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A major goal in the field of regenerative medicine is to improve our understanding of how biomaterial properties affect cells of the immune system. Systematic variation of defined chemical properties could help to understand which factors determine and modulate cellular responses. A series of copolymers poly[acrylonitrile-co-(N-vinylpyrrolidone)]s (P(AN-co-NVP)) served as model system, in which increasing hydrophilicity was adjusted by increasing the content related to the NVP based repeating units (nNVP) (0, 4.6, 11.8, 22.3, and 29.4 mol%). The influence of increasing nNVP contents on cellular response of human primary monocyte derived dendritic cells (DC), which play a key role in the initiation of immune responses, was investigated. It was shown using the LAL-Test as well as a macrophage-based assay, that the materials were free of endotoxins and other microbial contaminations, which could otherwise bias the readout of the DC experiments. The increasing nNVP content led to a slightly increased cell death of DC, whereas the activation status of DC was not systematically altered by the different P(AN-co-NVP)s as demonstrated by the expression of co-stimulatory molecule and cytokine secretion. Similarly, under inflammatory conditions mimicked by the addition of lipopolysaccharides (LPS), neither the expression of co-stimulatory molecules nor the release of cytokines was influenced by the different copolymers. Conclusively, our data showed that this class of copolymers does not substantially influence the viability and the activation status of DC.
During the epitaxial bottom up growth of nanowire (NW) arrays, occasional kinks in growth direction can lead to intersecting and consequently self-welded crystalline connections between NWs. In order to study these self-welded metallurgical NW junctions, a NW bridge device architecture which requires no post-growth processing was used to grow and stabilize Si NW junctions. Scanning Photocurrent Microscopy (SPCM) was used to study the optoelectronic properties of the NW junctions as well as the characteristics of the NW bridge devices. SPCM measurements show a bias dependent photocurrent (PC) response at the NW junction indicating local band bending at this location. A decay of the PC response away from the junction is also seen in the secondary NW channel ensuring an electrical connection. These junction properties may be important for ensemble NW optical devices.
We report a systematic study of polarization and magnetic field effects on the optical response of Fe3O4-silicone elastomer composite. The Fe3O4 particles were aligned in a silicone elastomer matrix with an external static magnetic field. Films of composites containing 5wt% of 20nm ≤ d ≤ 30nm Fe3O4 particles aligned in- and out-of-plane in the elastomer host were prepared. The optical spectra of the films were measured with the Perkin-Elmer Lambda 950 UV/vis/NIR spectrometer. We observed a systematic redshift in the optical response of the outof-plane composite films with increasing static magnetic field strength, which saturated near 600 Gauss. We obtained a maximum redshift of ∼46 nm at 600 Gauss. The observed redshift in the optical response of the out-of-plane composite film is attributed to the effect of the magnetic field. This facilitated the formation of the highly aligned particles that induced strong electric dipole in the aligned particles. Interestingly, there were no observable shifts with increasing magnetic field strength in the in-plane films, suggesting that the orientation (polarization) of the magnetic dipole and the induced electric dipole play a crucial role in the optical response.
Recently, Nb-Si based alloys have attracted considerable attention as potential candidate materials for ultra-high temperature applications, because of their low densities and high melting points. However, it is still very difficult to obtain materials with a good balance of high-temperature strength and room-temperature toughness. To address this issue, microstructure control is considered to be a promising method. In applying microstructure control to Nb-Si based alloys with a eutectic reaction (L → Nbss + Nb3Si) and a eutectoid reaction (Nb3Si → Nbss + Nb5Si3), the key is the control of Nb3Si phase stability. Nbss (Nb solid solution) is considered as a ductile phase. In previous reports, it was revealed that different elements had different effects on the stability of Nb3Si. In particular, Mo and W (>3 at %) destabilize the Nb3Si phase, while Ti and Ta stabilize it, and Zr acts as an accelerator for decomposition of Nb3Si. On the other hand, Cr is known to enhance the formation of the ductile Nbss phase. In the present study, we investigated the effects of adding combinations of stabilizing, destabilizing, and accelerating elements with Cr, such as Cr and W, Cr and Ta, Cr and Zr. According to SEM observation, different microstructures were obtained with different combination of additives, and the fracture toughness at room temperature of these samples were also evaluated to reveal the effects of the microstructure on the mechanical properties of Nb-Si based alloys.
Scanning Thermal Microscopy measurements with a resistive microprobe electrically heated were performed for different probe temperatures, for probe free in air and in contact with various specimens. The measured relative difference of Joule power dissipated in the probe when tip is in contact with a sample and when it is free in air is studied for different magnitude of the electrical current that heats the probe. A variation of this signal, never outlined before, is observed. A predictive modeling is used to explain these results and identify from the experimental data the global thermal conductance of the probe-sample thermal exchange for experiments performed in ambient conditions.
Relatively low efficiency is one of the main obstacles to overcome in the engineering of organic bulk heterojunction (BHJ) solar cells. Reduced graphene oxide (RGO), which has high conductivity, has been proposed to enhance the function of PCBM in the interfacial dissociation of excitons, but incorporating it into the hydrophobic photoactive polymers has proved challenging. Here we describe a novel technique for incorporating Au nanoparticles (AuNp) into the structure of the RGO. The AuNps then interact with the sulfur groups on the photoactive polymer component, while the RGO interacts via π – π stacking with the chemically similar PCBM, thereby anchoring the complex to the polymer interface. Graphene oxide was synthesized and then reduced in the presence of a gold salt. The resulting gold-functionalized RGO (AuRGO) sheets were characterized using TGA, FTIR, and TEM. The AuRGO was not soluble in chlorobenzene; however, in the presence of P3HT, the AuRGO dissolved, suggesting a reaction between the gold and the sulfur of the P3HT via a metal-thiolate bond. At 2 mg/ml, AuRGO increased the solar cell efficiency approximately 50% over the control, but higher concentrations produced large, columnar structures which blocked the electrode from having a uniform contact with the active layer.
The phase transformation of spinodal decomposition proceeds without nucleation and is affected by the alloy composition, temperature, interfaces and gradient energy, as well as the presence of lattice strain. As a consequence, a coherent spinodal can be depressed well below the chemical spinodal within the miscibility gap. Phase separation from a solid solution within the spinodal leads to the formation of characteristic composition wavelengths. In the nickel-based alloy system, a nanolaminate structure is used to initially create an artificial composition fluctuation with unique nanoscale wavelengths. The direct measurement of diffusivity at low temperatures in Cu-Ni and Cu-Ni(Fe), from the spinodal towards room temperature, requires sensitivity to the nanoscale fluctuations in composition. For this purpose, x-ray diffraction scans are used to assess changes in the short-range order of the composition fluctuation and the corresponding changes in the gradient energy, from which an evaluation of lattice distortion effects reveals a peak in strain energy for 2-3 nm composition wavelengths.
Silicon nanoparticles-based inks were investigated in respect of their suitability for photovoltaic and thermoelectric applications. Nanoparticles with a diameter ranging between 20 to 150 nm were functionalized in order to avoid oxidation as well as having a good stability in suspension. After inkjet-printing and drying, they were annealed up to 1000 °C under nitrogen atmosphere by both rapid thermal and microwave annealing. The influence of the annealing treatment on the structural, electrical, optical and thermal properties was investigated by Raman, SEM, electrical and optical measurements. SEM and Raman demonstrate evolution of the microstructure at temperature as low as 600 °C. Optical, electrical and thermal properties depend strongly on the annealing temperature and tend to exhibit a modification of physical properties above 800 °C when the smallest nanoparticles begin to melt. The annealing method has been identified to be of primary importance on the layer microstructure and its thermal behavior.
In this work we report on the characteristics of GaAs/AlGaAs heterostructures with a symmetric double two-dimensional electron gas (D-2DEG). Optical characterization was made by room temperature photoreflectance (PR) spectroscopy as well as electrical properties were determinated using the quantum Hall effect measurements at 2K. In order to study the surface effects on the conduction band profile, three samples with different GaAs cap layer thickness (25, 60 and 80 nm) were grown by the molecular beam epitaxy. Photoreflectance spectra at room temperature show the wide-period Franz-Keldysh oscillations between 1.42 and 1.70 eV originated by the surface electric field. The analysis of these oscillations shows that the surface electric field varies from 503 to 120 kV/cm whereas the thickness of the cap layer increases that was produced by the reduction of the depletion zone near the surface. Using QHE measurements we found that electron density increases if the surface electric field decreases.
It is well established that controlled high-temperature annealing of hydrogen silsesquioxane leads to the formation of small spherical silicon nanocrystals (∼3 nm). The present study outlines an investigation into the influence of annealing time and temperature. After prolonged annealing, crystal surfaces thermodynamically self-optimize to form a variety of faceted structures (e.g., cubic, truncated trigonal and hexagonal structures).
Organic solar cells consisting of Phthalocyaninatocopper (PcCu) as donor and the Buckminsterfullerene C60 as acceptor molecule were prepared by physical vapor deposition as planar or bulk heterojunctions. The devices were studied by IV-characterization as well as intensity-modulated photovoltage spectroscopy to determine the average lifetime of charge carriers formed subsequent to light absorption. An increasing charge carrier lifetime was determined for an increasing PcCu-content in the films. Back transfer of electrons at the undesired contact of C60 with PEDOT:PSS as well as recombination following hole trapping in interface states in the contact of PcCu with C60 or in isolated domains of PcCu are discussed as possible origins.
A sophomore level Materials Engineering course entitled, “Materials, Ethics, & Society” at Cal Poly analyzes the interactions between technology and society, and emphasizes the communication of societal and ethical impacts of technology to diverse audiences. Students study materials in a historical context, not only to highlight specific materials science concepts, but also to explore societal-technology connections. Starting from the Stone Age, advances in civilizations have come about through discoveries and new uses of materials. World geography, history, and culture become intertwined with the casting of metals, alloy development, ceramics, and phase diagrams. Students highlight the social relevancy of materials throughout history, and seek parallel themes in today’s world. While learning about the development of the atomic bomb, students also examine the ethical dilemmas of the scientists and the current NSPE Code of Ethics for Engineers. In addition, the role of the engineering profession is examined with the NAE Engineering Grand Challenges and current news items. Students investigate how materials engineering can help society through examples of appropriate technology solutions, such as designing porosity in ceramics for water filters and food storage pots. Students develop their analytical and communication skills by discussing C.P. Snow’s “two cultures” and debating a rationale for scientific literacy. Students are also trained in informal science learning in preparation for NanoDays with young and diverse audiences. At the same time, they learn about nano-scale science and technology principles, and the associated societal and ethical implications. The course culminates with student-created videos for the general public that highlight a material or technology of importance to society and integrates the material science with ethical, environmental, and societal dimensions.
Multiscale dislocation dynamics plasticity (MDDP) model is used to investigate the evolution of dislocation microstructure in copper single crystals subjected to low cycle fatigue loading. Half cycle total plastic strain simulations are carried out at strain amplitudes ranging from 1×10-3 to 8×10-3. The initial hardening is investigated and the micro-structural cause behind it is presented. In addition, the loading history is presented and the effect of the initial micro-structure and dislocation distribution on the hardening behavior is studied. In addition, the evolution of the microstructures is examined. In depth analyses of the dislocation microstructures show that: 1) dislocation planes that are parallel and very close to each other are formed, 2) these walls contain dipoles that keep on zipping and unzipping during the first few cycles until they reach some stable zipping configuration. We can see that the hardening rate decreases with the increase of the number of cycles where we have large hardening rate in the first cycles then we reach to somehow constant stress. Our results are qualitatively in good agreement with recent experimental results of low cycle fatigue deformation.
Single crystals of E21 (L12) Ni3AlC1-x were prepared by the unidirectional solidification using the optical floating zone melting method to determine their mechanical properties. Particularly the effects of interstitial carbon atoms on mechanical properties were evaluated by compression tests at room temperature. Operative slip system of E21 Ni3AlC is {111}<011> type which is the same as that of L12 Ni3Al. Strength of Ni3AlC single crystals increases with carbon concentration due to the solid solution effect, though the stress relief of yielding behavior is enhanced at the intermediate carbon content at around 3at%. A large gap appears in the carbon concentration dependence of critical resolved shear stress (as well as yield stress) at almost the same carbon content. This discontinuity in strengthening is attributed to the interaction between multiple solute carbon atoms and mobile dislocations.
We fabricated Cu2ZnSn(SxSe1-x)4 (CZTSSe) solar cells by a printing and high-pressure sintering (PHS) process. First, the CZTSSe solid solution powders were synthesized by heating the elemental mixtures at 550oC for 5 h in an N2 gas atmosphere. We fabricated CZTSSe films by a printing and high-pressure sintering (PHS) process. The obtained dense CZTSSe film was post-annealed at 550oC for 10 min under an N2 +5% H2S gas atmosphere. We fabricated CZTSSe solar cells with the device structure of Ag/ITO/i-ZnO/CdS/CZTSSe/Mo/soda-lime glass. The CZTSSe solar cell showed an efficiency of 2.1%, with Voc of 272 mV, Jsc of 18.0 mA/cm2 and FF of 0.44.
Making field effect transistors (FETs) on thin flake of single crystal isolated from layered materials was pioneered by the success of graphene. To overcome the difficulties of the zero band gap in graphene electronics, we report the fabrication of an electric double layer (EDL) transistor, a variant of FET, based on another layered material, MoS2. Using strong carrier tunability found in EDL coupled by ion movement, MoS2 transistor displayed an unambiguously ambipolar operation in addition to its commonly observed n-type transport. A high on/off ratio >104, large “ON” state conductivity of ∼mS, and a high reachable n2D ∼ 1×1014 cm-2 confirmed the high performance transistor operation being important for application. The high-density carriers of both holes and electrons can drive the MoS2 channel to metallic states indicating that new electronic phases could be accessed using the protocol established in making EDL gated transistors on layered materials.
Titanium (IV) oxide, TiO2, has been the object of intense scrutiny for energy applications. TiO2 is inexpensive, non-toxic, and has excellent corrosion resistance when exposed to electrolytes. A major drawback preventing the widespread use TiO2 for photolysis is its relatively large band gap of ∼3eV. Only light with wavelengths shorter than 400 nm, which is in the ultraviolet portion of the spectrum, has sufficient energy to be absorbed. Less than 14 percent of the solar irradiation reaching the earth’s surface has energy exceeding this band gap. Adding dopants such as transition metals has long been used to reduce the gap and increase photocatalytic activity by accessing the visible part of the solar spectrum. The degree to which the band gap is reduced using transition metals depends in part on the overlap of the d-orbitals of the transition metals with the oxygen p-orbitals. Therefore, doping with anions such as nitrogen to modify the cation-anion orbital overlap is another approach to reduce the gap. Recent studies suggest that using a combination of transition metals and nitrogen as dopants is more effective at introducing intermediate states within the band gap, effectively narrowing it. Here we report the synthesis of mesoporous TiO2 spheres, co-doped with transition metals and nitrogen that exhibit a nearly flat absorbance response across the visible spectrum extending into the near infrared.
Forming voltage (VForm) and initial resistance of NiO-based resistive switching (RS) cells with various NiO films were investigated. Deposited NiO films were 〈111〉-oriented and the lattice constant was larger than that of bulk. It was revealed from XRD analyses that there were residual compressive stresses in NiO films. The magnitude of the residual stress was different among NiO films depending on their deposition conditions, and VForm monotonically increases with the increase in the magnitude of the residual stress. The relationship between VForm and the residual stress may be ascribed to the changes in the density of oxygen vacancies in NiO films. NiO films were also post annealed in Ar at 450°C. RS cells with annealed NiO films having small oxygen composition exhibited forming-free behavior, indicating the generation of conductive filaments by the annealing. The region whose lattice constant is smaller than that of bulk appeared after annealing only in such NiO films, suggesting that the small lattice-constant region may be linked to the generation of the filaments.
The work takes advantage of a newly developed measurement system which enables to investigate the thermodynamic properties of thin films including battery layer sequences. This technique, Thin-Film Calorimetry (TFC), is based on the detection of resonance frequency shifts of bulk acoustic wave resonators. Thin films with a thickness of several micrometers of the material of interest are deposited on the resonators. By measuring the temperature dependent shift of the resonance frequency, the device is working as a precise temperature sensor. The production or consumption of latent heat by the active layer(s) results in temperature fluctuations with respect to the furnace where the sensor is placed. Those information enable to extract the temperature and time dependence of phase transformations as well as the associated enthalpies. To cover a temperature range from -20 to 900 °C high-temperature stable piezoelectric resonators made of langasite crystals (La3Ga5SiO14) are applied.
Initially, metallic layers of tin and aluminum are used to test and verify this approach. The temperatures and enthalpies of solid-liquid as well as of solid-solid phase transformation are observed in the correct manner. Further, the thermodynamic data of the battery materials Li(Ni0.8Co0.15Al0.05)O2-δ (NCA) and LiMn2O4-δ (LMO) obtained by TFC are determined and discussed. Both cathode materials are amorphous after deposition and show crystallization during heating at 460 °C (NCA) and 600 °C (LMO). The associated enthalpies are 5.3 kJ/mol (55 J/g) and 17.3 kJ/mol (96 J/g), respectively.
A large area nanogap electrode fabrication method combinig conventional lithography patterning with the of focused ion beam (FIB) is presented. Lithography and a lift-off process were used to pattern 50 nm thick platinum pads having an area of 300 μm × 300 μm. A range of 30-300 nm wide nanogaps (length from 300 μm to 10 mm ) were then etched using an FIB of Ga+ at an acceleration voltage of 30 kV at various beam currents. An investigation of Ga+ beam current ranging between 1-50 pA was undertaken to optimise the process for the current fabrication method. In this study, we used Monte Carlo simulation to calculate the damage depth in various materials by the Ga+. Calculation of the recoil cascades of the substrate atoms are also presented. The nanogap electrodes fabricated in this study were found to have empty gap resistances exceeding several hundred MΩ. A comparison of the gap length versus electrical resistance on glass substrates is presented. The results thus outline some important issues in low-conductance measurements. The proposed nanogap fabrication method can be extended to various sensor applications, such as chemical sensing, that employ the nanogap platform. This method may be used as a prototype technique for large-scale fabrication due to its simple, fast and reliable features.