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At least 19 records

Friction and wear of tin and tin alloys from minus 100 C to 150 C

Sliding friction experiments were conducted with an iron (110) single-crystal pin sliding on single and polycrystalline tin and tin alloys. Specimens were examined at various ambient temperatures from -100 to 150 C. Applied loads varied from 1 to 50 grams, and sliding velocity was constant at 0.7 mm/min. Results indicate that the crystal transformation of tin influences the friction coefficient. Friction was higher for the diamond structure (gray tin) than it was for the body-centered tetragonal structure (white tin). Bismuth arrested the crystal transformation, which resulted in constant friction over the temperature range -100 to 150 C. Both copper and aluminum enhanced the kinetics of transformation, with aluminum producing a nearly twofold change in friction with the crystal transformation.

Buckley, D. H.↗

Modeling the Effect of Surface Platinum–Tin Alloys on Propane Dehydrogenation on Platinum–Tin Catalysts

Uncertainty analysis, reported experimental literature data, and density functional theory were synthesized to model the effect of surface tin coverage on platinum-based catalysts for nonoxidative propane dehydrogenation to propylene. Here, this study tests four different platinum–tin skin surface models as potential catalytic sites, Pt 3 Sn/Pt(100), PtSn/Pt(100), Pt 3 Sn/Pt(111), and Pt 2 Sn/Pt(211), and compares them to the corresponding pure Pt surface sites using an uncertainty analysis methodology that uses BEEF-vdW with its ensembles (BMwE) to generate the uncertainty for the energies of the intermediates and transition states. One experimental data set with two experimental observations, selectivity to propylene and turnover frequency of propylene, was used as a calibration data set to evaluate the impact of the experimental data on informing the models. This study finds that the prior model for Pt 3 Sn/Pt(100) is the most active and Pt 2 Sn/Pt(211) is the most selective toward propylene. Active sites on the (100) facet have the highest probability of being responsible for C 1 and C 2 product formations (C–C bond cleavage). Increasing the Sn coverage on the (100) surface facet to a PtSn/Pt(100) active site leads to a significantly reduced rate and might explain the experimentally observed higher selectivity of Sn-doped catalysts relative to pure Pt catalysts. Next, this study finds that for all surfaces, except PtSn/Pt(100), the rate-controlling steps are the initial dehydrogenation steps alongside some partially rate-controlling second dehydrogenation steps. For PtSn/Pt(100), only the initial terminal dehydrogenation step to CH 3 CH 2 CH 2 * and second dehydrogenation steps are rate-controlling. Next, the calibrated models for all surfaces were found to be selective toward propylene production and model the reported turnover frequency successfully. Nevertheless, Pt 2 Sn/Pt(211) emerges as the active site with some (minor) evidence as the main active site based on Jeffreys’ scale interpretation of Bayes factors. This observation agrees with prior studies that also found step sites to be most likely the most relevant active sites for pure Pt catalysts. Overall, the results indicate that tin, in addition to affecting the binding strength of the adsorbed species, prevents deeper dehydrogenation (reducing coking) and cracking reactions through increasing activation barriers for unwanted side reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contact resistivities of sputtered TiN and Ti-TiN metallizations on solar-cell-type-silicon

The resistivities of TiN and Ti-TiN contacts on a shallow junction solar-cell-type silicon substrate have been determined by the method of the transmission line model. The contacts investigated are shown to be suitable for standard solar cells from an electrical point of view. Contact resistivity values of the order of 0.0001 ohm/sq cm as obtained for the n(+)Si-TiSi2-TiN contact system may be acceptable for concentrations up to 100 times, but lower values are necessary beyond this point.

Maenpaa, M.↗

Low gravity solidification structures in the tin-15 wt pct lead and tin-3 wt pct bismuth alloys

The tin-15 wt pct lead and tin-3 wt pct bismuth alloys have been solidified in the low-gravity environment provided by the Space Processing Applications Rocket (SPAR), on the KC-135 airplane, and at high 'g' levels in a centrifuge furnace. In each case the resultant cast structure was significantly different from that obtained in ground based experiments. Earlier low-gravity studies with the metal-model system NH4Cl-H2O presaged these results. This paper presents and discusses the influence of changes in the gravity force on the grain structure of these materials.

Johnston, M. H.↗

Design, Fabrication, and Testing of a TiN Ti TiN Trilayer KID Array for 3mm CMB Observations

Kinetic inductance detectors (KIDs) are a promising technology for astronomical observations over a wide range of wavelengths in the mm and sub-mm regime. Simple fabrication, in as little as one lithographic layer, and passive frequency-domain multiplexing, with readout of up to 1000 pixels on a single line with a single cold amplifier, make KIDs an attractive solution for high-pixel-count detector arrays. We are developing an array that optimizes KIDs for optical frequencies near 100GHz to expand their usefulness in mm-wave applications, with a particular focus on CMBB-mode measurement efforts in association with the QUBIC telescope. We have designed, fabricated, and tested a 20-pixel prototype array using a simple quasi lumped microstrip design and pulsed DC reactive magnetron-sputtered TiNTiTiN trilayer resonators, optimized for detecting 100GHz (3mm) signals. Here we present a discussion of design considerations for the array, as well as preliminary detector characterization measurements and results from a study of TiN trilayer properties.

passive frequency-domain multiplexing↗

(NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a Vacancy-Ordered Three-Dimensional Tin(II) Perovskite-Derived Semiconductor

Ordering vacancies in hybrid Sn(II) halide semiconductors provides a strategy for preventing uncontrolled oxidation and formation of mobile holes. In this study, we report the structure and optical and electronic properties of (NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a vacancy-ordered perovskite derivative with three-dimensional inorganic connectivity. The crystal structure resembles that of a Dion–Jacobson layered perovskite derivative, but with [SnI 5 ] square pyramids bridging the layers. UV–vis diffuse reflectance spectroscopy reveals a sharp onset of light absorption at 1.86(1) eV with the photoluminescence emission maximum at 1.90(1) eV. However, the maximum excitation occurs from 3.42 to 3.81 eV (325 to 370 nm), revealing a significant Stokes shift of 1.3 eV. The electronic properties determined from dark and time-resolved microwave conductivity measurements reveal a minimum carrier mobility of 4.3 × 10 –2 cm 2 V –1 s –1 and a maximum carrier density of 5.96 × 10 16 cm –3 , a uniquely low value for a hybrid Sn(II) halide semiconductor. The transport behavior in combination with first-principles calculations of the electronic band structure and dielectric permittivity suggest polaron-mediated electronic transport, yet the photogenerated carriers have a fast and fluence-dependent nonradiative recombination rate, suggestive of localized “defect-like” states at the band edge. The observed photoluminescence is most consistent with single-ion-like behavior of an asymmetric Sn(II) environment. Together, these results suggest that defect ordering presents a strategy for the reduction of mobile charge carriers at equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Conformal Coat on Tin Whisker Growth

A whisker from a tin plated part was blamed for the loss of a commercial spacecraft in 1998. Although pure tin finishes are prohibited by NASA, tin plated parts, such as hybrids, relays and commercial off the shelf (COTS) parts, are something discovered to have been installed in NASA spacecraft. Invariably, the assumption is that a conformal coat will prevent the growth of, or short circuits caused by, tin whiskers. This study measures the effect a Uralane coating has on the initiation and growth of tin whiskers, on the ability of this coating to prevent a tin whisker from emerging from the coating, and on the ability to prevent shorting. A sample of fourteen brass substrates (1 inch by 4 inches by 1/16 inch) were plated by two separate processes: half of the specimens were 'bright' tin plated directly over the brass substrate and half received a copper flash over the brass substrate prior to 'bright' tin plating. Each specimen was coated on one half of the substrate with three bi-directional sprays of Uralane 5750 to a nominal thickness of 25 to 75 micrometers (1 to 3 mils). Several specimens of both types, Cu and non-Cu flashed, were placed in an oven maintained at 50 C as others' work suggests that this is the optimal temperature for whisker formation. The remaining specimens were maintained at room ambient conditions. The surfaces of each specimen have been regularly inspected using both optical (15 to 400x power) and Scanning Electronic Microscopy (SEM). Many types of growths, including needle-like whiskers, first appeared approximately three months after plating on the non-conformally coated sides of all specimens. At four months, 4 to 5 times more growth sites were observed on the coated side; however, the density of growth sites on the non-conformally coated side has since increased rapidly, and now, at one year, is about the same for both sides. The density of growth sites is estimated at 90/sq mm with 30 percent of the sites growing whiskers (needle-like forms) with the potential to cause short circuit bridging. The average growth rate of the needle-like whiskers on the non-conformally coated areas is about 130 micrometers per year with some outliers reaching 800 micrometers after one year. It is more difficult to make growth measurements under the conformal coat. As yet no whiskers have been observed to penetrate through the coating surface, however, a number of tin nodules appear on the verge of breaking through the thinner regions of the coating surface. These domes are developing sharper and sharper tips, as if a growing whisker is about to push its way through a tough skin. Our observations are that the specimens with copper flash show a much lower density of nucleation sites and significantly slower whisker growth compared to the specimens that have only bright tin plating over brass. The specimens kept at room temperature have a higher whisker density than those stored at 50 C. This is an unexpected result and does not agree with the published findings of others. All of the whiskers originate from small surface defects (thin, tiny scratches) that appear over the entire surface of each specimen.

Kadesch, Jong S.↗

Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage. In addition, the unexpected polycrystalline structure seen in the focused ion beam (FIB) cross section in the first experiment was confirmed in this experiment using transmission electron microscopy (TEM). The FIB was also used to cross section two card guides to facilitate the measurement of the grain size of each card guide's tin plating to determine its finish .

Courey, Karim J.↗

Developing an Empirical Model for Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage. In addition, the unexpected polycrystalline structure seen in the focused ion beam (FIB) cross section in the first experiment was confirmed in this experiment using transmission electron microscopy (TEM). The FIB was also used to cross section two card guides to facilitate the measurement of the grain size of each card guide's tin plating to determine its finish.

Courey, Karim J.↗

Estimating the Probability of Electrical Short Circuits from Tin Whiskers

To comply with lead-free legislation, many manufacturers have converted from tin-lead to pure tin finishes of electronic components. However, pure tin finishes have a greater propensity to grow tin whiskers than tin-lead finishes. Since tin whiskers present an electrical short circuit hazard in electronic components, simulations have been developed to quantify the risk of said short circuits occurring. Existing risk simulations make the assumption that when a free tin whisker has bridged two adjacent exposed electrical conductors, the result is an electrical short circuit. This conservative assumption is made because shorting is a random event that had an unknown probability associated with it. Note however that due to contact resistance electrical shorts may not occur at lower voltage levels. In our first article we developed an empirical probability model for tin whisker shorting. In this paper, we develop a more comprehensive empirical model using a refined experiment with a larger sample size, in which we studied the effect of varying voltage on the breakdown of the contact resistance which leads to a short circuit. From the resulting data we estimated the probability distribution of an electrical short, as a function of voltage.

Courey, Karim J.↗

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗

Self-Assembled TiN-Metal Nanocomposites Integrated on Flexible Mica Substrates towards Flexible Devices

The integration of nanocomposite thin films with combined multifunctionalities on flexible substrates is desired for flexible device design and applications. For example, combined plasmonic and magnetic properties could lead to unique optical switchable magnetic devices and sensors. In this work, a multiphase TiN-Au-Ni nanocomposite system with core–shell-like Au-Ni nanopillars embedded in a TiN matrix has been demonstrated on flexible mica substrates. The three-phase nanocomposite film has been compared with its single metal nanocomposite counterparts, i.e., TiN-Au and TiN-Ni. Magnetic measurement results suggest that both TiN-Au-Ni/mica and TiN-Ni/mica present room-temperature ferromagnetic property. Tunable plasmonic property has been achieved by varying the metallic component of the nanocomposite films. The cyclic bending test was performed to verify the property reliability of the flexible nanocomposite thin films upon bending. This work opens a new path for integrating complex nitride-based nanocomposite designs on mica towards multifunctional flexible nanodevice applications.

42 ENGINEERING↗

Superlative TINs

TIN is short for 'triangulated irregular network,' which is a piecewise planar model of a surface. If properly constructed, a TIN can be more than 30 times as efficient as a regular triangulation. In our project (a ground combat simulation to support U.S. Army training exercises), the TIN is used to represent the Earth's surface and is used primarily to determine whether line of sight is blocked by terrain. High efficiency requires accurate identification of ridgelines with as few triangles as possible. The work currently in progress is the implementation of a TINning process that we hope will produce superlative TINs. This presentation describes that process.

Triangulated Irregular Networks TIN Delaunay trian↗

Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo 2 N Model Surfaces and Powder Catalysts

Transition metal nitrides (TMNs) have been explored as effective supports for Pt due to their Pt-like electronic properties. However, there is a lack of fundamental understanding regarding the behavior of Pt on different TMNs (Pt/TMN). Herein two TMNs, Mo 2 N and TiN, were modified with Pt and compared using methanol decomposition as a probe reaction via both ultrahigh vacuum (UHV) studies on thin films and ambient-pressure batch reactor studies of powder catalysts. Temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements were conducted under UHV conditions with Mo 2 N and TiN thin films. Mo 2 N was shown to favor C–H bond scission to form CO with a 56.2% selectivity, while TiN favored C–O bond scission to form CH 4 with a 74.5% selectivity. The addition of 0.9 monolayers (MLs) of Pt increased C–H bond scission selectivity to 89.7% and 49.2% for Mo 2 N and TiN respectively. Density functional theory (DFT) calculations on model surfaces revealed that the binding energy of O (BE *O ) was significantly reduced on Pt/TMNs, from −4.02 eV on Mo 2 N to −1.31 eV on Pt/Mo 2 N and −4.74 eV on TiN to −1.37 eV on Pt/TiN. As a result, C–O bond scission pathways were suppressed, leading to the preferential C–H bond scission that was observed experimentally. The C–O and C–H bond scission trends observed on thin films were then extended to powder catalysts, which demonstrated similar trends toward methanol decomposition. In conclusion, results from the current study establish that by combining UHV studies and DFT calculations over model surfaces, one can effectively predict the catalytic behavior of realistic TMN powder catalysts.

08 HYDROGEN↗

Cage Balancing Enhances Optoelectronic and Lasing Performance in Stable Quasi-2D Tin Iodide Perovskites

Two-dimensional (2D) tin halide perovskites are highly tunable and low-toxicity semiconductors, promising for next-generation optoelectronics. However, achieving air stability and excellent photophysical properties simultaneously necessitates deliberate structure tuning using organic spacer cations and A-site cations. Here, we report a series of new quasi-2D Ruddlesden–Popper tin halide perovskites using a fluorinated aromatic spacer cation, 4-fluorophenethylammonium (4FPEA), and systematically investigate the impacts of layer thickness, spacer cation, and A-site cation on the crystal structures and optical properties of (4FPEA) 2 (A) n−1 S n I 3n+1 . These 4FPEA-based 2D tin perovskites, further tuned by the A-cations, exhibit uniquely undistorted 180° out-of-plane Sn–I–Sn bond angles and low octahedral distortions compared to other quasi-2D perovskites and demonstrate prolonged air stability, excellent photophysics, and amplified spontaneous emission and lasing in exfoliated microflakes. A comprehensive survey of reported n = 2 lead and tin iodide perovskites reveals that all structures can be classified into three types (tilted, balanced, and buckled) based on the structural distortion parameters of their perovskite cages. Notably, (4FPEA) 2 (A)Sn 2 I 7 are among the handful of “balanced” n = 2 perovskites with minimal distortion and excellent optoelectronic performance. Furthermore, the structural insights and cage-balancing approach revealed herein motivate the deliberate design of quasi-2D perovskites through the synergy of the spacer and cage cations, further paving the way for high-performance optoelectronic applications of stable tin halide perovskites.

Cations↗

The critical currents in superconducting tin films

The nonlinear current-voltage curves exhibited by tin films in the flux flow state have made studies of the amount of heating present in the sample necessary. The samples in this work consisted of an evaporated tin film on one side of a 2 mm thick crystal quartz substrate and a carbon film of the same configuration as the tin film on the back of the substrate. The carbon film was used as a thermometer to measure the temperature rise of the tin film above the bath temperature. The heating results indicate negligible effects in the samples. Temperature ratios as small as 0.80 for the tin samples have been investigated and the current-voltage characteristics are still nonlinear, indicating that the source of the nonlinearity is not Joule heating in the samples.

Payne, J. E.↗

Effects on stress rupture life and tensile strength of tin additions to Inconel 718

Because Inconel 718 represents a major use of columbium and a large potential source of columbium for aerospace alloys could be that of columbium derived from tin slags, the effects of tin additions to Inconel 718 at levels which might be typical of or exceed those anticipated if tin slag derived columbium were used as a melting stock were investigated. Tin was added to 15 pound Inconel 718 heats at levels varying from none added to approximately 10,000 ppm (1 wt%). Limited 1200 F stress rupture testing was performed at stresses from 68,000 to 115,000 psi and a few tensile tests were performed at room temperature, 800 and 1200 F. Additions of tin in excess of 800 ppm were detrimental to ductility and stress rupture life.

Dreshfield, R. L.↗

Infrared emission spectrophotometric study of the changes produced by TiN coating of metal surfaces in an operating EHD contact

Infrared emission spectra and related measurements were obtained from an operating ball/plate EHD sliding contact under a variety of operating conditions. In order to be able to compare the effect of the ball surface, some of the steel balls were coated with a thin layer of titanium nitride (TiN) by vapor deposition. Polyphenyl ether (5P4E) was used as the lubricant and 1 percent of 1,1,2-trichloroethane TCE) as an additive with a high affinity for steel but a low affinity for TiN. TiN is chemically inert, but its thermal conductivity is lower than that of steel. Therefore, the overall temperatures with TiN-coated balls were higher. Nevertheless, no scuffng was observed with the coated balls under conditions giving rise to scuffing with the uncoated balls. Tractions were lower with the TiN-coated balls and with the steel balls when TCE was added to the 5P4E. These findings were found to be inversely related to the degree of polarization of the spectral emission bands. The intensity and the dichroism of these bands were related to shear rates and inlet conditions of the EHD contact.

Keller, L. E.↗