Crystallographic Texture Evolution in 3D Printed Polyethylene Reactor Blends.

In this work, crystallographic texture evolution in 3D printed trimodal polyethylene (PE) blends and high-density PE (HDPE) benchmark material were investigated to quantify the resulting material anisotropy, and the results were compared to materials made from conventional injection molded (IM) samples. Trimodal PE reactor blends consisting of HDPE, ultrahigh molecular weight PE (UHMWPE), and HDPE_wax have been used for 3D printing and injection molding. Changes in the preferred orientation and distribution of crystallites, i.e., texture evolution, were quantified utilizing the wide angle X-ray diffraction through pole figures and orientation distribution functions (ODFs) for 3D printed and IM samples. Since the change in weight-average molecular weight (Mw) of the blend was expected to significantly affect the resulting crystallinity and orientation, the overall Mw of the trimodal PE blend was varied while keeping the UHMWPE component weight fraction to 10% in the blend. The resulting texture was analyzed by varying the overall Mw of the trimodal blend and the process parameters in 3D printing and compared to the texture of conventional IM samples. The printing speed and orientation (defined with respect to the axis along the length of the samples) were used as the variable process parameters for 3D printing. The degree of anisotropy increases with an increase in the nonuniform distribution of intensities in pole figures and ODFs. All the highest intensity major texture components in IM and 3D printed samples (0° printing orientation) of reactor blends are observed to have crystals oriented in [001] or [001̅]. Overall, for the same throughput, 3D printed samples in the 0° orientation showed greater texture evolution and higher anisotropy compared to IM samples. Most notably, an increase in 3D printing speed increased the crystalline distribution closer to the 0° direction, increasing the anisotropy, while deviation from this printing orientation reduced crystalline distribution closer to the 0° direction, thus increasing isotropy. This demonstrates that tailoring material properties in specific directions can be achieved more effectively with 3D printing than with the injection molding process. Change in the overall Mw of the trimodal PE blend changed the preferential orientation distribution of the crystal planes to some degree. However, the degree of anisotropy remained the same in almost all cases, indicating that the effect of molecular weight distribution is not as significant as the printing speed and printing orientation in tailoring the resulting properties. The 3D printing process parameters (speed and orientation) were shown to have more influence on the texture than the material parameters associated with the blend.

Characterization of hardness and elastic modulus using nanoindentation and correlation with wear behavior of UHMWPE during uniaxial tension.

UHMWPE is the material of choice for bearing surfaces in total joint arthroplasty making its wear and mechanical properties important factors of contribution in longevity of prosthetic hip/knee implants. In this study, the variation of hardness and elastic modulus with applied load in textured UHMWPE has been investigated. Texture has been induced through uniaxial tension of UHMWPE modifying its microstructure which in turn influences the wear resistance and hence the mechanical properties of the material. Previous studies have shown hardness to be a major factor influencing wear resistance. However, recently, the ratio of hardness (H) to elastic modulus (E) has been recognized as a more influential parameter of wear resistance. The validity of predicting wear resistance using H/E ratio has been examined in this work. Power law variation with load for the bioimplant material UHMWPE has been investigated at different strain levels. It has been observed that power law exponent of 2 can only be achieved at higher load levels. Overall, this work provides an insight into influencing the properties of bioimplant material UHMWPE by modifying the microstructure of the material through inducing texture which ultimately affects the longevity of the prosthetic implants.

Opposite Sensing Response of Heterojunction Gas Sensors Based on SnO2-Cr2O3 Nanocomposites to H2 against CO and Its Selectivity Mechanism.

Metal oxide semiconductor (MOS) gas sensors show poor selectivity when exposed to mixed gases. This is a challenge in gas sensors and limits their wide applications. There is no efficient way to detect a specific gas when two homogeneous gases are concurrently exposed to sensing materials. The p-n nanojunction of xSnO2-yCr2O3 nanocomposites (NCs) are prepared and used as sensing materials (x/y shows the Sn/Cr molar ratio in the SnO2-Cr2O3 composite and is marked as SnxCry for simplicity). The gas sensing properties, crystal structure, morphology, and chemical states are characterized by employing an electrochemical workstation, an X-ray diffractometer, a transmission electron microscope, and an X-ray photoelectron spectrometer, respectively. The gas sensing results indicate that SnxCry NCs with x/y greater than 0.07 demonstrate a p-type behavior to both CO and H2, whereas the SnxCry NCs with x/y < 0.07 illustrate an n-type behavior to the aforementioned reduced gases. Interestingly, the SnxCry NCs with x/y = 0.07 show an n-type behavior to H2 but a p-type to CO. The effect of the operating temperature on the opposite sensing response of the fabricated sensors has been investigated. Most importantly, the mechanism of selectivity opposite sensing response is proposed using the aforementioned characterization techniques. This paper proposes a promising strategy to overcome the drawback of low selectivity of this type of sensor.

Y-doped CaZrO3/Co3O4 as novel dense diffusion barrier materials for a limiting current oxygen sensor.

Herein, we illustrate a feasible strategy to strengthen the gas sensing of Y-doped CaZrO3 (YxCa1-xZr0.7O3-δ (x = 0.05, 0.06, and 0.07))/0.1Co3O4 used as sensing materials. This compound was prepared via a solid-state reaction technique. The structural, morphological, electrical, and sensing features such as phase identification, microstructure, ionic conductivity, total conductivity and sensitivity of the fabricated sensors were evaluated via X-ray diffraction, scanning electron microscopy, electron-blocking method, electrochemical impedance spectroscopy and cyclic voltammetry. In addition, the influence of the Y-dopant on the properties of YxCa1-xZr0.7O3-δ/Co3O4 was thoroughly studied. XRD results revealed the formation of the orthorhombic perovskite phase of YxCa1-xZr0.7O3-δ. Moreover, the obtained results from the electrical properties elucidated high electronic and low ionic conductivities, and small polaron conduction of YxCa1-xZr0.7O3-δ/Co3O4. Furthermore, the results confirmed an excellent limiting current plateau for the fabricated oxygen sensor based on YxCa1-xZr0.7O3-δ/Co3O4. In particular, experimental observation indicates that Y-doping at the Ca site and/or Zr site might be difficult.

Conductivity and mixed conductivity of a novel dense diffusion barrier and the sensing properties of limiting current oxygen sensors.

First-principles calculations were used to explore the effect of various Y-doping levels on the electrical conductivity of SrTiO3. Herein, we prepared ((Y0.07Sr0.93Ti0.6Fe0.4-xO3-δ)/x/3Co3O4 (x = 0.1, 0.2, 0.3)) composites using a solid state reaction method. The properties of these sensing materials and the fabricated sensors including crystal phase composition, microstructures, oxygen ionic conductivity, total conductivity and sensor performance were investigated in detail. XRD demonstrates the formation of a highly cubic perovskite structure. The introduction of Co3O4 promotes remarkably the electronic conductivity of the Y0.07Sr0.93Ti0.6Fe0.4-xO3-δ/x/3Co3O4 composites due to the formation of n-type CoO and p-type Co2O3. A limiting current oxygen sensor based on (Y0.07Sr0.93Ti0.6Fe0.4-xO3-δ)/x/3Co3O4 as a dense diffusion barrier shows excellent sensing performance. The recovery time is less than the response time, indicating that Co2O3 promotes the gas desorption reaction which results in a shorter recovery time. The obtained results demonstrate a direct relationship between limiting current (IL) and oxygen content.

Analytical Thermal Modeling of Powder Bed Metal Additive Manufacturing Considering Powder Size Variation and Packing.

This work presents a computationally efficient predictive model based on solid heat transfer for temperature profiles in powder bed metal additive manufacturing (PBMAM) considering the heat transfer boundary condition and powder material properties. A point moving heat source model is used for the three-dimensional temperature prediction in an absolute coordinate. The heat loss from convection and radiation is calculated using a heat sink solution with a mathematically discretized boundary considering non-uniform temperatures and heat loss at the boundary. Powder material properties are calculated considering powder size statistical distribution and powder packing. The spatially uniform and temperature-independent material properties are employed in the temperature prediction. The presented model was tested in PBMAM of AlSi10Mg under different process conditions. The calculations of material properties are needed for AlSi10Mg because of the significant difference in thermal conductivity between powder form and solid bulk form. Close agreement is observed upon experimental validation on the molten pool dimensions.

Analytical Thermal Modeling of Metal Additive Manufacturing by Heat Sink Solution.

Metal additive manufacturing can produce geometrically complex parts with effective cost. The high thermal gradients due to the repeatedly rapid heat and solidification cause defects in the produced parts, such as cracks, porosity, undesired residual stress, and part distortion. Different techniques were employed for temperature investigation. Experimental measurement and finite element method-based numerical models are limited by the restricted accessibility and expensive computational cost, respectively. The available physics-based analytical model has promising short computational efficiency without resorting to finite element method or any iteration-based simulations. However, the heat transfer boundary condition cannot be considered without the involvement of finite element method or iteration-based simulations, which significantly reduces the computational efficiency, and thus the usefulness of the developed model. This work presents an explicit and closed-form solution, namely heat sink solution, to consider the heat transfer boundary condition. The heat sink solution was developed from the moving point heat source solution based on heat transfer of convection and radiation. The part boundary is mathematically discretized into many heats sinks due to the non-uniform temperature distribution, which causes non-uniform heat loss. The temperature profiles, thermal gradients, and temperature-affected material properties are calculated and presented. Good agreements were observed upon validation against experimental molten pool measurements.

Heat Source Modeling in Selective Laser Melting.

Selective laser melting (SLM) is an emerging additive manufacturing (AM) technology for metals. Intricate three-dimensional parts can be generated from the powder bed by selectively melting the desired location of the powders. The process is repeated for each layer until the part is built. The necessary heat is provided by a laser. Temperature magnitude and history during SLM directly determine the molten pool dimensions, thermal stress, residual stress, balling effect, and dimensional accuracy. Laser-matter interaction is a crucial physical phenomenon in the SLM process. In this paper, five different heat source models are introduced to predict the three-dimensional temperature field analytically. These models are known as steady state moving point heat source, transient moving point heat source, semi-elliptical moving heat source, double elliptical moving heat source, and uniform moving heat source. The analytical temperature model for all of the heat source models is solved using three-dimensional differential equations of heat conduction with different approaches. The steady state and transient moving heat source are solved using a separation of variables approach. However, the rest of the models are solved by employing Green's functions. Due to the high temperature in the presence of the laser, the temperature gradient is usually high which has a substantial impact on thermal material properties. Consequently, the temperature field is predicted by considering the temperature sensitivity thermal material properties. Moreover, due to the repeated heating and cooling, the part usually undergoes several melting and solidification cycles, and this physical phenomenon is considered by modifying the heat capacity using latent heat of melting. Furthermore, the multi-layer aspect of the metal AM process is considered by incorporating the temperature history from the previous layer since the interaction of the layers have an impact on heat transfer mechanisms. The proposed temperature field models based on different heat source approaches are validated using experimental measurement of melt pool geometry from independent experimentations. A detailed explanation of the comparison of models is also provided. Moreover, the effect of process parameters on the balling effect is also discussed.

Analytical Modeling of In-Process Temperature in Powder Bed Additive Manufacturing Considering Laser Power Absorption, Latent Heat, Scanning Strategy, and Powder Packing.

Temperature distribution gradient in metal powder bed additive manufacturing (MPBAM) directly controls the mechanical properties and dimensional accuracy of the build part. Experimental approach and numerical modeling approach for temperature in MPBAM are limited by the restricted accessibility and high computational cost, respectively. Analytical models were reported with high computational efficiency, but the developed models employed a moving coordinate and semi-infinite medium assumption, which neglected the part dimensions, and thus reduced their usefulness in real applications. This paper investigates the in-process temperature in MPBAM through analytical modeling using a stationary coordinate with an origin at the part boundary (absolute coordinate). Analytical solutions are developed for temperature prediction of single-track scan and multi-track scans considering scanning strategy. Inconel 625 is chosen to test the proposed model. Laser power absorption is inversely identified with the prediction of molten pool dimensions. Latent heat is considered using the heat integration method. The molten pool evolution is investigated with respect to scanning time. The stabilized temperatures in the single-track scan and bidirectional scans are predicted under various process conditions. Close agreements are observed upon validation to the experimental values in the literature. Furthermore, a positive relationship between molten pool dimensions and powder packing porosity was observed through sensitivity analysis. With benefits of the absolute coordinate, and high computational efficiency, the presented model can predict the temperature for a dimensional part during MPBAM, which can be used to further investigate residual stress and distortion in real applications.

A screen printed carbon electrode modified with carbon nanotubes and gold nanoparticles as a sensitive electrochemical sensor for determination of thiamphenicol residue in milk.

Antibiotic residues in milk are of great concern for health regulatory agencies, milk consumers, and dairy farmers due to their destructive effects, ranging from allergic reactions, antibiotic resistance and the ability to interfere with the production of fermented products (i.e. cheese and yogurt). Therefore, a reliable, fast, and simple method needs to be developed to monitor antibiotic residues in milk samples before distribution to consumers. In this study, the first sensitive electrochemical sensor is presented for the determination of thiamphenicol (TAP), a broad-spectrum antibiotic in bovine milk. In the fabrication process, a screen printed electrode (SPE) was modified with gold nanoparticles (AuNPs) and carbon nanotubes (CNTs) using ethylenediamine (en) as a cross linker. Cyclic voltammetry studies showed an adsorptive control process for the electro-oxidation of TAP at -0.1 V on the modified electrode of SPE/CNT/en/AuNPs. Differential pulse voltammetry (DPV) was applied for the quantitative determination of TAP under optimized conditions (0.1 M citrate buffer, pH 6.0, accumulation potential -0.7 V, and accumulation time 150 s). A DPV study for TAP shows a wide linear calibration range of 0.1-30 µM with the detection limit of 0.003 µM. Furthermore, the developed sensor displays high sensitivity, reproducibility, repeatability, and good stability for the detection of TAP. The proposed sensor was successfully applied for the determination of spiked TAP in bovine milk with satisfactory results.

Efficient three-phase reconstruction of heterogeneous material from 2D cross-sections via phase-recovery algorithm.

Digital reconstruction of a complex heterogeneous media from the limited statistical information, mostly provided by different imaging techniques, is the key to the successful computational analysis of this important class of materials. In this study, a novel approach is presented for three-dimensional (3D) reconstruction of a three-phase microstructure from its statistical information provided by two-dimensional (2D) cross-sections. In this three-step method, first two-point correlation functions (TPCFs) are extracted from the cross-section(s) using a spectral method suitable for the three-phase media. In the next step, 3D TPCFs are approximated for all vectors in a representative volume element (RVE). Finally, the 3D microstructure is realized from the full-set TPCFs obtained in the previous step, using a modified phase-recovery algorithm. The method is generally applicable to any complex three-phase media, here illustrated for an SOFC anode microstructure. The capabilities and shortcomings of the method are then investigated by performing a qualitative comparison between example cross-sections obtained computationally and their experimental equivalents. Finally, it is shown that the method almost conserves key microstructural properties of the media including tortuosity, percolation and three-phase boundary length (TPBL).

Synthesis and growth mechanism of thin-film TiO2 nanotube arrays on focused-ion-beam micropatterned 3D isolated regions of titanium on silicon.

In this paper, the fabrication and growth mechanism of net-shaped micropatterned self-organized thin-film TiO2 nanotube (TFTN) arrays on a silicon substrate are reported. Electrochemical anodization is used to grow the nanotubes from thin-film titanium sputtered on a silicon substrate with an average diameter of ~30 nm and a length of ~1.5 µm using aqueous and organic-based types of electrolytes. The fabrication and growth mechanism of TFTN arrays from micropatterned three-dimensional isolated islands of sputtered titanium on a silicon substrate is demonstrated for the first time using focused-ion-beam (FIB) technique. This work demonstrates the use of the FIB technique as a simple, high-resolution, and maskless method for high-aspect-ratio etching for the creation of isolated islands and shows great promise toward the use of the proposed approach for the development of metal oxide nanostructured devices and their integration with micro- and nanosystems within silicon-based integrated-circuit devices.

Mechanical behavior of a cellulose-reinforced scaffold in vascular tissue engineering.

Scaffolds constitute an essential structural component in tissue engineering of a vascular substitute for small grafts by playing a significant role in integrating the overall tissue constructs. The microstructure and mechanical properties of such scaffolds are important parameters to promote further cellular activities and neo-tissue development. Cellulose nanowhiskers (CNWs), an abundant, biocompatible material, could potentially constitute an acceptable candidate in scaffolding of a tissue-engineered vessel. Inspired by the advantages of cellulose and its derivatives, we have designed a biomaterial comprising CNWs embedded in a matrix of cellulose acetate propionate to fabricate a fully bio-based scaffold. To ensure uniform distribution, CNWs were delicately extracted from a multi-stage process and dispersed in an acetone suspension prior to the composite fabrication. Comparable to carbon nanotubes or kevlar, CNWs impart significant strength and directional rigidity even at 0.2 wt% and almost double that at only 3.0 wt%. To ensure the accuracy of our experimental data and to predict the unusual reinforcing effect of CNWs in a cellulose-based composite, homogenization schemes such as the mean field approach and the percolation technique were also investigated. Based on these comparisons, the tendency of CNWs to interconnect with one another through strong hydrogen bonding confirmed the formation of a three-dimensional rigid percolating network, fact which imparted an excellent mechanical stability to the entire structure at such low filler contents. Hence, our fibrous porous microstructure with improved mechanical properties could introduce a potential scaffold to withstand the physiological pressure and to mimic the profile features of native extracellular matrix in a human vessel. We believe that our nanohybrid design not only could expand the biomedical applications of renewable cellulose-based materials but also could provide a potential scaffold candidate in tissue engineering of small diameter grafts.

Self-standing crystalline TiO2 nanotubes/CNTs heterojunction membrane: synthesis and characterization.

In the present study, we report for the first time synthesis of TiO(2) nanotubes/CNTs heterojunction membrane. Chemical vapor deposition (CVD) of CNTs at 650 °C in a mixture of H(2)/He atmosphere led to in situ detachment of the anodically fabricated TiO(2) nanotube layers from the Ti substrate underneath. Morphological and structural evolution of TiO(2) nanotubes after CNTs deposition were investigated by field- emission scanning electron microscopy (FESEM), glancing angle X-ray diffraction (GAXRD), and X-ray photoelectron spectroscopy (XPS) analyses.

Uniform directional alignment of single-walled carbon nanotubes in viscous polymer flow.

In this work, we probed the effects of shear flow on the alignment of dispersed single-walled carbon nanotubes in polymer solutions. Two different systems were compared: Single-walled carbon nanotubes dispersed using an anionic surfactant and single-walled carbon nanotubes dispersed using an anionic surfactant and a weakly binding polymer. It was determined that the addition of the weakly binding polymer increased the degree of dispersion of the carbon nanotubes and the ability to induce their alignment when subjected to shear forces.