Sarah D. Shepherd

Conformal and highly adsorptive metal–organic framework thin films via layer-by-layer growth on ALD-coated fiber mats

Integration of metal–organic frameworks (MOFs) on textiles shows promise for enabling facile deployment and expanding MOF applications. While MOFs deposited on flat substrates can show relatively smooth surface texture, most previous reports of MOFs integrated on fibers show poor conformality with many individual crystal domains. Here we report a new low-temperature (<70 °C) method to deposit uniform and smooth MOF thin films on fiber surfaces using an energy enhanced layer-by-layer (LbL) method with an ALD Al2O3 nucleation layer. Cross-sectional TEM images show a well-defined core@shell structure of the MOF-functionalized fiber, and SEM shows a flat MOF surface texture. We analyze the thickness and mass increase data of LbL HKUST-1 MOF thin films on ALD-coated polypropylene fibers and find the growth rate to be 288–290 ng cm−2 per LbL cycle. Unlike planar LbL MOF embodiments where adsorption capacities are difficult to quantify, the large volume quantity on a typical fiber mat enables accurate surface area measurement of these unique MOF morphologies. After 40 LbL cycles the MOFs on fibers exhibit N2 adsorption BET surface areas of up to 93.6 m2 gMOF+fiber−1 (∼535 m2 gMOF−1) and breakthrough test results reveal high dynamic loadings for NH3 (1.37 molNH3 kgMOF+fiber−1) and H2S (1.49 molH2S kgMOF+fiber−1). This synthesis route is applicable to many polymer fibers, and the fiber@ALD@MOF structure is promising for gas filtration, membrane separation, catalysis, chemical sensing and other applications.

Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition

Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

Insights into accelerated aging of SSL luminaires

Although solid-state lighting (SSL) products are often intended to have product lifetimes of 15 years or more, the rapid change in technology has created a need for accelerated life tests (ALTs) that can be performed in the span of several months. A critical element of interpreting results from any systems-level ALT is understanding of the impact of the test environment on each component. Because of its ubiquity in electronics, the use of temperature-humidity environments as potential ALTs for SSL luminaires was investigated. Results from testing of populations of three commercial 6” downlights in environments of 85°C and 85% relative humidity (RH) and 75°C and 75% RH are reported. These test environments were found to accelerate lumen depreciation of the entire luminaire optical system, including LEDs, lenses, and reflectors. The effects of aging were found to depend strongly on both the optical materials that were used and the design of the luminaire; this shows that the lumen maintenance behavior of SSL luminaires must be addressed at the optical systems level. Temperature-Humidity ALTs can be a useful test in understand lumainaire depreciation provided that proper consideration is given to the different aging rates of various materials. Since the impact of the temperature-humidity environment varies among components of the optical system, uniform aging of all system components in a single test is difficult to achieve.

New understandings of failure modes in SSL luminaires

As SSL products are being rapidly introduced into the market, there is a need to develop standard screening and testing protocols that can be performed quickly and provide data surrounding product lifetime and performance. These protocols, derived from standard industry tests, are known as ALTs (accelerated life tests) and can be performed in a timeframe of weeks to months instead of years. Accelerated testing utilizes a combination of elevated temperature and humidity conditions as well as electrical power cycling to control aging of the luminaires. In this study, we report on the findings of failure modes for two different luminaire products exposed to temperature-humidity ALTs. LEDs are typically considered the determining component for the rate of lumen depreciation. However, this study has shown that each luminaire component can independently or jointly influence system performance and reliability. Material choices, luminaire designs, and driver designs all have significant impacts on the system reliability of a product. From recent data, it is evident that the most common failure modes are not within the LED, but instead occur within resistors, capacitors, and other electrical components of the driver. Insights into failure modes and rates as a result of ALTs are reported with emphasis on component influence on overall system reliability.

A moldable sustained release bupivacaine formulation for tailored treatment of postoperative dental pain

A moldable and biodegradable dental material was designed for customized placement and sustained delivery of bupivacaine (BP) within an extraction cavity. Microparticles comprising poly(lactic-co-glycolic acid) (PLGA) containing BP were generated via solvent-evaporation and combined with absorbable hemostat Gelfoam®. Kinetics of drug release were evaluated by in vitro dialysis assays, showing higher release within the first 24 hours, with subsequent tapering of release kinetics. Formulations of Gelfoam® and BP-PLGA microparticles (GelBP), with three targeted dosing profiles (0.25, 0.5, and 1 mg/kg/day), were evaluated alongside acute subcutaneous BP injections (2 mg/kg) to determine analgesic efficacy in a rat model of tooth extraction pain. Molar extraction resulted in mechanical and thermal cold hyperalgesia in male and female rats. GelBP outperformed acute BP in blocking post-surgical dental pain, with the 0.25 mg/kg GelBP dose preventing hypersensitivity to mechanical (p < 0.01) and thermal cold stimuli (p = 0.05). Molar extraction also resulted in decreased food consumption and weight. Males receiving acute BP and 0.25 mg/kg GelBP maintained normal food consumption (p < 0.002) and weight (p < 0.0001) throughout 7 days. Females, receiving 0.25 mg/kg GelBP maintained weight on days 5–7 (p < 0.04). Customized, sustained release formulation of anesthetic within a tooth extraction cavity holds potential to eliminate post-operative dental pain over several days.