Development of combinatorial chemistry methods for coatings: high-throughput adhesion evaluation and scale-up of combinatorial leads

Coupling of combinatorial chemistry methods with high-throughput (HT) performance testing and measurements of resulting properties has provided a powerful set of tools for the 10-fold accelerated discovery of new high-performance coating materials for automotive applications. Our approach replaces labor-intensive steps with automated systems for evaluation of adhesion of 8 x 6 arrays of coating elements that are discretely deposited on a single 9 x 12 cm plastic substrate. Performance of coatings is evaluated with respect to their resistance to adhesion loss, because this parameter is one of the primary considerations in end-use automotive applications. Our HT adhesion evaluation provides previously unavailable capabilities of high speed and reproducibility of testing by using a robotic automation, an expanded range of types of tested coatings by using the coating tagging strategy, and an improved quantitation by using high signal-to-noise automatic imaging. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several coatings leads. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and adhesion loss testing. These validation results have confirmed the superb performance of combinatorially developed coatings over conventional coatings on the traditional scale.     

Patient-specific bronchoscopy visualization through BRDF estimation and disocclusion correction

This paper presents an image-based method for virtual bronchoscope with photo-realistic rendering. The technique is based on recovering bidirectional reflectance distribution function (BRDF) parameters in an environment where the choice of viewing positions, directions, and illumination conditions are restricted. Video images of bronchoscopy examinations are combined with patient-specific three-dimensional (3-D) computed tomography data through two-dimensional (2-D)/3-D registration and shading model parameters are then recovered by exploiting the restricted lighting configurations imposed by the bronchoscope. With the proposed technique, the recovered BRDF is used to predict the expected shading intensity, allowing a texture map independent of lighting conditions to be extracted from each video frame. To correct for disocclusion artefacts, statistical texture synthesis was used to recreate the missing areas. New views not present in the original bronchoscopy video are rendered by evaluating the BRDF with different viewing and illumination parameters. This allows free navigation of the acquired 3-D model with enhanced photo-realism. To assess the practical value of the proposed technique, a detailed visual scoring that involves both real and rendered bronchoscope images is conducted.     

Electrodeposited Cu2ZnSnSe4 thin film solar cell with 7% power conversion efficiency

High performance Cu₂ZnSnSe₄ (CZTSe) photovoltaic materials were synthesized by electrodeposition of metal stack precursors followed by selenization. A champion solar cell with 7.0% efficiency is demonstrated. This is the highest efficiency among all of the CZTSe solar cells prepared from electrodeposited metallic precursors reported to‐date. Device parameters are discussed from the perspective of material microstructure and composition in order to improve performance. In addition, a high performance electrodeposited CZTS (S only) solar cell was demonstrated and its device characteristics were compared against the CZTSe (Se only) cell. Using secondary ion mass spectrometry for the analysis of the chemical composition of the absorber layer, a higher concentration of oxygen in the electrodeposited absorber is thought to be the root cause of the lower performance of the electrodeposited CZTS or CZTSe solar cells with respect to a solar cell fabricated by evaporation. The grain boundary areas of Sn‐rich composition are thought to be responsible for the lower shunt resistance commonly observed in CZTSe devices. We measured the longest minority carrier lifetime of 18 ns among all reported kesterite devices. This work builds a good baseline for obtaining higher efficiency earth‐abundant solar cells, while it highlights electrodepositon as a low cost and feasible method for earth‐abundant thin film solar cell fabrication. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of dense bovine cancellous bone tissue microstructure by ultrasonic backscattering using weak scattering models

A weak scattering model was proposed for the ultrasonic frequency-dependent backscatter in dense bovine cancellous bone, using two autocorrelation functions to describe the medium: one with discrete homogeneities (spherical distribution of equal spheres) and another, which considers tissue as an inhomogeneous continuum (densely populated medium). The inverse problem to estimate trabecular thickness of bone tissue has been addressed. A combination of the two autocorrelation functions was required to closely approximate the backscatter from bovine bone with various microarchitecture, given that the shape of trabeculae ranges from a rodlike to a platelike shape. Because of the large variation in trabecular thickness, both at an intraspecimen and an interspecimen level, thickness distributions for individual trabeculae for each bone specimen were obtained, and dominant trabecular sizes were determined. Comparison of backscatter measurements to theoretical predictions indicated that there were more than one dominant trabecular sizes that scatter sound for most specimens. Linear regression, performed between dominant trabecular thickness and estimated correlation length, showed significant linear correlation (R(2)=0.81). Attenuation due to scattering by a continuous distribution of scatterers was predicted to be linear over a frequency range from 0.3 to 0.9 MHz, suggesting a possibility that scattering may be a significant source of attenuation.     

Nonrigid 2-D/3-D registration for patient specific bronchoscopy simulation with statistical shape modeling: phantom validation

This paper presents a nonrigid registration two-dimensional/three-dimensional (2-D/3-D) framework and its phantom validation for subject-specific bronchoscope simulation. The method exploits the recent development of five degrees-of-freedom miniaturized catheter tip electromagnetic trackers such that the position and orientation of the bronchoscope can be accurately determined. This allows the effective recovery of unknown camera rotation and airway deformation, which is modelled by an active shape model (ASM). ASM captures the intrinsic variability of the tracheo-bronchial tree during breathing and it is specific to the class of motion it represents. The method reduces the number of parameters that control the deformation, and thus greatly simplifies the optimisation procedure. Subsequently, pq-based registration is performed to recover both the camera pose and parameters of the ASM. Detailed assessment of the algorithm is performed on a deformable airway phantom, with the ground truth data being provided by an additional six degrees-of-freedom electromagnetic (EM) tracker to monitor the level of simulated respiratory motion.     

Influence of microarchitecture alterations on ultrasonic backscattering in an experimental simulation of bovine cancellous bone aging

An experimental model which can simulate physical changes that occur during aging was developed in order to evaluate the effects of change of mineral content and microstructure on ultrasonic properties of bovine cancellous bone. Timed immersion in hydrochloric acid was used to selectively alter the mineral content. Scanning electron microscopy and histological staining of the acid-treated trabeculae demonstrated a heterogeneous structure consisting of a mineralized core and a demineralized layer. The presence of organic matrix contributed very little to normalized broadband ultrasound attenuation (nBUA) and speed of sound. All three ultrasonic parameters, speed of sound, nBUA and backscatter coefficient, were sensitive to changes in apparent density of bovine cancellous bone. A two-component model utilizing a combination of two autocorrelation functions (a densely populated model and a spherical distribution) was used to approximate the backscatter coefficient. The predicted attenuation due to scattering constituted a significant part of the measured total attenuation (due to both scattering and absorption mechanisms) for bovine cancellous bone. Linear regression, performed between trabecular thickness values and estimated from the model correlation lengths, showed significant linear correlation, with R(2)=0.81 before and R(2)=0.80 after demineralization. The accuracy of estimation was found to increase with trabecular thickness.     

Electrochemical characterization of thin film electrodes toward developing a DNA transistor

The DNA-Transistor is a device designed to control the translocation of single-stranded DNA through a solid-state nanopore. Functionality of the device is enabled by three electrodes exposed to the DNA-containing electrolyte solution within the pore and the application of a dynamic electrostatic potential well between the electrodes to temporarily trap a DNA molecule. Optimizing the surface chemistry and electrochemical behavior of the device is a necessary (but by no means sufficient) step toward the development of a functional device. In particular, effects to be eliminated are (i) electrochemically induced surface alteration through corrosion or reduction of the electrode surface and (ii) formation of hydrogen or oxygen bubbles inside the pore through water decomposition. Even though our motivation is to solve problems encountered in DNA transistor technology, in this paper we report on generic surface chemistry results. We investigated a variety of electrode-electrolyte-solvent systems with respect to their capability of suppressing water decomposition and maintaining surface integrity. We employed cyclic voltammetry and long-term amperometry as electrochemical test schemes, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning, as well as transmission electron microscopy as analytical tools. Characterized electrode materials include thin films of Ru, Pt, nonstoichiometric TiN, and nonstoichiometric TiN carrying a custom-developed titanium oxide layer, as well as custom-oxidized nonstoichiometric TiN coated with a monolayer of hexadecylphosphonic acid (HDPA). We used distilled water as well as aqueous solutions of poly(ethylene glycol) (PEG-300) and glycerol as solvents. One millimolar KCl was employed as electrolyte in all solutions. Our results show that the HDPA-coated custom-developed titanium oxide layer effectively passivates the underlying TiN layer, eliminating any surface alterations through corrosion or reduction within a voltage window from -2 V to +2 V. Furthermore, we demonstrated that, by coating the custom-oxidized TiN samples with HDPA and increasing the concentration of PEG-300 or glycerol in aqueous 1 mM KCl solutions, water decomposition was suppressed within the same voltage window. Water dissociation was not detected when combining custom-oxidized HDPA-coated TiN electrodes with an aqueous 1 mM KCl-glycerol solution at a glycerol concentration of at least 90%. These results are applicable to any system that requires nanoelectrodes placed in aqueous solution at voltages that can activate electrochemical processes.     

Development of combinatorial chemistry methods for coatings: high-throughput weathering evaluation and scale-up of combinatorial leads

Combinatorial screening of materials formulations followed by the scale-up of combinatorial leads has been applied for the development of high-performance coating materials for automotive applications. We replaced labor-intensive coating formulation, testing, and measurement with a "combinatorial factory" that includes robotic formulation of coatings, their deposition as 48 coatings on a 9x12-cm plastic substrate, accelerated performance testing, and automated spectroscopic and image analysis of resulting performance. This high-throughput (HT) performance testing and measurement of the resulting properties provided a powerful set of tools for the 10-fold accelerated discovery of these coating materials. Performance of coatings is evaluated with respect to their weathering, because this parameter is one of the primary considerations in end-use automotive applications. Our HT screening strategy provides previously unavailable capabilities of (1) high speed and reproducibility of testing by using robotic automation and (2) improved quantification by using optical spectroscopic analysis of discoloration of coating-substrate structure and automatic imaging of the integrity loss of coatings. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several cost-competitive coatings leads that match the performance of more costly coatings. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and weathering testing. These validation results have confirmed the improved weathering performance of combinatorially developed coatings over conventional coatings on the traditional scale.     

An experimental and a DFT study on the synthesis, spectroscopic characterization, and reactivity of the adducts of dimethyl- and diphenyltin(IV) dichlorides with γ-pyrones [4H-pyran-4-one (PYR) and 2,6-dimethyl-4H-pyran-4-one (DMP)]: Crystal structure of Ph2SnCl2(PYR)

The Sn(IV) R₂SnCl₂(γ-pyrone)_n [R = Me or Ph; γ-pyrone = 4H-pyran-4-one (PYR) or 2,6-dimethyl-4H-pyran-4-one (DMP); n = 1 or 2] adducts have been synthesized and investigated. The adducts Ph₂SnCl₂(PYR) (1), Me₂SnCl₂(PYR)₂ (2), Ph₂SnCl₂(DMP) (3) and Me₂SnCl₂(PYR)(PNO) (4), (PNO = 4-methylpyridine N-oxide) have been prepared by the addition of the corresponding γ-pyrone to chloroform solution of R₂SnCl₂. The new compounds have been characterized by elemental analysis and spectroscopic (IR, ¹H, ¹³C NMR and Mössbauer) means. The single-crystal diffraction study of 1 shows the Sn(IV) to be five-coordinate, [Sn-O and Sn-Cl(1), Sn-Cl(2) distances of 2.3190(13) and 2.4312(6), 2.3653(7), respectively], and the Cl-Sn-Cl bond angle to be 91.17°. The reactivity of 2 towards bipy, Ph₃PO, QNO (Q = quinoline) resulted in complete displacement of PYR and formation of already known compounds whereas, the PNO displaced only one equivalent of PYR, causing the preparation of the new mixed complex 4, possibly through a S_N¹ formation mechanism. DFT/B3LYP molecular orbital calculations were carried out for the 1-4 complexes, their precursors, Ph₂SnCl₂, (5) and Me₂SnCl₂, (6) and the ligands, PYR, DMP and PNO in an attempt to explain the structures and reactivity of the complexes. Optimized resulting geometries, vibrational frequencies, and the electron-accepting ability of the complexes and the precursors towards nucleophiles are discussed.