by 60% with the deployment of the meta-structure, alongside an enhancement of the second harmonic S0 mode waves at different sensing distances. Finally, the designed meta-structure is fabricated via 3D printing technique and tested experimentally on an aluminum plate subjected to thermal aging treatment for monitoring the heating-induced microstructural changes inside the structure. Experimental results confirm an increase in the wave amplitudes of the linear S0 mode waves with the assistance of the meta-structure. The developed system improves the sensitivity of nonlinear Lamb wave-based monitoring methods in characterizing material microstructural changes, which shows great promise for detecting incipient damage in practical structural health monitoring applications.

Toward high-resolution 3D-printing of pharmaceutical implants - A holistic analysis of relevant material properties and process parameters.

In this work, filament-based 3D-printing, the most widely used sub-category of material extrusion additive manufacturing (MEAM), is presented as a promising manufacturing platform for the production of subcutaneous implants. Print nozzle diameters as small as 100 µm were utilized demonstrating MEAM of advanced porous internal structures at the given cylindrical implant geometry of 2 mm × 40 mm. The bottlenecks related to high-resolution MEAM of subcutaneous implants are systematically analyzed and the print process is optimized accordingly. Custom synthesized biodegradable phase-separated poly(ether ester) multiblock copolymers exhibiting appropriate melt viscosity at comparatively low printing temperatures of 135 °C and 165 °C were utilized as 3D-printing feedstock. The print process was optimized to minimize thermomechanical polymer degradation by employing print speeds of 30 mm∙s-1 in combination with a nozzle diameter of 150 µm at layer heights of 110 µm. These results portray the basis for further development of subcutaneous implantable drug delivery systems where drug release profiles can be tailored through the adaption of the internal implant structure, which cannot be achieved using existing manufacturing techniques.

Evaluation of Material Integrity Using Higher-Order Harmonic Generation in Propagating Shear Horizontal Ultrasonic Waves.

Material nonlinearity is explored for the assessment of structural integrity. Crack-wave interactions are of particular interest. The major focus is on higher-order harmonics, generated in propagating shear horizontal (SH) waves. These harmonics are generated due to global material nonlinearity and local effects such as fatigue cracks. The theoretical background of the proposed method is explained. The method is examined using numerical simulations and experimental tests. The former involves the Local Interaction Simulation Approach (LISA), implemented for the nonlinear shear horizontal wavefield. The latter is based on a high-frequency shear excitation approach. Experimental tests are conducted using a series of beam specimens with fatigue cracks. Low-profile, surface-bonded piezoceramic shear actuators are used for excitation. The excitation frequency is selected to minimize the number of generated modes in the examined specimens. Nonlinear ultrasonic responses are collected using a non-contact laser vibrometer. The results show that higher-order harmonic generation-based on shear horizontal wave propagation-can be used for crack detection in the presence of global material nonlinearity.

In Vivo Investigation of 3D-Printed Calcium Magnesium Phosphate Wedges in Partial Load Defects.

Bone substitutes are ideally biocompatible, osteoconductive, degradable and defect-specific and provide mechanical stability. Magnesium phosphate cements (MPCs) offer high initial stability and faster degradation compared to the well-researched calcium phosphate cements (CPCs). Calcium magnesium phosphate cements (CMPCs) should combine the properties of both and have so far shown promising results. The present study aimed to investigate and compare the degradation and osseointegration behavior of 3D powder-printed wedges of CMPC and MPC in vivo. The wedges were post-treated with phosphoric acid (CMPC) and diammonium hydrogen phosphate (MPC) and implanted in a partially loaded defect model in the proximal rabbit tibia. The evaluation included clinical, in vivo µ-CT and X-ray examinations, histology, energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) for up to 30 weeks. SEM analysis revealed a zone of unreacted material in the MPC, indicating the need to optimize the manufacturing and post-treatment process. However, all materials showed excellent biocompatibility and mechanical stability. After 24 weeks, they were almost completely degraded. The slower degradation rate of the CMPC corresponded more favorably to the bone growth rate compared to the MPC. Due to the promising results of the CMPC in this study, it should be further investigated, for example in defect models with higher load.

Utah array characterization and histological analysis of a multi-year implant in non-human primate motor and sensory cortices.

Objective.The Utah array is widely used in both clinical studies and neuroscience. It has a strong track record of safety. However, it is also known that implanted electrodes promote the formation of scar tissue in the immediate vicinity of the electrodes, which may negatively impact the ability to record neural waveforms. This scarring response has been primarily studied in rodents, which may have a very different response than primate brain.Approach.Here, we present a rare nonhuman primate histological dataset (n= 1 rhesus macaque) obtained 848 and 590 d after implantation in two brain hemispheres. For 2 of 4 arrays that remained within the cortex, NeuN was used to stain for neuron somata at three different depths along the shanks. Images were filtered and denoised, with neurons then counted in the vicinity of the arrays as well as a nearby section of control tissue. Additionally, 3 of 4 arrays were imaged with a scanning electrode microscope to evaluate any materials damage that might be present.Main results.Overall, we found a 63% percent reduction in the number of neurons surrounding the electrode shanks compared to control areas. In terms of materials, the arrays remained largely intact with metal and Parylene C present, though tip breakage and cracks were observed on many electrodes.Significance.Overall, these results suggest that the tissue response in the nonhuman primate brain shows similar neuron loss to previous studies using rodents. Electrode improvements, for example using smaller or softer probes, may therefore substantially improve the tissue response and potentially improve the neuronal recording yield in primate cortex.

Modeling and simulation of zero-group velocity combined harmonic generated by guided waves mixing.

In this paper, modelling and numerical perspective of zero-group velocity (ZGV) combined harmonic generated by guided waves mixing are investigated. The conditions for the generation of the ZGV combined harmonic are analyzed by S0-S0 and SH0-SH0 guided waves mixing in an isotropic plate, respectively. The generation of ZGV combined harmonics at sum frequency caused by counter-directional guided waves mixing is observed. It is confirmed that the ZGV combined harmonic with a considerable magnitude can be generated by this counter-directional guided waves mixing when both the internal resonant condition and non-zero power flux are satisfied. The application of generated ZGV combined harmonics for localized material degradation assessment is numerically examined in the given plate. The obtained results indicate that the generated ZGV combined harmonic induced by the counter-directional guided waves mixing can be used to assess the localized material degradation with improved signal-to-noise ratio. This study provides an insight into the physical process of the ZGV combined harmonic generation, and meanwhile offer a promising means for localized material degradation assessment by ZGV combined harmonics generated by guided waves mixing.

A Simplified Approach for the Corrosion Fatigue Assessment of Steel Structures in Aggressive Environments.

Fatigue performance is often a key aspect when dealing with existing steel structures such as steel bridges or offshore constructions. This issue proves to be more critical as these structures are usually located in aggressive environments and are thus exposed to progressive degradation. Indeed, disruptive phenomena such as corrosion can severely worsen the fatigue performance of the steel components. Currently, the normative standards do not provide a codified procedure for the fatigue checks of steel structures subjected to ongoing corrosion. Within this framework, in this paper a simplified approach for the life-cycle assessment of corroded steel structures is proposed. For this purpose, the concept of "critical corrosion degree" is introduced, allowing the expression of corrosion fatigue checks in a more direct "demand vs. capacity" form with respect to the currently available methods. A first validation of such methodology is reported for the corrosion fatigue tests drawn from the literature. The predicted levels of critical corrosion are in good agreement with the values of artificially induced corrosion (i.e., 4, 8, and 12% of mass loss, respectively), with a maximum relative error of ≈9.3% for the most corroded specimen. Finally, parametrical analyses are performed, highlighting the influence of the model parameters on the corrosion fatigue performance of the steel elements.

Review of the Performance of High-Voltage Composite Insulators.

In the present literature survey, we focused on the performance of polymeric materials encompassing silicone rubber (SiR), ethylene propylene diene monomer (EPDM) and epoxy resins loaded with micro, nano, and micro/nano hybrid fillers. These insulators are termed as composite insulators. The scope of the added fillers/additives was limited to the synthetic inorganic family. Special attention was directed to understanding the effect of fillers on the improvement of the thermal conductivity, dielectric strength, mechanical strength, corona discharge resistance, and tracking and erosion resistance performance of polymeric materials for use as high-voltage transmission line insulators. The survey showed that synthetic inorganic fillers, which include silica (SiO2) and hexagonal boron nitride (h-BN), are potential fillers to improve insulation performance of high-voltage insulators. Furthermore, nano and micro/nano filled composites performed better due to the better interaction between the filler and polymer matrix as compared to their only micro- or nano filled counterparts. Finally, some aspects requiring future work to further exploit fillers are identified and discussed.

Cubic nonlinearity parameter measurement and material degradation detection using nonlinear ultrasonic three-wave mixing.

Early detection of accumulated damage or material degradation in structures is important to ensure their structural safety. Nonlinear ultrasonic techniques are widely used to measure the quadratic nonlinearity parameter that represents the third-order elastic constants of materials for material degradation detection. In addition, there are ongoing efforts to exploit both the third- and fourth-order elastic constants that describe the cubic nonlinearity parameter to detect material degradation. This study develops a nonlinear ultrasonic three-wave mixing technique to generate and measure third-order combined harmonics (TOCH) in plate-like structures and to measure cubic nonlinearity parameter. The proposed three-wave mixing technique generates three primary Lamb waves in the target structure and measures the TOCH produced by nonlinear cross-interaction of the primary Lamb waves. A theoretical model is developed to describe the generation of TOCH in a nonlinear elastic and homogeneous plate, and the effectiveness of the theoretical model is validated experimentally. Measurements of the TOCH are conducted for intact and degraded aluminum specimens with different degradation levels. Because inherent material nonlinearity and material degradation alter the third- and fourth-order elastic constants of a structure, the three-wave mixing technique for measuring the TOCH can be used to identify the inherent material nonlinearity and material degradation. In particular, the experimental results indicate that the proposed technique is more sensitive to early-stage material degradation than existing nonlinear ultrasonic techniques such as two-wave mixing, and third harmonic generation techniques.

Degradation Characteristics of Electrospun Gas Diffusion Layers with Custom Pore Structures for Polymer Electrolyte Membrane Fuel Cells.

Electrospinning has been demonstrated to be a versatile technique for producing hydrophobic gas diffusion layers (GDLs) with customized pore structures for the enhanced performance of polymer electrolyte membrane (PEM) fuel cells. However, the degradation characteristics of custom hydrophobic electrospun GDLs (eGDLs) have not yet been explored. Here, for the first time, we investigate the degradation characteristics of custom hydrophobic eGDLs via an ex situ accelerated degradation protocol using H2O2. The surface contact angle of degraded eGDLs (44 ± 12°) was lower than that of pristine eGDLs (137 ± 6°). The loss of hydrophobicity was attributed to the degradation (via hydrolysis) of the fluorinated monolayers (formed via a direct fluorination treatment) on the electrospun carbon fiber surfaces as evidenced by the reduction in surface fluorine content. Degradation of the surface monolayers affected fuel cell performance under multiple operating conditions. At 100% relative humidity (RH), the loss of monolayers led to higher liquid water content and lower cell voltages compared to the pristine eGDL. At 50% RH, the degraded eGDL led to lower cell voltages due to the lower electrical conductivity of the degraded materials. The lower electrical conductivity was attributed to the oxidation of carbon fibers upon loss of the monolayers. Our results indicate the importance of designing robust hydrophobic surface treatments for the advancement of customized GDLs for effective long-term fuel cell operation.

Aircraft Impact Effects on an Aged NPP.

The impact of an aircraft is widely known to be one of the worst events that can occur during the operation of a plant (classified for this reason as beyond design). This can become much more catastrophic and lead to the loss of strength of/collapse of the structures when it occurs in the presence of ageing (degradation and alteration) materials. Therefore, since the performance of all plant components may be affected by ageing, there is a need to evaluate the effect that aged components have on system performance and plant safety. This study addresses the numerical simulation of an aged Nuclear Power Plant (NPP) subjected to a military aircraft impact. The effects of impact velocity, direction, and location were investigated together with the more unfavorable conditions to be expected for the plant. The modelling method was also validated based on the results obtained from the experiments of Sugano et al., 1993. Non-linear analyses by means of finite element (FE) MARC code allowed us to simulate the performance of the reinforced concrete containment building and its impact on plant availability and reliability. The results showed that ageing increases a plant's propensity to suffer damage. The damage at the impact area was confirmed to be dependent on the type of aircraft involved and the target wall thickness. The greater the degradation of the materials, the lower the residual resistance capacity, and the greater the risk of wall perforation.

Experimental study on the chemico-physical interaction between a two-component cyanoacrylate glue and the material of PICCs.

INTRODUCTION: The use of cyanoacrylate glue as sealant on the exit site of peripherally inserted central catheters (PICCs) may offer some important clinical advantages. However, concerns exist about the potential interaction between cyanoacrylate and the material of the catheter itself. The aim of this study was to investigate the possibility of damage to the catheter secondary to a long-term contact with a two-component skin glue (N-butyl + octyl cyanoacrylate). METHODS: Twelve PICCs of different brands and types were selected (11 made of polyurethane and one made of silicon). PICCs were glued onto artificial skin pads, slightly wetted with Earle solution. The pads were kept in an egg incubator at 34°C and 60% humidity, for up to twelve weeks. Possible signs of degradation were monitored by surface analyses and mechanical tests. Scanning electron microscopy observations, surface roughness measurements, pressure strength and uniaxial tests were performed. RESULTS: Samples were analyzed after 4, 8 and 12 weeks of contact with the glue. No chemical reaction between the glue and the material of the catheters was evident. The mechanical strength of PICCs was consistently within the ranges of ISO standards. An expected increase in the stiffness of the samples covered with glue was observed in uniaxial tests. The silicon catheter was weaker than the polyurethane catheters and was damaged while trying to remove it from the pad for tests. CONCLUSIONS: The long-term use of N-butyl + octyl cyanoacrylate glue on polyurethane PICCs is not expected to be associated to any damage to the catheter.

Real-time imaging tracking of a dual-fluorescent drug delivery system based on doxorubicin-loaded globin- polyethylenimine nanoparticles for visible tumor therapy.

Elucidation of the pathway of drug delivery and carrier degradation in vivo is essential for the fabrication of a feasible drug delivery system. Multispectral fluorescence imaging can track a drug delivery system simultaneously based on the separation of fluorescence at multiple wavelengths without interference. In this study, the Doxorubicin loaded genipin-crosslinked globin and PEI nanoparticles (Gb-G-PEI/Dox NPs) were designed as a dual fluorescent drug delivery system to track the drug release and carrier degradation process. Both confocal laser scanning microscopy and flow cytometric results showed that Gb-G-PEI/Dox NPs had a higher cellular uptake efficiency than Doxorubicin in the Bel-7402 cell line due to its small size and positively charged surface. The in vivo metabolism experiments tracked by the multispectral fluorescence imaging system elucidated the sustained drug release and carrier degradation process of the Gb-G-PEI/Dox NPs. Furthermore, the in vivo antitumor effects study by the bioluminescence imaging showed that Gb-G-PEI/Dox NPs reduced the tumor size most significantly on hepatoma-bearing nude mice. As a result, Gb-G-PEI/Dox NPs were demonstrated to be a highly efficient, feasible and visible drug delivery system for tumor therapy.

Time-Variant Reliability Analysis for Rubber O-Ring Seal Considering Both Material Degradation and Random Load.

Due to the increase in working hours, the reliability of rubber O-ring seals used in hydraulic systems of transfer machines will change. While traditional methods can only analyze one of the material properties or seal properties, the failure of the O-ring is caused by these two factors together. In this paper, two factors are mainly analyzed: the degradation of material properties and load randomization by processing technology. Firstly, the two factors are defined in terms of material failure and seal failure, before the experimental methods of rubber materials are studied. Following this, the time-variant material properties through experiments and load distribution by monitoring the processing can be obtained. Thirdly, compressive stress and contact stress have been calculated, which was combined with the reliability model to acquire the time-variant reliability for the O-ring. Finally, the life prediction and effect of oil pressure were discussed, then compared with the actual situation. The results show a lifetime of 12 months for the O-ring calculated in this paper, and compared with the replacement records from the maintenance workshop, the result is credible.