Richard P. Padbury

Temperature and Exposure Dependence of Hybrid Organic–Inorganic Layer Formation by Sequential Vapor Infiltration into Polymer Fibers

The characteristic processing behavior for growth of a conformal nanoscale hybrid organic-inorganic modification to polyamide 6 (PA6) by sequential vapor infiltration (SVI) is demonstrated. The SVI process is a materials growth technique by which exposure of organometallic vapors to a polymeric material promotes the formation of a hybrid organic-inorganic modification at the near surface region of the polymer. This work investigates the SVI exposure temperature and cycling times of sequential exposures of trimethylaluminum (TMA) on PA6 fiber mats. The result of TMA exposure is the preferential subsurface organic-inorganic growth by diffusion into the polymer and reaction with the carbonyl in PA6. Mass gain, infrared spectroscopy, and transmission electron microscopy analysis indicate enhanced materials growth and uniformity at lower processing temperatures. The inverse relationship between mass gain and exposure temperature is explained by the formation of a hybrid layer that prevents the diffusion of TMA into the polymer to react with the PA6 upon subsequent exposure cycles. As few as 10 SVI exposure cycles are observed to saturate the growth, yielding a modified thickness of ∼75 nm and mass increase of ∼14 wt %. Removal of the inherent PA6 moisture content reduces the mass gain by ∼4 wt % at low temperature exposures. The ability to understand the characteristic growth process is critical for the development of the hybrid materials fabrication and modification techniques.

Conformal Atomic Layer Deposition of Alumina on Millimeter Tall, Vertically-Aligned Carbon Nanotube Arrays

Atomic layer deposition (ALD) can be used to coat high aspect ratio and high surface area substrates with conformal and precisely controlled thin films. Vertically aligned arrays of multiwalled carbon nanotubes (MWCNTs) with lengths up to 1.5 mm were conformally coated with alumina from base to tip. The nucleation and growth behaviors of Al2O3 ALD precursors on the MWCNTs were studied as a function of CNT surface chemistry. CNT surfaces were modified through a series of post-treatments including pyrolytic carbon deposition, high temperature thermal annealing, and oxygen plasma functionalization. Conformal coatings were achieved where post-treatments resulted in increased defect density as well as the extent of functionalization, as characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. Using thermogravimetric analysis, it was determined that MWCNTs treated with pyrolytic carbon and plasma functionalization prior to ALD coating were more stable to thermal oxidation than pristine ALD coated samples. Functionalized and ALD coated arrays had a compressive modulus more than two times higher than a pristine array coated for the same number of cycles. Cross-sectional energy dispersive X-ray spectroscopy confirmed that Al2O3 could be uniformly deposited through the entire thickness of the vertically aligned MWCNT array by manipulating sample orientation and mounting techniques. Following the ALD coating, the MWCNT arrays demonstrated hydrophilic wetting behavior and also exhibited foam-like recovery following compressive strain.

Systematic study of trimethyl aluminum infiltration in polyethylene terephthalate and its effect on the mechanical properties of polyethylene terephthalate fibers

Hybrid organic–inorganic materials are of increasing interest in the development of novel materials that unite characteristic properties of both organic and inorganic constituents. This work provides a mechanistic understanding of the processing space necessary to utilize hybrid modifications to produce advanced high strength fibrous and textile materials. The infiltration of organometallic precursors into fiber forming polymers and the subsequent formation of a hybrid material interface is detailed. To explore this in more detail, in-situ quartz crystal microgravimetry is employed to investigate the infiltration of trimethyl aluminum (TMA) into polyethylene terephthalate polymer films. Specifically, films with varied crystallinities are explored demonstrating that an increase in crystallinity results in a decrease in mass uptake of trimethyl aluminum. Subsequently, the authors highlight the structure–property relationships between modified and unmodified fibers infiltrated with TMA. For the first time, increases in peak load and elongation is observed by facile exposure to organometallic vapors. The combined peak load and elongation increase is an exciting outcome typically not observed in synthetic fibers.

Temperature-Dependent Infiltration of Polymers during Sequential Exposures to Trimethylaluminum

Atomic layer deposition provides the opportunity to introduce nanoscale inorganic coatings to organic polymers creating coatings of varied compositions of finish with distinctive interfaces. Prior research has shown that ALD materials nucleation on polymers varies in composition and structure based on how the precursor interacts with the polymer chemistry and the process conditions. To study this in more detail, in situ quartz crystal microgravimetry is employed to understand the infiltration and saturation behavior of trimethylaluminum in polyamide-6, poly(acrylic acid), poly(ethylene terephthalate), and poly(methyl methacrylate). Emphasis is placed on understanding reactive vapor diffusion into these polymers as the exposure temperature is varied. Finally, we propose potential growth mechanisms based on the temperature-dependent observations in this work that enables the ability to produce a customized interface for ALD materials growth on polymer substrates.

Comparison of precursor infiltration into polymer thin films via atomic layer deposition and sequential vapor infiltration using in-situ quartz crystal microgravimetry

Previous research exploring inorganic materials nucleation behavior on polymers via atomic layer deposition indicates the formation of hybrid organic–inorganic materials that form within the subsurface of the polymer. This has inspired adaptations to the process, such as sequential vapor infiltration, which enhances the diffusion of organometallic precursors into the subsurface of the polymer to promote the formation of a hybrid organic–inorganic coating. This work highlights the fundamental difference in mass uptake behavior between atomic layer deposition and sequential vapor infiltration using in-situ methods. In particular, in-situ quartz crystal microgravimetry is used to compare the mass uptake behavior of trimethyl aluminum in poly(butylene terephthalate) and polyamide-6 polymer thin films. The importance of trimethyl aluminum diffusion into the polymer subsurface and the subsequent chemical reactions with polymer functional groups are discussed.

Thermal stability of gold nanoparticles embedded within metal oxide frameworks fabricated by hybrid modifications onto sacrificial textile templates.

The stability and spatial separation of nanoparticles (NPs) is essential for employing their advantageous nanoscale properties. This work demonstrates the entrapment of gold NPs embedded in a porous inorganic matrix. Initially, gold NPs are decorated on fibrous nylon-6, which is used as an inexpensive sacrificial template. This is followed by inorganic modification using a novel single exposure cycle vapor phase technique resulting in distributed NPs embedded within a hybrid organic-inorganic matrix. The processing is extended to the synthesis of porous nanoflakes after calcination of the modified nylon-6 yielding a porous metal oxide framework surrounding the disconnected NPs with a surface area of 250 m(2)/g. A unique feature of this work is the use of a transmission electron microscope (TEM) equipped with an in situ annealing sample holder. The apparatus affords the opportunity to explore the underlying nanoscopic stability of NPs embedded in these frameworks in a single step. TEM analysis indicates thermal stability up to 670 °C and agglomeration characteristics thereafter. The vapor phase processes developed in this work will facilitate new complex NP/oxide materials useful for catalytic platforms.

Silver decorated polymer supported semiconductor thin films by UV aided metalized laser printing

A facile ultraviolet assisted metalized laser printing technique is demonstrated through the ability to control selective photodeposition of silver on flexible substrates after atomic layer deposition pretreatment with zinc oxide and titania. The photodeposition of noble metals such as silver onto high surface area, polymer supported semiconductormetal oxides exhibits a new route for nanoparticle surface modification of photoactive enhanced substrates. Photodeposited silver is subsequently characterized using low voltage secondary electron microscopy, x-ray diffraction, and time of flight secondary ion mass spectroscopy. At the nanoscale, the formation of specific morphologies, flake and particle, is highlighted after silver is photodeposited on zinc oxide and titania coated substrates, respectively. The results indicate that the morphology and composition of the silver after photodeposition has a strong dependency on the morphology, crystallinity, and impurity content of the underlying semiconductor oxide. At the macroscale, this work demonstrates how the nanoscale features rapidly coalesce into a printed pattern through the use of masks or an X-Y gantry stage with virtually unlimited design control.