Publications

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The lubrication of silicon surfaces with alcohol vapors has recently been demonstrated. With a sufficient concentration of pentanol vapor present, sliding of a silica ball on an oxidized silicon wafer can proceed with no measurable wear. The initial results of time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of wear surfaces revealed a reaction product having thickness on the order of a monolayer, and with an ion spectrum that included fragments having molecular weights of 200 or more that occurred only inside the wear tracks. The parent alcohol molecule pentanol, has molecular weight of 88amu, suggesting that reactions of adsorbed alcohols on the wearing surfaces allowed polymerization of the alcohols to form higher molecular weight species. In addition to pin-on-disk studies, lubrication of silicon surfaces with pentanol vapors has also been demonstrated using MicroElectroMechanical Systems (MEMS) devices. Recent investigations of the reaction mechanisms of the alcohol molecules with the oxidized silicon surfaces have shown that wearless sliding requires a concentration of the alcohol vapor that is dependent upon the contact stress during sliding, with higher stress requiring a greater concentration of alcohol. Different vapor precursors including those with acid functionality, olefins, and methyl termination also produce polymeric reaction products, and can lubricate the silica surfaces. Doping the operating environment with oxygen was found to quench the formation of the polymeric reaction product, and demonstrates that polymer formation is not necessary for wearless sliding.

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An overwhelming majority of metamaterial designs that have been proposed thus far rely on the use of metallic resonators to afford properties that are unprecedented in nature. Though well suited for applications at radio and microwave frequencies, metals experience severe ohmic losses at higher frequencies rendering their use at such frequencies impractical. Certainly the future of metamaterials lies in their implementation in the visible and long wavelength infrared (LWIR, 8-12 {micro}m). Thus, alternative design protocols and material components tailored specifically for these frequencies are highly attractive. Herein, we present low permittivity, low permeability polymer dielectric materials that are well suited substrates for LWIR-metamaterial applications. These materials lack vibrational absorption bands in the 8-12 {micro}m range are 3D fabrication compatible, photopatternable, and high temperature tolerant. Thus, these materials are ideal for fabrication of 3D metamaterial structures operating in the LWIR and can also serve as negative photoresists for contact lithography applications.

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Materials with switchable states are desirable in many areas of science and technology. The ability to thermally transform a dielectric material to a conductive state should allow for the creation of electronics with built-in safety features. Specifically, the non-desirable build-up and discharge of electricity in the event of a fire or over-heating would be averted by utilizing thermo-switchable dielectrics in the capacitors of electrical devices (preventing the capacitors from charging at elevated temperatures). We have designed a series of polymers that effectively switch from a non-conductive to a conductive state. The thermal transition is governed by the stability of the leaving group after it leaves as a free entity. Here, we present the synthesis and characterization of a series of precursor polymers that eliminate to form poly(p-phenylene vinylene) (PPV's).

Materials with switchable states are desirable in many areas of science and technology. The ability to thermally transform a dielectric material to a conductive state should allow for the creation of electronics with built-in safety features. Specifically, the non-desirable build-up and discharge of electricity in the event of a fire or over-heating would be averted by utilizing thermo-switchable dielectrics in the capacitors of electrical devices (preventing the capacitors from charging at elevated temperatures). We have designed a series of polymers that effectively switch from a non-conductive to a conductive state. The thermal transition is governed by the stability of the leaving group after it leaves as a free entity. Here, we present the synthesis and characterization of a series of precursor polymers that eliminate to form poly(p-phenylene vinylene) (PPV's).

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A gradient array apparatus was constructed for the study of porous polymers produced using the process of chemically-induced phase separation (CIPS). The apparatus consisted of a 60 element, two-dimensional array in which a temperature gradient was placed in the y-direction and composition was varied in the x-direction. The apparatus allowed for changes in opacity of blends to be monitored as a function of temperature and cure time by taking images of the array with time. The apparatus was validated by dispense a single blend composition into all 60 wells of the array and curing them for 24 hours and doing the experiment in triplicate. Variations in micron scale phase separation were readily observed as a function of both curing time and temperature and there was very good well-to-well consistency as well as trial-to-trial consistency. Poragen of samples varying with respect to cure temperature was removed and SEM images were obtained. The results obtained showed that cure temperature had a dramatic affect on sample morphology, and combining data obtained from visual observations made during the curing process with SEM data can enable a much better understanding of the CIPS process and provide predictive capability through the relatively facile generation of composition-process-morphology relationships. Data quality could be greatly enhanced by making further improvements in the apparatus. The primary improvements contemplated include the use of a more uniform light source, an optical table, and a CCD camera with data analysis software. These improvements would enable quantification of the amount of scattered light generated from individual elements as a function of cure time. In addition to the gradient array development, porous composites were produced by incorporating metal particles into a blend of poragen, epoxy resin, and crosslinker. The variables involved in the experiment were metal particle composition, primary metal particle size, metal concentration, and poragen composition. A total of 16 different porous composites were produced and characterized using SEM. In general, the results showed that pore morphology and the distribution of metal particles was dependent on multiple factors. For example, the use of silver nanoparticles did not significantly affect pore morphology for composites derived from decanol as the poragen, but exceptionally large pores were obtained with the use of decane as the poragen. With regard to the effect of metal particle size, silver nanoparticles were essentially exclusively dispered in the polymer matrix while silver microparticles were found in pores. For nickel particles, both nanoparticles and microparticles were largely dispersed in the polymer matrix and not in the pores.

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This paper presents the development of a sensor to detect the oxidative and radiation induced degradation of polypropylene. Recently we have examined the use of crosslinked assemblies of nanoparticles as a chemiresistor-type sensor for the degradation products. We have developed a simple method that uses a siloxane matrix to fabricate a chemiresistor-type sensor that minimizes the swelling transduction mechanism while optimizing the change in dielectric response. These sensors were exposed with the use of a gas chromatography system to three previously identified polypropylene degradation products including 4-methyl-2-pentanone, acetone, and 2-pentanone. The limits of detection 210 ppb for 4-methy-2-pentanone, 575 ppb for 2-pentanone, and the LoD was unable to be determined for acetone due to incomplete separation from the carbon disulfide carrier.

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Both conventional and combinatorial approaches were used to study the pore formation process in epoxy based polymer systems. Sandia National Laboratories conducted the initial work and collaborated with North Dakota State University (NDSU) using a combinatorial research approach to produce a library of novel monomers and crosslinkers capable of forming porous polymers. The library was screened to determine the physical factors that control porosity, such as porogen loading, polymer-porogen interactions, and polymer crosslink density. We have identified the physical and chemical factors that control the average porosity, pore size, and pore size distribution within epoxy based systems.

Conductive polymers have become an extremely useful class of materials for many optical applications. We have developed an electrochemical growth method for depositing highly conductive ({approx}100 S/cm) polypyrrole. Additionally, we have adapted advanced fabrication methods for use with the polypyrrole resulting in gratings with submicron features. This conductive polymer micro-wire grid provides an optical polarizer with unique properties. When the polymer is exposed to ionizing radiation, its conductivity is affected and the polarization properties of the device, specifically the extinction ratio, change in a corresponding manner. This change in polarization properties can be determined by optically interrogating the device, possibly from a remote location. The result is a passive radiation-sensitive sensor with very low optical visibility. The ability to interrogate the device from a safe standoff distance provides a device useful in potentially dangerous environments. Also, the passive nature of the device make it applicable in applications where external power is not available. We will review the polymer deposition, fabrication methods and device design and modeling. The characterization of the polymer's sensitivity to ionizing radiation and optical testing of infrared polarizers before and after irradiation will also be presented. These experimental results will highlight the usefulness of the conductive infrared polarizer to many security and monitoring applications.

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Remote detection of radiation is a difficult problem due to the 1/r 2 fall-off Recent advances in polymer research and nanoscale fabrication methods along with advances in optical Polarimetrie remote sensing systems suggest a solution. The basic device uses a micro-wiregrid infrared polarizer fabricated in conductive polymer. When the polymer is exposed to hard radiation, its conductivity will be affected and the polarization properties of the device will change in a corresponding manner. This change in polarization properties can be determined by optically interrogating the device, possibly from a remote location. We will report on the development of a radiation-sensitive passive dosimeter polymer with very low optical visibility. Progress on material development, lithographic fabrication and optical characterization will be presented.

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Conductive polymers have become an extremely useful class of materials for many optical applications. Additionally, advanced fabrication methods have led to the development of metal based micro-wiregrid polarizers utilizing submicron features. Adapting these fabrication approaches for use with polymer materials leads to optical polarizers with unique properties. The patterning of conductive polymers with the small features required for wiregrid polarizers leads to several challenges. First, the deposition of the polymer must provide a layer thick enough to provide a polarizer with a useful extinction ratio that also has high conductivity and environmental stability. Two deposition approaches have been investigated, spin coating and electrochemical growth, and results of this work will be presented. Also, the polymers considered here are not compatible with basic photoresist processes. Various tactics have been examined to overcome this difficulty including the use of hard bakes of the polymer, protective overcoats and patterned growth. The adaptations required for successfully patterning the polymer will be reviewed. Finally, fabricated devices will be shown and their optical characterization presented.

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Polymer electronic devices and materials have vast potential for future microsystems and could have many advantages over conventional inorganic semiconductor based systems, including ease of manufacturing, cost, weight, flexibility, and the ability to integrate a wide variety of functions on a single platform. Starting materials and substrates are relatively inexpensive and amenable to mass manufacturing methods. This project attempted to plant the seeds for a new core competency in polymer electronics at Sandia National Laboratories. As part of this effort a wide variety of polymer components and devices, ranging from simple resistors to infrared sensitive devices, were fabricated and characterized. Ink jet printing capabilities were established. In addition to promising results on prototype devices the project highlighted the directions where future investments must be made to establish a viable polymer electronics competency.

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The gas-phase {mu}ChemLab{trademark} developed by Sandia can detect volatile organics and semi-volatiles organics via gas phase sampling . The goal of this three year Laboratory Directed Research and Development (LDRD) project was to adapt the components and concepts used by the {mu}ChemLab{trademark} system towards the analysis of water-borne chemicals of current concern. In essence, interfacing the gas-phase {mu}ChemLab{trademark} with water to bring the significant prior investment of Sandia and the advantages of microfabrication and portable analysis to a whole new world of important analytes. These include both chemical weapons agents and their hydrolysis products and disinfection by-products such as Trihalomethanes (THMs) and haloacetic acids (HAAs). THMs and HAAs are currently regulated by EPA due to health issues, yet water utilities do not have rapid on-site methods of detection that would allow them to adjust their processes quickly; protecting consumers, meeting water quality standards, and obeying regulations more easily and with greater confidence. This report documents the results, unique hardware and devices, and methods designed during the project toward the goal stated above. It also presents and discusses the portable field system to measure THMs developed in the course of this project.

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Molecular electronic based chemical vapor sensors were assembled using noble metal nanoparticles and short conjugated phenylene ethynylene (PE) based molecules. Sacrificial capping ligands on the nanoparticles were replaced by tighter binding PE ligands. The films were assembled between pairs of electrodes by iteratively exposing the substrates to solutions of the nanoparticles and PE crosslinking bridging ligands. Some of the conjugated bridging molecules contained an electron deficient phenol to provide a simple platform for developing sensor applications. The phenol is calculated to have a significant change in its HOMO/LUMO gap in the presence of specific analytes. Judicious combination of nanoparticle size and ligand structure provides a film in which the organic bridging ligands dramatically affect film conductance. Specifically, {pi}-conjugated ligands lower resistance more in films with smaller particles. Thus the sensing mechanism of these films is not based on the typical swelling mechanism but rather on the modulation of the molecular electronic structure of the conducting PE bridging ligands. Interdigitated Au electrodes built on quartz substrates were first silanized with tetrakis(dimethylamino)silane. The remaining amino functionalities were displaced with 1,8-octanedithiol (ODT) to give a thiolated surface capable of binding nanoparticles. The substrate was then incubated in a solution of dodecylamine-capped nanoparticles. The film thickness was increased via alternating exposure to solutions of bifunctional crosslinking molecules and nanoparticles (Figure 1). Nanoparticles and assembled films were characterized by TEM and AFM prior to electrical characterization. After verifying the selectivity of this new attachment chemistry, a novel robotic sample preparation was employed to build nanoparticle films of different thickness on prepared electrodes. By preparing the nanoparticle films using a robot, many problems with irregularities of the deposited films were eliminated. This sample preparation system was designed with the capability to measure the resistivity of the nanoparticle films after assembly of each layer. Using such a sample preparation system is vital for developing mass-produced sensors from nanoparticle films. The robotic system was used to deposit and measure the electrical properties of Pt and Au nanoparticles linked with different ligands such as ODT and meta-PE diisocyanide. Figure 2 is a plot showing the resistance vs. film layer for several combinations of nanoparticles and linker-ligands. The data shows that the resistance of the film drops and eventually saturates as additional nanoparticle layers are deposited. There is also an inversion in the resistance per layer that depends on the nanoparticle's type and the ligand used to crosslink the film. This data is significant because it shows how the selection of certain nanoparticle properties (such as size and material) and selection of an appropriate linking ligand can be used to tune the conductance of a film composed of nanoparticles. It is well known that smaller nanoparticles have a higher charging potential. This coupled with the inherent variability of organic molecules ensures that a film in which the organic molecules dominate conductivity can be achieved. In addition to the experiments above, nanoparticle films were assembled using cross-linkers that can be modified by an analyte. Figure 3 shows a typical I(V) curve for a Au nanoparticle film crosslinked with a phenylene ethynylene based electron deficient phenol. There is a clear reversible change in the resistance of the film when exposed first to acid and then base. The generation of a new response mechanism for nanoparticle films greatly increases the scope of organic/nanoparticle films for sensor applications. Their crosslinked nature increases their robustness and allows for use in both aqueous as well as organic solutions. In summary, we have developed a novel reproducible sample preparation system for the deposition of crosslinked nanoparticle films on a variety of substrates. This system has the ability to acquire electrical data during the sample deposition. Data collected for several nanoparticle film depositions demonstrated the ability to tune the conduction of the film by the selection of nanoparticle size and the cross-linking ligand. The material we have developed is a hybrid intermediate between a true organic conducting polymer and a classical nanoparticle film. The nanoparticles provide a scaffold on which to assemble various conducting/sensing oligomers and ligands without the problems inherent to conducting polymers.

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Nanoparticles have received much attention and have been the subject of many reviews. Nanoparticles have also been used to form super molecular structures for molecular electronic, and sensor applications. However, many limitations exist when using nanoparticles, including the ability to manipulate the particles post synthesis. Current methods to prepare nanoparticles employ functionalities like thiols, amines, phosphines, isocyanides, or a citrate as the metal capping agent. While these capping agents prevent agglomeration or precipitation of the particles, most are difficult to displace or impede packing in nanoparticle films due to coulombic repulsion. It is in this vein that we undertook the synthesis of nanoparticles that have a weakly bound capping agent that is strong enough to prevent agglomeration and in the case of the platinum particles allow for purification, but yet, easily displaced by other strongly binding ligands. The nanoparticles where synthesized according to the Brust method except stearonitrile was used instead of an aliphatic thiol. Both platinum and gold were examined in this manner. A representative procedure for the synthesis of platinum nanoparticles involved the phase transfer of chloroplatinic acid (0.37 g, 0.90 mmol) dissolved in water (30 mL) to a solution of tetraoctylammonium bromide (2.2 g, 4.0 mmol) in toluene (80 mL). After the chloroplatinic acid was transferred into the organic phase the aqueous phase was removed. Stearonitrile (0.23 g, 0.87 mmol) was added and sodium borohydride (0.38 g, 49 mmol) in water (25 mL) was added. The solution turned black almost immediately and after 15 min the organic phase was separated and passed through a 0.45 {micro}m Teflon filter. The resulting solution was concentrated and twice precipitated into ethanol ({approx}200 mL) to yield 0.11 g of black platinum nanoparticles. TGA experiments showed that the Pt particles contained 35% by mass stearonitrile. TEM images showed an average particle size of 1.3 {+-} 0.3 nm. A representative procedure for the synthesis of gold nanoparticles involved the transfer of hydrogen tetrachloroaurate (0.18 g, 0.53 mmol) dissolved in water (15 mL) to a solution of tetraoctylammonium bromide (1.1 g, 2.0 mmol) in toluene (40 mL). After the gold salt transferred into the organic phase the aqueous phase was removed. Stearonitrile (0.23 g, 0.87 mmol) was added and sodium borohydride (0.19 g, 5.0 mmol) in water (13 mL) was added. The solution turned dark red almost immediately, and after 15 min the organic phase was separated and passed through a 0.45 {micro}m Teflon filter. The resulting solution was used without purification via precipitation because attempts at precipitation with ethanol resulted in agglomeration. TEM images showed an average particle size of 5.3 {+-} 1.3 nm. The nanoparticles synthesized were also characterized using atomic force microscopy in tapping mode. The AFM images agree with the TEM images and show a relatively monodispersed collection of nanoparticles. Platinum nanoparticles were synthesized without stearonitrile to show that the particles were in fact capped with the stearonitrile and not the tetraoctylammonium bromide. In the absence of stearonitrile the nanoparticles would not redissolve in hexane or toluene after precipitation. While it is possible the tetraoctylammonium bromide helps prevent agglomeration by solvation into the capping stearonitrile ligand layer on the particles recovery of a quantitative amount of the starting tetraoctylammonium bromide was difficult and we cannot rule out that some small amount of tetraoctylammonium bromide serves in a synergistic capacity to help solubilize the isolated platinum particles. Several exchange reactions were carried out using the isolated Pt nanoparticles. The stearonitrile cap was exchanged for hexadecylmercaptan, octanethiol, and benzeneethylthiol. In a typical exchange reaction, Pt nanoparticles (10 mg) were suspended in hexane (10 mL) and the exchange ligand was added (50 {micro}L). The solutions were allowed to stir overnight and precipitated twice using ethanol. TGA experiments confirmed ligand exchange. We have also shown that these particles may be assembled in a layer by layer (LBL) fashion to build up three dimensional assemblies. As an example of this LBL assembly a substrate consisting of gold electrodes separated by 8 {micro}m on a quartz wafer was first functionalized by immersing in a solution of 1,8-octanedithiol (50 {micro}L) in hexane (10 mL) for 15 min, rinsed with hexane (10 mL), ethanol (10 mL), and dried under a stream of nitrogen. The scaffold was then placed in a toluene solution containing Au nanoparticles capped with stearonitrile (10 mg/mL) for 15 minutes. The scaffold was then rinsed with hexane (10 mL), ethanol (10 mL), and dried under a stream of nitrogen. The substrate was then immersed iteratively between the 1,8-octanedithiol and the Au nanoparticle solution 4 more times.