Seong H. Kim

Nanotribology and MEMS

The tribological phenomena of adhesion, friction, and wear arise when solid objects make contact. As the size of devices shrinks to micro- and nanoscales, the surface-to-volume ratio increases and the effects of body forces (gravity and inertia) become insignificant compared with those of surface forces (van der Waals, capillary, electrostatic, and chemical bonding). In microelectromechanical systems (MEMS), tribological and static interfacial forces are comparable with forces driving device motion. In this situation, macroscale lubrication and wear mitigation methods, such as the use of bulk fluids and micrometer thick coatings, are ineffective; new nano-engineering approaches must be employed for MEMS devices with moving structures. We review fundamental tribological problems related to micro- and nanoscale mechanical contacts and developments in MEMS lubrications.

Preparation of biocatalytic nanofibres with high activity and stability via enzyme aggregate coating on polymer nanofibres.

We have developed a unique approach for the fabrication of enzyme aggregate coatings on the surfaces of electrospun polymer nanofibres. This approach employs covalent attachment of seed enzymes onto nanofibres consisting of a mixture of polystyrene and poly(styrene-co-maleic anhydride), followed by a glutaraldehyde (GA) treatment that cross-links additional enzyme molecules and aggregates from the solution onto the covalently attached seed enzyme molecules. These cross-linked enzyme aggregates, covalently attached to the nanofibres via the linkers of seed enzyme molecules, are expected to improve the enzyme activity due to increased enzyme loading, and also the enzyme stability. To demonstrate the principle, we coated α-chymotrypsin (CT) on nanofibres electrospun from a mixture of polystyrene and poly(styrene-co-maleic anhydride). The initial activity of CT-aggregate-coated nanofibres was nine times higher than nanofibres with just a layer of covalently attached CT molecules. The enzyme stability of CT-aggregate-coated nanofibres was greatly improved with essentially no measurable loss of activity over a month of observation under rigorous shaking conditions. This new approach of enzyme coating on nanofibres, yielding high activity and stability, creates a useful new biocatalytic immobilized enzyme system with potential applications in bioconversion, bioremediation, and biosensors.

Effects of adsorbed water layer structure on adhesion force of silicon oxide nanoasperity contact in humid ambient

The origin of the large relative-humidity (RH) dependence of the adhesion force in the single-asperity contact between silicon oxide surfaces is elucidated. As RH increases, the adhesion force measured with an atomic force microscopy (AFM) initially increases, reaches a maximum, and then decreases at high RH. The capillary force alone cannot explain the observed magnitude of the RH dependence. The origin of the large RH dependence is due to the presence of an icelike structured water adsorbed at the silicon oxide surface at room temperature. A solid-adsorbate-solid model is developed calculating the contributions from capillary forces, van der Waals interactions, and the rupture of an ice-ice bridge at the center of the contact region. This model illustrates how the structure, thickness, and viscoelastic behavior of the adsorbed water layer influence the adhesion force of the silicon oxide nanoasperity contact.

Growth and characterization of InGaAs/InGaP quantum dots for midinfrared photoconductive detector

We report InGaAs quantum dot intersubband infrared photodetectors grown by low-pressure metalorganic chemical vapor deposition on semi-insulating GaAs substrates. The optimum growth conditions were studied to obtain uniform InGaAs quantum dots constructed in an InGaP matrix. Normal incidence photoconductivity was observed at a peak wavelength of 5.5 μm with a high responsivity of 130 mA/W and a detectivity of 4.74×107 cm H1/2/W at 77 K.

AFM and SFG studies of pHEMA-based hydrogel contact lens surfaces in saline solution: adhesion, friction, and the presence of non-crosslinked polymer chains at the surface

The surfaces of two types of soft contact lenses neutral and ionic hydrogels--were characterized by atomic force microscopy (AFM) and sum-frequency-generation (SFG) vibrational spectroscopy. AFM measurements in saline solution showed that the presence of ionic functional groups at the surface lowered the friction and adhesion to a hydrophobic polystyrene tip. This was attributed to the specific interactions of water and the molecular orientation of hydrogel chains at the surface. Friction and adhesion behavior also revealed the presence of domains of non-crosslinked polymer chains at the lens surface. SFG showed that the lens surface became partially dehydrated upon exposure to air. On this partially dehydrated lens surface, the non-crosslinked domains exhibited low friction and adhesion in AFM. Fully hydrated in saline solution, the non-crosslinked domains extended more than tens of nanometers into solution and were mobile.

Selective Detection of Crystalline Cellulose in Plant Cell Walls with Sum-Frequency-Generation (SFG) Vibration Spectroscopy

The selective detection of crystalline cellulose in biomass was demonstrated with sum-frequency-generation (SFG) vibration spectroscopy. SFG is a second-order nonlinear optical response from a system where the optical centrosymmetry is broken. In secondary plant cell walls that contain mostly cellulose, hemicellulose, and lignin with varying concentrations, only certain vibration modes in the crystalline cellulose structure can meet the noninversion symmetry requirements. Thus, SFG can be used to detect and analyze crystalline cellulose selectively in lignocellulosic biomass without extraction of noncellulosic species from biomass or deconvolution of amorphous spectra. The selective detection of crystalline cellulose in lignocellulosic biomass is not readily achievable with other techniques such as XRD, solid-state NMR, IR, and Raman analyses. Therefore, the SFG analysis presents a unique opportunity to reveal the cellulose crystalline structure in lignocellulosic biomass.

Highly stable trypsin-aggregate coatings on polymer nanofibers for repeated protein digestion

A stable and robust trypsin‐based biocatalytic system was developed and demonstrated for proteomic applications. The system utilizes polymer nanofibers coated with trypsin aggregates for immobilized protease digestions. After covalently attaching an initial layer of trypsin to the polymer nanofibers, highly concentrated trypsin molecules are crosslinked to the layered trypsin by way of a glutaraldehyde treatment. This process produced a 300‐fold increase in trypsin activity compared with a conventional method for covalent trypsin immobilization, and proved to be robust in that it still maintained a high level of activity after a year of repeated recycling. This highly stable form of immobilized trypsin was resistant to autolysis, enabling repeated digestions of BSA over 40 days and successful peptide identification by LC‐MS/MS. This active and stable form of immobilized trypsin was successfully employed in the digestion of yeast proteome extract with high reproducibility and within shorter time than conventional protein digestion using solution phase trypsin. Finally, the immobilized trypsin was resistant to proteolysis when exposed to other enzymes (i.e., chymotrypsin), which makes it suitable for use in “real‐world” proteomic applications. Overall, the biocatalytic nanofibers with trypsin aggregate coatings proved to be an effective approach for repeated and automated protein digestion in proteomic analyses.

A mathematical model for chemical–mechanical polishing based on formation and removal of weakly bonded molecular species

Abstract This paper presents a mathematical model that describes the chemical–mechanical synergy and mechanism of material removal in chemical–mechanical polishing (CMP). The physical basis of the model is that chemical reactions convert strongly bonded surface atoms/molecules to weakly bonded molecular species while the mechanical action delivers the energy that is needed to break the weak molecular bonds, thereby removing the surface materials at the molecular scale. Three key variables are defined to describe the chemical–mechanical synergetic effects. Close-form equations are derived relating these variables to the process parameters, making use of the concepts of chemical–mechanical equilibrium, chemical kinetics, contact mechanics, molecular binding energy and random-process probability. The model is applied to the process of silicon-wafer CMP. The governing equation of the material removal reveals some insights into the process. It also offers some sensible explanations to the effects of the operating and material parameters on the rate of material removal and process quality.

Characterization of crystalline cellulose in biomass: Basic principles, applications, and limitations of XRD, NMR, IR, Raman, and SFG

Cellulose is among the most important and abundant biopolymers in biosphere. It is the main structural component of a vast number of plants that carries vital functions for plant growth. Cellulose-based materials have been used in a variety of human activities ranging from papers and fabrics to engineering applications including production of biofuels. However, our understanding of the cellulose structure in its native form is quite limited because the current experimental methods often require separation or purification processes and provide only partial information of the cellulose structure. This paper aims at providing a brief background of the cellulose structure and reviewing the basic principles, capabilities and limitations of the cellulose characterization methods that are widely used by engineers dealing with biomass. The analytical techniques covered in this paper include x-ray diffraction, nuclear magnetic resonance, and vibrational spectroscopy (infrared, Raman, and sum-frequency-generation). The scope of the paper is restricted to the application of these techniques to the structural analysis of cellulose.

Fabrication of Superhydrophobic Surfaces

Superhydrophobicity has recently drawn a great deal of attention from both fundamental and practical application points of view. This paper summarizes the basic principles involved in creation of superhydrophobicity and reviews the diverse methods recently developed to make superhydrophobic surfaces and coatings. The hydrophobic property of materials can be amplified through the surface roughness. This was first addressed theoretically in the 1930s and 1940s. Although there have been significant advances made in superhydrophobicity theories, the basic design principles to fabricate superhydrophobic surfaces and coatings remain essentially the same. Recent developments in fabrication of superhydrophobic surfaces can be categorized in three different strategies — (1) roughening hydrophobic surfaces, (2) creating rough topographic features on substrates followed by application of hydrophobic surface modification methods and (3) depositing hydrophobic materials with rough surface textures. Various methods found in the literature are grouped and described in these categories. Finally, future challenges and issues involved in utilizing and understanding superhydrophobicity are discussed.