Air, Water Vapor, and Aerosol Transport through Textiles with Surface Functional Coatings of Metal Oxides and Metal-Organic Frameworks.

Currently, air permeable chemical/biological (CB) protective garments are based on activated carbon technology, which reduces moisture vapor transport needed for evaporative cooling and has potential to absorb and concentrate toxic materials. Researchers are exploring classes of sorbent materials that can selectively accumulate and decompose target compounds for potential to enhance protective suits and allow for novel filtration devices. Here, the metal-organic frameworks (MOFs) UiO-66-NH2 and HKUST-1 have been identified as such materials. To better understand how MOFs can perform in future CB protective systems, atomic layer deposition (ALD) and solution deposition were used to modify nonwoven polypropylene and flame-resistant fabrics with HKUST-1 and UiO-66-NH2. Air permeation, water vapor transport, filtration efficiency, and chemical reactivity against chemical agent simulants were assessed in relation to ALD thickness and MOF crystal size. MOF deposition on substrates decreased both air and chemical permeation while increasing filtration efficiency and chemical sorption. Moisture vapor transport was not affected by MOF growth on substrates, which is promising when considering thermal properties of protective garments. Future work should continue to explore how MOF deposition onto fiber and textile substrates impacts transport properties and chemical absorbance.

Investigation of the Corrosion Behavior of Atomic Layer Deposited Al2O3/TiO2 Nanolaminate Thin Films on Copper in 0.1 M NaCl.

Fifty nanometers of Al2O3 and TiO2 nanolaminate thin films deposited by atomic layer deposition (ALD) were investigated for protection of copper in 0.1 M NaCl using electrochemical techniques. Coated samples showed increases in polarization resistance over uncoated copper, up to 12 MΩ-cm², as measured by impedance spectroscopy. Over a 72-h immersion period, impedance of the titania-heavy films was found to be the most stable, as the alumina films experienced degradation after less than 24 h, regardless of the presence of dissolved oxygen. A film comprised of alternating Al2O3 and TiO2 layers of 5 nm each (referenced as ATx5), was determined to be the best corrosion barrier of the films tested based on impedance spectroscopy measurements over 72 h and equivalent circuit modeling. Dissolved oxygen had a minimal effect on ALD film stability, and increasing the deposition temperature from 150 °C to 250 °C, although useful for increasing film quality, was found to be counterproductive for long-term corrosion protection. Implications of ALD film aging and copper-based surface film formation during immersion and testing are also discussed briefly. The results presented here demonstrate the potential for ultra-thin corrosion barrier coatings, especially for high aspect ratios and component interiors, for which ALD is uniquely suited.

UiO-66-NH2 Metal-Organic Framework (MOF) Nucleation on TiO2, ZnO, and Al2O3 Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants.

Metal-organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al2O3, ZnO, or TiO2) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH2 MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO2 ALD layers lead to the most effective overall MOF/fiber adhesion, uniformity, and a rapid catalytic degradation rate for a CWA simulant, dimethyl p-nitrophenyl phosphate (DMNP) with t1/2 = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles. Interestingly, compared to ALD TiO2 and Al2O3, ALD ZnO induces a larger MOF yield in solution and mass loading on PP fibrous mats. However, this larger MOF yield is ascribed to chemical instability of the ZnO layer under MOF formation condition, leading to Zn2+ ions that promote further homogeneous MOF growth. Insights presented here improve understanding of compatibility between active MOF materials and substrate surfaces, which we believe will help advanced MOF composite materials for a variety of useful functions.

Large-Area Nanolattice Film with Enhanced Modulus, Hardness, and Energy Dissipation.

We present an engineered nanolattice material with enhanced mechanical properties that can be broadly applied as a thin film over large areas. The nanolattice films consist of ordered, three-dimensional architecture with thin-shell tubular elements, resulting in favorable modulus-density scaling (n ~ 1.1), enhanced energy dissipation, and extremely large material recoverability for strains up to 20% under normal compressive loading. At 95.6% porosity, the nanolattice film has demonstrated modulus of 1.19 GPa and specific energy dissipation of 325.5 kJ/kg, surpassing previously reported values at similar densities. The largest length scale in the reported nanolattice is the 500 nm unit-cell lattice constant, allowing the film to behave more like a continuum material and be visually unobservable. Fabricated using three-dimensional colloidal nanolithography and atomic layer deposition, the process can be scaled for large-area patterning. The proposed nanolattice film can find applications as a robust multifunctional insulating film that can be applied in integrated photonic elements, optoelectronic devices, and microcircuit chips.

Corrosion Protection of Copper Using Al2O3, TiO2, ZnO, HfO2, and ZrO2 Atomic Layer Deposition.

Atomic layer deposition (ALD) is a viable means to add corrosion protection to copper metal. Ultrathin films of Al2O3, TiO2, ZnO, HfO2, and ZrO2 were deposited on copper metal using ALD, and their corrosion protection properties were measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Analysis of ∼50 nm thick films of each metal oxide demonstrated low electrochemical porosity and provided enhanced corrosion protection from aqueous NaCl solution. The surface pretreatment and roughness was found to affect the extent of the corrosion protection. Films of Al2O3 or HfO2 provided the highest level of initial corrosion protection, but films of HfO2 exhibited the best coating quality after extended exposure. This is the first reported instance of using ultrathin films of HfO2 or ZrO2 produced with ALD for corrosion protection, and both are promising materials for corrosion protection.

Ultra-Fast Degradation of Chemical Warfare Agents Using MOF-Nanofiber Kebabs.

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal-organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF-nanofiber kebab structures for fast degradation of CWAs. We found TiO2 coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH2 , and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF-nanofiber textile composites capable of ultra-fast degradation of CWAs.

Wicking Enhancement in Three-Dimensional Hierarchical Nanostructures.

Wicking, the absorption of liquid into narrow spaces without the assistance of external forces, has drawn much attention due to its potential applications in many engineering fields. Increasing surface roughness using micro/nanostructures can improve capillary action to enhance wicking. However, reducing the structure length scale can also result in significant viscous forces to impede wicking. In this work, we demonstrate enhanced wicking dynamics by using nanostructures with three-dimensional (3D) hierarchical features to increase the surface area while mitigating the obstruction of liquid flow. The proposed structures were engineered using a combination of interference lithography and hydrothermal synthesis of ZnO nanowires, where structures at two length scales were independently designed to control wicking behavior. The fabricated hierarchical 3D structures were tested for water and ethanol wicking properties, demonstrating improved wicking dynamics with intermediate nanowire lengths. The experimental data agree with the derived fluid model based on the balance of capillary and vicious forces. The hierarchical wicking structures can be potentially used in applications in water harvesting surfaces, microfluidics, and integrated heat exchangers.

Facile Conversion of Hydroxy Double Salts to Metal-Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates.

Rapid room-temperature synthesis of metal-organic frameworks (MOFs) is highly desired for industrial implementation and commercialization. Here we find that a (Zn,Cu) hydroxy double salt (HDS) intermediate formed in situ from ZnO particles or thin films enables rapid growth (<1 min) of HKUST-1 (Cu3(BTC)2) at room temperature. The space-time-yield reaches >3 × 10(4) kg·m(-3)·d(-1), at least 1 order of magnitude greater than any prior report. The high anion exchange rate of (Zn,Cu) hydroxy nitrate HDS drives the ultrafast MOF formation. Similarly, we obtained Cu-BDC, ZIF-8, and IRMOF-3 structures from HDSs, demonstrating synthetic generality. Using ZnO thin films deposited via atomic layer deposition, MOF patterns are obtained on pre-patterned surfaces, and dense HKUST-1 coatings are grown onto various form factors, including polymer spheres, silicon wafers, and fibers. Breakthrough tests show that the MOF-functionalized fibers have high adsorption capacity for toxic gases. This rapid synthesis route is also promising for new MOF-based composite materials and applications.

Precise Nanoscale Surface Modification and Coating of Macroscale Objects: Open-Environment in Loco Atomic Layer Deposition on an Automobile.

The fundamental chemical reaction conditions that define atomic layer deposition (ALD) can be achieved in an open environment on a macroscale surface too large and complex for typical laboratory reactor-based ALD. We describe the concept of in loco ALD using conventional modulated reactant flow through a surface-mounted "ALD delivery head" to form a precise nanoscale Al2O3 film on the window of a parked automobile. Analysis confirms that the processes eliminated ambient water contamination and met other conditions that define ALD growth. Using this tool, we demonstrate open-ambient patterned deposition, metal corrosion protection, and polymer surface modification.

Atomic layer deposition of metal oxide patterns on nonwoven fiber mats using localized physical compression.

Patterning is an essential part of many industrial processes from printing to semiconductor manufacturing. In this work, we demonstrate a new method to pattern and selectively coat nonwoven textiles by atomic layer deposition (ALD) using compressive mask patterning. A physical mask combined with mechanical compression allows lateral definition and fidelity of the ALD coating to be controlled. We produce features of several sizes on different nonwoven fiber materials and demonstrate the ability to limit diffusion effects to within <200 µm of the pattern edge. Lateral and vertical penetration of reactive growth species into nonwoven mats is investigated by plan-view and cross-sectional imaging. Vertical growth is also analyzed by imaging coating depth into fiber mat stacks. We develop a fully quantitative transport model that describes well the effect of fiber structure and mechanical compression on the extent of coating under the physical mask. This method could be implemented for high-volume patterning for applications including flexible electronics.

Atmospheric pressure atomic layer deposition of Al2O3 using trimethyl aluminum and ozone.

High throughput spatial atomic layer deposition (ALD) often uses higher reactor pressure than typical batch processes, but the specific effects of pressure on species transport and reaction rates are not fully understood. For aluminum oxide (Al2O3) ALD, water or ozone can be used as oxygen sources, but how reaction pressure influences deposition using ozone has not previously been reported. This work describes the effect of deposition pressure, between ∼2 and 760 Torr, on ALD Al2O3 using TMA and ozone. Similar to reports for pressure dependence during TMA/water ALD, surface reaction saturation studies show self-limiting growth at low and high pressure across a reasonable temperature range. Higher pressure tends to increase the growth per cycle, especially at lower gas velocities and temperatures. However, growth saturation at high pressure requires longer O3 dose times per cycle. Results are consistent with a model of ozone decomposition kinetics versus pressure and temperature. Quartz crystal microbalance (QCM) results confirm the trends in growth rate and indicate that the surface reaction mechanisms for Al2O3 growth using ozone are similar under low and high total pressure, including expected trends in the reaction mechanism at different temperatures.

Highly conductive and flexible nylon-6 nonwoven fiber mats formed using tungsten atomic layer deposition.

Low-temperature vapor-phase tungsten atomic layer deposition (ALD) using WF6 and dilute silane (SiH4, 2% in Ar) can yield highly conductive coatings on nylon-6 microfiber mats, producing flexible and supple nonwovens with conductivity of ∼1000 S/cm. We find that an alumina nucleation layer, reactant exposure, and deposition temperature all influence the rate of W mass uptake on 3D fibers, and film growth rate is calibrated using high surface area anodic aluminum oxide. Transmission electron microscopy (TEM) reveals highly conformal tungsten coatings on nylon fibers with complex "winged" cross-section. Using reactant gas "hold" sequences during the ALD process, we conclude that reactant species can transport readily to reactive sites throughout the fiber mat, consistent with conformal uniform coverage observed by TEM. The conductivity of 1000 S/cm for the W-coated nylon is much larger than found in other conductive nonwovens. We also find that the nylon mats maintain 90% of their conductivity after being flexed around cylinders with radii as small as 0.3 cm. Metal ALD coatings on nonwovens make possible the solvent-free functionalization of textiles for electronic applications.

Fiber containment for improved laboratory handling and uniform nanocoating of milligram quantities of carbon nanotubes by atomic layer deposition.

The presence of nanostructured materials in the workplace is bringing attention to the importance of safe practices for nanomaterial handling. We explored novel fiber containment methods to improve the handling of carbon nanotube (CNT) powders in the laboratory while simultaneously allowing highly uniform and controlled atomic layer deposition (ALD) coatings on the nanotubes, down to less than 4 nm on some CNT materials. Moreover, the procedure yields uniform coatings on milligram quantities of nanotubes using a conventional viscous flow reactor system, circumventing the need for specialized fluidized bed or rotary ALD reactors for laboratory-scale studies. We explored both fiber bundles and fiber baskets as possible containment methods and conclude that the baskets are more suitable for coating studies. An extended precursor and reactant dose and soak periods allowed the gases to diffuse through the fiber containment, and the ALD coating thickness scaled linearly with the number of ALD cycles. The extended dose period produced thicker coatings compared to typical doses on CNT controls not encased in the fibers, suggesting some effects due to the extended reactant dose. Film growth was compared on a range of single-walled NTs, double-walled NTs, and acid-functionalized multiwalled NTs, and we found that ultrathin coatings were most readily controlled on the multiwalled NTs.