Aaron M. Forster

Robust conductive mesoporous carbon–silica composite films with highly ordered and oriented orthorhombic structures from triblock-copolymer template co-assembly

In this work, we describe a facile approach to improve the robustness of conductive mesoporous carbon-based thin films by the addition of silica to the matrix through the triconstituent organic–inorganic–organic co-assembly of resol (carbon precursor) and tetraethylorthosilicate (silica precursor) with triblock-copolymer Pluronic F127. The pyrolysis of the resol–silica–pluronic F127 film yields a porous composite thin film with well-defined mesostructure. X-Ray diffraction (XRD), grazing incidence small angle X-ray scattering (GISAXS), and electron microscopy measurements indicate that the obtained carbon-based thin films have a highly ordered orthorhombic mesostructure (Fmmm) with uniform large pore size (∼3 nm). The orthorhombic mesostructure is oriented and the (010) plane is parallel to the silicon wafer substrate. The addition of silica to the matrix impacts the pore size, surface area, porosity, modulus and conductivity. For composite films with approximately 40 wt% silica, the conductivity is decreased by approximately an order of magnitude in comparison to a pure carbon mesoporous film, but the conductivity is comparable to typical printed carbon inks used in electrochemical sensing, ∼10 S cm−1. The mechanical properties of these mesoporous silica–carbon hybrid films are similar to the pure carbon analogs with a Youngs modulus between 10 GPa and 15 GPa, but the material is significantly more porous. Moreover, the addition of silica to the matrix appears to improve the adhesion of the mesoporous film to a silicon wafer. These mesoporous silica–carbon composite films have appropriate characteristics for use in sensing applications.

Improving performance of dental resins by adding titanium dioxide nanoparticles

OBJECTIVE The objective of this study is to improve the performance of dental resins by adding a small amount of titanium dioxide nanoparticles (TiO₂ NPs), which have outstanding mechanical properties and unique photoactivities. METHODS Acrylic acid modified TiO₂ NPs (AP25) were prepared and added to a mixture of bis-phenol-A-dimethacrylate and triethylene glycol dimethacrylate (mass ratio 1:1) at seven mass fractions. Disks made of these resins were subjected to FTIR microspectroscopy, nanoindentation, microindentation, and 3-point bending to determine the degree of vinyl conversion (DC) modulus and hardness. The shear bond strengths (SBS) of dentin adhesives containing various amount of AP25 were also examined. RESULTS The DC increased as a function of mass fraction of AP25 and reached a plateau at 0.1%. The DC of the resin mixture was improved by ≈7% up to 91.7 ± 0.8%. The elastic modulus and hardness of the composites increased initially as more AP25 were added, and decreased after reached the maximum value at approximately 0.06% mass fraction of AP25. The maximum elastic modulus was ≈48% higher than that of the NP-free resin, and the maximum hardness was more than twice higher than that of the NP-free resin. Using these resin composites as dental adhesives, the mean SBS using resins with 0.1% mass fraction of AP25 was ≈30% higher than those using NP-free resin. SIGNIFICANCE By adding a small amount of AP25 to the resin, the DC and the mechanical properties of resins were improved dramatically. These findings could lead to better performing dental adhesives.

Cubic Silsesquioxanes as a Green, High-Performance Mold Material for Nanoimprint Lithography

Optical lithography deep in the UV spectrum is the predominate route for high-resolution, high-volume nanoscale pattering. However, state-of-the-art optical lithography tools are exceedingly expensive and this places serious limitations on the applications, technical sectors, and markets where highresolution patterning can be implemented. To date the only substantial market for high-end optical lithography tools has been semiconductor fabrication. Nanoimprint lithography (NIL) has recently emerged as an alternative to optical lithography and combines the potential of sub-fi ve-nanometer patterning resolution with the low cost and simplicity of a stamping process. [ 1–4 ] This has led to signifi cant efforts to implement NIL methods, not only for semiconductor logic devices, but also in fi elds as diverse as the direct patterning of interlayer dielectrics (ILDs) for back-end-of-line (BEOL) interconnect structures, [ 5–7 ] bitpatterned magnetic media for data storage, [ 8 , 9 ] and high-brightness light-emitting diodes (LEDs). [ 10 ] Some of these are new areas where nanoscale patterning has previously not been considered, and are made possible here by the low cost and simplicity of the NIL stamping processes.

Effects of filler type and content on mechanical properties of photopolymerizable composites measured across two-dimensional combinatorial arrays.

Multicomponent formulations coupled with complex processing conditions govern the final properties of photopolymerizable dental composites. In this study, a single test substrate was fabricated to support multiple formulations with a gradient in degree of conversion (DC), allowing the evaluation of multiple processing conditions and formulations on one specimen. Mechanical properties and damage response were evaluated as a function of filler type/content and irradiation. DC, surface roughness, modulus, hardness, scratch deformation and cytotoxicity were quantified using techniques including near-infrared spectroscopy, laser confocal scanning microscopy, depth-sensing indentation, scratch testing and cell viability. Scratch parameters (depth, width, percent recovery) were correlated to composite modulus and hardness. Total filler content, nanofiller and irradiation time/intensity all affected the final properties, with the dominant factor for improved properties being a higher DC. This combinatorial platform accelerates the screening of dental composites through the direct comparison of properties and processing conditions across the same sample.

Effect of Pigment Dispersion on Durability of a TiO 2 Pigmented Epoxy Coating During Outdoor Exposure

The effect of pigment dispersion on durability of a TiO 2 pigmented epoxy coating during outdoor exposure has been investigated. Well-dispersed and poorly dispersed coating samples were prepared through the addition or absence of a dispersant in the coating formulation. Ultra small angle neutron scattering (USANS) and scanning electron microscopy (SEM) showed that pigment aggregation occurs in the absence of dispersant. A thin, clear layer of epoxy was observed at the air/exposed surface interface in both the dispersed and non-dispersed samples. Chemical degradation and physical changes during UV exposure were measured by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM), and laser scanning confocal microscopy (LSCM). Results showed that the degree of pigment dispersion and the thickness of the clear layer contributed to weathering. Changes in surface topography and gloss loss during UV degradation were correlated with degree of pigment dispersion. Ripples and bumps on the top surface of the poorly dispersed coating greatly affected gloss. Bulk and surface mechanical properties were investigated using dynamic mechanical thermal analysis (DMTA) and instrumented indentation, respectively. Relative to the neat epoxy coatings, the addition of TiO 2 particles into the epoxy coatings increased elastic modulus but decreased the glass transition temperatures (T g ) of both of the pigmented coatings. Relationships between surface and bulk mechanical property changes and chemical degradation are discussed.

A multilens measurement platform for high-throughput adhesion measurements ∗

Current high-throughput methodologies for measuring interfacial adhesion typically rely on serial or sequential testing of discrete or continuous libraries. We have developed a measurement platform that employs an array of micro-lenses to simultaneously measure adhesion at multiple points on a planar specimen library. This technique relies on the accurate measurement of the overall lens array displacement, rather than load and individual lens contact areas to quantify the work of adhesion using the Johnson, Kendall and Roberts (JKR) model. We demonstrate the ability of this technique to measure the work of adhesion (loading) and energy release rate (unloading) for a polydimethylsiloxane lens array against glass, and we compare our work of adhesion measurements to the traditional single-lens geometry. We find the work of adhesion measured with the multilens array is 18.9 mJ m−2 ± 9.4 mJ m−2 compared to 20 mJ m−2 ± 5 mJ m−2 for a single-lens experiment. Also, the micro-lens array deviates from the JKR model when the lens array displacement is comparable to lens height.

Indentation device for in situ Raman spectroscopic and optical studies

Instrumented indentation is a widely used technique to study the mechanical behavior of materials at small length scales. Mechanical tests of bulk materials, microscopic, and spectroscopic studies may be conducted to complement indentation and enable the determination of the kinetics and physics involved in the mechanical deformation of materials at the crystallographic and molecular level, e.g., strain build-up in crystal lattices, phase transformations, and changes in crystallinity or orientation. However, many of these phenomena occurring during indentation can only be observed in their entirety and analyzed in depth under in situ conditions. This paper describes the design, calibration, and operation of an indentation device that is coupled with a Raman microscope to conduct in situ spectroscopic and optical analysis of mechanically deformed regions of Raman-active, transparent bulk material, thin films or fibers under contact loading. The capabilities of the presented device are demonstrated by in situ studies of the indentation-induced phase transformations of Si thin films and modifications of molecular conformations in high density polyethylene films.

Lightweight, Flexible, High-Performance Carbon Nanotube Cables Made by Scalable Flow Coating

Coaxial cables for data transmission are ubiquitous in telecommunications, aerospace, automotive, and robotics industries. Yet, the metals used to make commercial cables are unsuitably heavy and stiff. These undesirable traits are particularly problematic in aerospace applications, where weight is at a premium and flexibility is necessary to conform with the distributed layout of electronic components in satellites and aircraft. The cable outer conductor (OC) is usually the heaviest component of modern data cables; therefore, exchanging the conventional metallic OC for lower weight materials with comparable transmission characteristics is highly desirable. Carbon nanotubes (CNTs) have recently been proposed to replace the metal components in coaxial cables; however, signal attenuation was too high in prototypes produced so far. Here, we fabricate the OC of coaxial data cables by directly coating a solution of CNTs in chlorosulfonic acid (CSA) onto the cable inner dielectric. This coating has an electrical conductivity that is approximately 2 orders of magnitude greater than the best CNT OC reported in the literature to date. This high conductivity makes CNT coaxial cables an attractive alternative to commercial cables with a metal (tin-coated copper) OC, providing comparable cable attenuation and mechanical durability with a 97% lower component mass.

Thermoviscoelastic Analysis and Creep Testing of Ambient Temperature Cure Epoxies Used in Adhesive Anchor Applications

Thermoviscoelastic properties and creep response of two commercial ambient temperature cure epoxy structural adhesives were analyzed and compared. The adhesives were formulated by the same manufacturer and appeared to be chemically similar; however, one system contained accelerators to shorten its cure time. In the laboratory, dynamic mechanical temperature/frequency sweeps were performed on both systems to generate dynamic mechanical and creep compliance master curves using time-temperature superposition principles. Differences were observed in the dynamic mechanical properties of the two adhesive systems as well as in their calculated creep compliance, which have been attributed to differences in their curing agent(s) and accelerator(s). Full-scale creep tests were carried out on anchors installed in concrete slabs and subjected to sustained loads for 82 days. These results were in good agreement with the creep compliance estimated using time-temperature superposition, suggesting that dynamic mechanical...

Evaluation of temperature-dependent adhesive performance via combinatorial probe tack measurements

We describe the design and application of a temperature gradient probe tack apparatus for investigating the adhesive performance of model pressure-sensitive adhesives (PSAs). In particular, we illustrate a probe tack apparatus for studying the effect of temperature on three critical adhesion identifiers: adhesion energy, elongation at break, and debonding mechanisms. The measurement temperature is varied across the PSA film using a gradient temperature stage constructed from a transparent sapphire plate with a heating and cooling source positioned at opposite ends. The transparent substrate allows visualization of the contact area and debonding mechanisms during the test. The gradient temperature stage is integrated onto a motorized x-y stage, enabling a matrix of probe tack tests to be conducted across the PSA film at different sample temperatures. We use a spherical probe to evaluate the adhesive performance of a 150μm thick model poly(styrene-b-isoprene-b-styrene) PSA film between a temperature range of 10 °C to 100 °C. We demonstrate that this apparatus is a viable combinatorial design for tack measurements and may be extended to more complicated two-dimensional gradient films.We describe the design and application of a temperature gradient probe tack apparatus for investigating the adhesive performance of model pressure-sensitive adhesives (PSAs). In particular, we illustrate a probe tack apparatus for studying the effect of temperature on three critical adhesion identifiers: adhesion energy, elongation at break, and debonding mechanisms. The measurement temperature is varied across the PSA film using a gradient temperature stage constructed from a transparent sapphire plate with a heating and cooling source positioned at opposite ends. The transparent substrate allows visualization of the contact area and debonding mechanisms during the test. The gradient temperature stage is integrated onto a motorized x-y stage, enabling a matrix of probe tack tests to be conducted across the PSA film at different sample temperatures. We use a spherical probe to evaluate the adhesive performance of a 150μm thick model poly(styrene-b-isoprene-b-styrene) PSA film between a temperature range o...