ICMCTF2006 Session H1: Nanostructured Coatings and Novel Deposition Strategies

Tuesday, May 2, 2006 1:30 PM in Room Terrace Pavilion

Tuesday Afternoon

Time Period TuA Sessions | Abstract Timeline | Topic H Sessions | Time Periods | Topics | ICMCTF2006 Schedule

Start Invited? Item
1:30 PM H1-1 Carbon Nanotubes for Human Space Flight Applications
S. Arepalli (ERC Inc/ESCG/NASA-Johnson Space Center)

Research activities on carbon nanotubes at NASA-Johnson Space Center include production, purification, characterization and their applications for human space flight. In-situ diagnostics during nanotube production by laser oven process resulted in a better understanding of the nanotube growth [1]. Details of the results from the â?oparametric study of the pulsed laser ablation process indicate the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence [2]. A recently established NASA-JSC protocol [3] for SWCNT characterization is undergoing revision with feedback from nanotube community. Efforts at JSC over the past five years in composites have centered on structural polymer/nanotube systems. Recent activities broadened this focus to multifunctional materials, supercapaciotrs, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large surface area as well as high electrical and thermal conductivity exhibited by SWCNTs.

[1] Carl. D. Scott, Sivaram Arepalli, Pavel Nikolaev and R. E. Smalley, "Growth Mechanisms for Single-wall Carbon Nanotubes in a Laser Ablation Process", Applied Physics A, Vol. 72, May 2001, pp. 573-580 (2001)

[2] Arepalli S., Holmes W. A., Nikolaev P., Hadjiev V. G., and Scott C. D., "A Parametric Study of Single-Wall Carbon Nanotube Growth by Laser Ablation", J. Nanosci and Nanotech. Vol. 4, 737-747 (2004).

[3] Arepalli S., Nikolaev P., Gorelik O., Hadjiev V. G., Holmes W. A., Files B. S., and Yowell L., "Protocol for the Characterization of Single-Wall Carbon Nanotube Material Quality", Carbon, Vol. 42, p. 1783-1791 (2004).

2:10 PM H1-3 Development and Understanding of Nano-Reinforced Polymer and Fluid Systems
K. Lozano (The University of Texas Pan American)
Nanofibers, nanotubes and nanoparticles in general have shown promise as reinforcements for polymeric materials, metallic materials and fluids in general. This presentation will address experimental, theoretical and manufacturing issues associated with the development of carbon nanotube/nanofibers, metallic nanowires, and fullerene particles reinforced polymeric and liquid systems. Aspects such as purification and functionalization of the nanoreinforcements as well as incorporation of the materials will be covered. Mechanical, electrical, thermo-physical, rheological and electrorheological characterization of the developed systems will be addressed. Attractive potential applications of the developed systems will also be discussed.
2:50 PM H1-5 Room-Temperature Deposition of Carbon Nanomaterials by Excimer Laser Ablation
G. Radhakrishnan, P.M. Adams (The Aerospace Corporation)
Numerous investigations have been reported on the pulsed laser deposition of carbon nanotubes, mostly using the Nd:YAG laser for ablation. In all cases the depositions have been conducted at high-temperatures and high pressures. Here we report on the deposition of very interesting carbon nanostructures at room temperature using excimer laser radiation at 248 nm to ablate mixed graphite-nickel/cobalt targets. We find that the formation of the carbon nanomaterials is dependent on the particular ambient gas employed. In presence of O2 gas, carbon nanotubes and nano-onions are produced. The carbon nanotubes have notably large channel diameters of 100-200 nm and the carbon nano-onion structures are 100-200 nm in diameter, also much larger than those produced by other methods. High-resolution, in-situ, time-resolved emission spectroscopy has been used to follow the production of molecular carbon species such as C2 and C3, as well as metals such as Ni or Co in the different ambients employed. Mechanistic details of the formation of carbon nanotubes and nano-onions, and in-situ optical emission spectroscopy will be described.
3:10 PM H1-6 Analysis of Nanostructured Coatings Synthesized by Ballistic Impaction of Nanoparticles
J. Hafiz, R. Mukherjee, X. Wang, J.V.R. Heberlein, P.H. McMurry, S.L. Girshick (University of Minnesota)

SiC, TiN, and Si-Ti-N nanostructured coatings were deposited using a novel synthesis process by ballistic impaction of nanoparticles. The nanoparticles were synthesized by injecting chemical reactants into a thermal plasma that underwent a rapid expansion through a converging nozzle, resulting in gas-phase nucleation. The deposition rates of the coatings varied from 1 to 60 µm/min, depending on reactant flow rates while substrate temperatures during deposition ranged from 400 to 9000C. Molybdenum, polished silicon wafers, and two types of steel (high speed and aircraft grade steel) were used as substrate material. The reactants were silicon tetrachloride, and/or titanium tetrachloride, with methane additionally injected to produce the carbides, and ammonia to produce the nitrides. Experiments were conducted with a copper gettering system to reduce oxygen contamination, which is believed to have a detrimental effect on film hardness.

In-situ particle size distribution measurements were performed using a sampling probe interfaced to an extraction/dilution system in series with a scanning electrical mobility spectrometer. Measured distributions from the sampling probe show that particle size distributions peak between 10 to 20 nm under typical operating conditions.

Microstructural characterization of the films was performed using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Mechanical properties were evaluated using a nanoindenter and a tribometer. Chemical and elemental compositional profiles of the coatings were obtained using Auger electron spectroscopy (AES) depth profiles. Compositional profiles combined with other characterization techniques provided insight into the mechanism of coating formation and growth, enabling the optimization of operating conditions to achieve desired film properties.

3:30 PM H1-7 The Thermal Stability of Nanocrystalline AuCu Alloys
A.F. Jankowski (Lawrence Livermore National Laboratory)

The development of deposition methods to control the nanocrystalline grain structure promotes the enhancement of physical properties as strength and surface hardness. Recent work in pulsed electro-deposition enables the synthesis of AuCu alloys with grain sizes as small as 5 nm. The thermal stability of AuCu nanocrystalline structures, as subjected to isothermal anneal treatments, is now investigated to assess the fundamental difference between two dominant diffusion mechanisms - - bulk and grain growth. The mobility of grain boundaries and the resultant coarsening of grain size are distinguished from the process of bulk diffusion as assessed through microscopic changes in composition gradients. The use of x-ray diffraction reveals changes in the grain size through broadening of Bragg reflections as quantified using the Debye-Scherrer formulation. The assessment of bulk diffusion kinetics at low temperatures by x-ray diffraction is approached through the use of concentration waves and the microscopic theory of diffusion. This approach provides a low-temperature benchmark for reference to high-temperature isotope diffusion. Energy dispersive x-ray spectroscopy is used to spatially resolve the time-temperature dependence of artificially introduced composition gradients. Although the kinetics of bulk diffusion are slow at temperatures below 500 K, less than 10-20 cm2-sec, the kinetics of grain boundary diffusion appear much faster at rates greater than 10-16 cm2-sec. The present result suggests that the mechanical gains appreciated in as-deposited nanocrystalline AuCu are quite sensitive to low-temperature anneal treatments. A path to stabilize the nanostructure of the binary AuCu alloy is proposed through a ternary alloy addition.

This work was performed under the auspices of the U. S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48.

3:50 PM H1-8 Spatially Defined Arrays of Metal Oxide Quantum Dots
J.F. Groves (University of Virginia)
Within the collaborative environment of the Center for Nanoscopic Materials Design, a National Science Foundation Materials Research Science and Engineering Center (MRSEC) located at the University of Virginia, research is underway into guided growth of self-assembling quantum dots on single crystal substrates. While the Center's core research focuses upon the Si-Ge system, exploratory work is determining if the guided growth processes extend to metal oxide systems that form similar quantum dot structures. This talk will describe the metal oxide guided self-assembly research performed in Cu2O on SrTiO3. Work to date has demonstrated an ability to specify the growth location of metal oxide quantum dots, with growth location being defined by localized focused ion beam surface modifications. This work will be described in detail. Having validated the concept of guided metal oxide quantum dot growth, efforts are now underway to identify quantum dot forming metal oxide systems with properties valuable in a range of applications. A portion of this search is being performed within an interdisciplinary societal and ethical implications of nanotechnology environment. This talk will highlight the impact that this interdisciplinary environment has had upon the direction of the research.
4:30 PM H1-10 Spray Pyrolysis Deposition of Nanostructured Zinc Oxide Films
M. Krunks, T. Dedova, I. Oja (Tallinn University of Technology, Estonia)
Highly structured ZnO films were prepared by simple and cost effective spray pyrolysis technique using aqueous or aqueous-alcoholic solutions containing ZnCl2 as a zinc source. The layers were characterized by SEM, TEM, XRD and PL spectroscopy. The effect of the deposition parametres such as the stock solution composition and the concentration of the precursors in solution, the growth temperature and the solution feeding rate onto the rod size, the aspect ratio and the orientation of ZnO crystals in the films and on the substrate coverage have been studied. Structured layers are consisting of well-developed hexagonal rods of ZnO with length from 50 nm up to six-seven microns, the diameter of rods could be varied from some tens of nanometers up to 1 micron. The aspect ratio (length to diameter) of the crystals could be changed from 1.5 up to 50. Such nanorods are individual single crystals with high purity.
4:50 PM H1-11 Photocatalytic Properties of Porous TiO2 /Ag Thin Films
C.-C. Chang, J.-Y. Chen, C.-K. Lin, C.-C. Chan (Feng Chia University, Taiwan)

In the present study, nanocrystalline TiO2/Ag composite thin films were prepared by a sol-gel spin coating technique. By introducing polystyrene (PS) microshperes into the precursor solution, porous TiO2/Ag thin films can be prepared after calcination at a temperature of 500°C for 2 hours. Three different sizes of PS microspheres will be used to prepare porous TiO2 films. The as-prepared TiO2 and TiO2/Ag thin films were characterized by X-ray diffractometry, and scanning electron microscopy to reveal the structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.

After calcination, the as-prepared TiO2 films exhibited different porous structure when different size PS microspheres were introduced. XRD results showed that all TiO2/Ag films exhibited a major anatase phase. The photodegradation of porous TiO2 thin film prepared with 200 nm PS microspheres and doped with 1 % mol Ag exhibited the best photocatalytic efficiency where ~ 100% methylene blue can be decomposed after UV exposure for 8 hours.

5:10 PM H1-12 Electrochromic Properties of Nanocrystalline MoO3 Thin Films
C.-S. Hsu, C.-K. Lin, C.-C. Chan, H.-T. Huang (Feng Chia University, Taiwan)

Electrochromism have attracted many Research and Development (R&D) interests due to potential applications such as automobile and building glazings, energy saving, etc. Among the transition metal oxides possessing electrochromic properties, tungsten trioxide (WO3) exhibits the best properties and being studied by many researchers. Molybdenum trioxide (MoO3) also exhibits electrochromic properties that can change color from bluish (bleached state) to deep blue (colored state).

In the present study, MoO3 thin films were prepared by a sol gel spin coating technique. The spin-coated thin films were amorphous and, after calcining, nanocrystalline MoO3 thin films were prepared successfully. The effect of annealing temperature ranged from room temperature to 500 °C was investigated. Preliminary results showed that the 350°C heat-treated MoO3 thin films exhibited the best electrochromic properties among the films examined in the present study.

5:30 PM H1-13 Nanoparticle Disperse-Strengthened Coatings and Electrode Materials for Electrospark Deposition
E.A. Levashov, P.V. Vakaev, E.I. Zamulaeva, A.E. Kudryashov, Yu.S. Pogozhev, D.V. Shtansky (Moscow State Institute of Steel and Alloys (Technological University), Russia); A.A. Voevodin (Air Force Research Laboratory); A. Sanz (SKF Engineering & Research Center, Sweden)
Combustion synthesis (SHS) and powder metallurgy technologies were used to develop and fabricate advanced composite electrodes for electrospark deposition (ESD) of thick tribological coatings which are disperse-strengthened by incorporation of nanosized particles of NbC, WC, W, WC-Co, ZrO2, Al2O3, and Si3N4. It was shown that introduction of small amount of nanosized refractory compounds into the charge provides a significant modification of electrode material grains structure made of titanium carbide and diboride. Coating material science and technological aspects were considered for various electrode compositions in production of nanopartilce disperse-hardening alloys. Hard alloys based on TiC were developed using the SHS technology and annealing, which have simultaneous strengthening of both metallic binder and carbide grains in result of nanoparticle incorporations. Carbide grains contained MeVC or (MeV-Ti) nucleations. Metallic binder contained nanoparticle extractions of gamma prime phase. Two mechanisms of particle concentration separation from supersaturated solid solution in combustion zone were proposed. Nanostructured electrodes in the shape of disks and rods were produced, which were made of cemented carbides with a WC grain size less than 120 nm and incorporated nanosized plasma chemical powders of WC, WC-Co and sol-gel Co. Novel ESD- equipment with attachments for coating process mechanization was developed and used. Wear resistant coatings with excellent properties were deposited on iron, nickel and titanium alloy substrates. Positive effects of nanosized additives and nucleations on the coating technological process, microstructure, and properties are discussed.
Time Period TuA Sessions | Abstract Timeline | Topic H Sessions | Time Periods | Topics | ICMCTF2006 Schedule