Ultrathin amorphous carbon films synthesized by filtered cathodic vacuum arc used as protective overcoats of heat-assisted magnetic recording heads.

Despite numerous investigations of amorphous carbon (a-C) films, a comprehensive study of the feasibility and optimization of sub-5-nm-thick a-C films deposited onto the write pole of heat-assisted magnetic recording (HAMR) heads is lacking. The main objective of this study was to identify the role of pulse substrate bias voltage and C+ ion incidence angle on the structure and thickness of 1-4-nm-thick a-C films deposited by a rather new thin-film deposition method, known as filtered cathodic vacuum arc (FCVA). The cross-sectional structure of a-C films synthesized under various FCVA conditions was examined by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). It was found that film growth under process conditions of low-to-intermediate substrate bias voltage (in the range of -25 to -100 V), low ion incidence angle (10°), very short deposition time (6 s), and fixed other deposition parameters (65% duty cycle of substrate pulse biasing and 1.48 × 1019 ions/m2·s ion flux) yields a-C films of thickness ≤4 nm characterized by a significant content (~50-60 at%) of tetrahedral (sp3) carbon atom hybridization. A threshold where sp3 hybridization is greatly reduced due to limited film growth was determined from the HRTEM/STEM and EELS measurements. The results of this study demonstrate the viability of FCVA to produce extremely thin and uniform protective a-C films with relatively high sp3 contents for HAMR heads.

Nanostructure, structural stability, and diffusion characteristics of layered coatings for heat-assisted magnetic recording head media.

The intense laser heating in heat-assisted magnetic recording (HAMR) has been a major hindrance to HAMR technology from becoming commercially viable. Thermal damage of the near-field transducer (NFT) and write pole (WP) embedded in the trailing edge of the magnetic head due to failure of the protective carbon overcoat after prolonged heating at an elevated temperature are major obstacles. Therefore, the main objective of this study was to develop an effective coating method for HAMR heads. This was accomplished by introducing a new class of layered coatings consisting of ultrathin amorphous carbon (a-C) overcoat, adhesion (SiN) layer, and buffer (NiCr or TaOx) layer sequentially deposited onto Au and FeCo base layers to mimic the layer stacking of NFT and WP elements, respectively. The structural stability of the a-C overcoats and diffusion characteristics of each comprising layer under conditions of heating at 350 °C for 30 min in an Ar atmosphere were investigated by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). For most stacking configurations the HRTEM/STEM and EELS results generally revealed some layer intermixing and minute carbon atom rehybridization in the heated a-C overcoats. The findings of this investigation suggest that further optimization of the developed layered coatings can provide a viable solution to thermal damage of HAMR heads.

Single-cell mechanics--An experimental-computational method for quantifying the membrane-cytoskeleton elasticity of cells.

The membrane-cytoskeleton system plays a major role in cell adhesion, growth, migration, and differentiation. F-actin filaments, cross-linkers, binding proteins that bundle F-actin filaments to form the actin cytoskeleton, and integrins that connect the actin cytoskeleton network to the cell plasma membrane and extracellular matrix are major cytoskeleton constituents. Thus, the cell cytoskeleton is a complex composite that can assume different shapes. Atomic force microscopy (AFM)-based techniques have been used to measure cytoskeleton material properties without much attention to cell shape. A recently developed surface chemical patterning method for long-term single-cell culture was used to seed individual cells on circular patterns. A continuum-based cell model, which uses as input the force-displacement response obtained with a modified AFM setup and relates the membrane-cytoskeleton elastic behavior to the cell geometry, while treating all other subcellular components suspended in the cytoplasmic liquid (gel) as an incompressible fluid, is presented and validated by experimental results. The developed analytical-experimental methodology establishes a framework for quantifying the membrane-cytoskeleton elasticity of live cells. This capability may have immense implications in cell biology, particularly in studies seeking to establish correlations between membrane-cytoskeleton elasticity and cell disease, mortality, differentiation, and migration, and provide insight into cell infiltration through nonwoven fibrous scaffolds. The present method can be further extended to analyze membrane-cytoskeleton viscoelasticity, examine the role of other subcellular components (e.g., nucleus envelope) in cell elasticity, and elucidate the effects of mechanical stimuli on cell differentiation and motility. STATEMENT OF SIGNIFICANCE: This is the first study to decouple the membrane-cytoskeleton elasticity from cell stiffness and introduce an effective approach for measuring the elastic modulus. The novelty of this study is the development of new technology for quantifying the elastic stiffness of the membrane-cytoskeleton system of cells. This capability could have immense implications in cell biology, particularly in establishing correlations between various cell diseases, mortality, and differentiation with membrane-cytoskeleton elasticity, examining through-tissue cell migration, and understanding cell infiltration in porous scaffolds. The present method can be further extended to analyze membrane-cytoskeleton viscous behavior, identify the contribution of other subcellular components (e.g., nucleus envelope) to load sharing, and elucidate mechanotransduction effects due to repetitive compressive loading and unloading on cell differentiation and motility.

In vitro measurement of the mechanical properties of skin by nano/microindentation methods.

The elastic behaviors of stratum corneum, viable epidermis, dermis, and whole skin were investigated by nano/microindentation techniques. Insignificant differences in reduced elastic modulus of skin samples obtained from three different porcine breeds revealed breed type independent measurements. The reduced elastic modulus of stratum corneum is shown to be about three orders of magnitude higher than that of dermis. As a result, for relatively shallow and deep indentations, skin elasticity is controlled by that of stratum corneum and dermis, respectively. Skin deformation is interpreted in the context of a layered structure model consisting of a stiff and hard surface layer on a compliant and soft substrate, supported by microscopy observations and indentation measurements.

Plasma-assisted heparin conjugation on electrospun poly(L-lactide) fibrous scaffolds.

Heparin conjugation on poly(L-lactide) fibrous scaffolds fabricated by electrospinning was accomplished by surface functionalization with amine (-NH2) groups using a sequential treatment with Ar-NH3 and H2 plasmas. The density of the incorporated -NH2 groups was determined by combining a chemical derivatization method with X-ray photoelectron spectroscopy. The time of Ar-NH3 plasma treatment significantly affected the N/C, -NH2 /N, and -NH2 /C fractions, whereas the plasma power, Ar-NH3 gas composition, and time of H2 plasma treatment only influenced the -NH2 /N and -NH2 /C fractions. Scaffold surface functionalization by -NH2 groups significantly increased the amount of covalently bonded heparin compared to a hydrolysis method. The function of immobilized heparin was confirmed by the decrease of platelet attachment during the exposure of the scaffolds to blood from Sprague-Dawley rats. In vitro experiments with bovine aorta endothelial cells demonstrated that heparin conjugation enhanced cell infiltration through the fibrous scaffolds, regardless of the amount of covalently immobilized heparin.

Skin viscoelasticity studied in vitro by microprobe-based techniques.

Time-dependent deformation of porcine skin was studied in vitro using specialized microprobe instruments. The deformation behavior of stratum corneum, dermis, and whole skin is examined in the context of results of creep strain, elastic stiffness, and viscoelastic constants obtained in terms of the hold time, loading/unloading rate, and maximum indentation depth (load). Skin time-dependent deformation is significantly influenced by dermis viscoelasticity up to a critical indentation depth (load) beyond which it is controlled by the outermost hard epidermis, particularly stratum corneum. Skin viscoelastic behavior under constant load (creep) and constant displacement (stress relaxation) is interpreted in the light of phenomenological observations and experimental trends.

Tribological altruism: A sacrificial layer mechanism of synovial joint lubrication in articular cartilage.

Boundary lubrication is characterized by sliding surfaces separated by a molecularly thin film that reduces friction and wear of the underlying substrate when fluid lubrication cannot be established. In this study, the wear and replenishment rates of articular cartilage were examined in the context of friction coefficient changes, protein loss, and direct imaging of the surface ultrastructure, to determine the efficiency of the boundary lubricant (BL) layer. Depletion of cartilage lubricity occurred with the concomitant loss of surface proteoglycans. Restoration of lubrication by incubation with synovial fluid was much faster than incubation with culture media and isolated superficial zone protein. The replenishment action of the BL layer in articular cartilage was rapid, with the rate of formation exceeding the rate of depletion of the BL layer to effectively protect the tissue from mechanical wear. The obtained results indicate that boundary lubrication in articular cartilage depends in part on a sacrificial layer mechanism. The present study provides insight into the natural mechanisms that minimize wear and resist tissue degeneration over the lifetime of an organism.

The role of lubricant entrapment at biological interfaces: reduction of friction and adhesion in articular cartilage.

Friction and adhesion of articular cartilage from high- and low-load-bearing regions of bovine knee joints were examined with a tribometer under various loads and equilibration times. The effect of trapped lubricants was investigated by briefly unloading the cartilage sample before friction testing, to allow fluid to reflow into the contact interface and boundary lubricants to rearrange. Friction and adhesion of high-load-bearing joint regions were consistently lower than those of low-load-bearing regions. This investigation is the first to demonstrate the regional variation in the friction and adhesion properties of articular cartilage. Friction coefficient decreased with increasing contact pressure and decreasing equilibration time. Briefly unloading cartilage before the onset of sliding resulted in significantly lower friction and adhesion and a loss of the friction dependence on contact pressure, suggesting an enhancement of the cartilage tribological properties by trapped lubricants. The results of this study reveal significant differences in the friction and adhesion properties between high- and low-load-bearing joint regions and elucidate the role of trapped lubricants in cartilage tribology.

Dependence of nanoscale friction and adhesion properties of articular cartilage on contact load.

Boundary lubrication of articular cartilage by conformal, molecularly thin films reduces friction and adhesion between asperities at the cartilage-cartilage contact interface when the contact conditions are not conducive to fluid film lubrication. In this study, the nanoscale friction and adhesion properties of articular cartilage from typical load-bearing and non-load-bearing joint regions were studied in the boundary lubrication regime under a range of physiological contact pressures using an atomic force microscope (AFM). Adhesion of load-bearing cartilage was found to be much lower than that of non-load-bearing cartilage. In addition, load-bearing cartilage demonstrated steady and low friction coefficient through the entire load range examined, whereas non-load-bearing cartilage showed higher friction coefficient that decreased nonlinearly with increasing normal load. AFM imaging and roughness calculations indicated that the above trends in the nanotribological properties of cartilage are not due to topographical (roughness) differences. However, immunohistochemistry revealed consistently higher surface concentration of boundary lubricant at load-bearing joint regions. The results of this study suggest that under contact conditions leading to joint starvation from fluid lubrication, the higher content of boundary lubricant at load-bearing cartilage sites preserves synovial joint function by minimizing adhesion and wear at asperity microcontacts, which are precursors for tissue degeneration.

Increased friction coefficient and superficial zone protein expression in patients with advanced osteoarthritis.

OBJECTIVE: To quantify the concentration of superficial zone protein (SZP) in the articular cartilage and synovial fluid of patients with advanced osteoarthritis (OA) and to further correlate the SZP content with the friction coefficient, OA severity, and levels of proinflammatory cytokines. METHODS: Samples of articular cartilage and synovial fluid were obtained from patients undergoing elective total knee replacement surgery. Additional normal samples were obtained from donated body program and tissue bank sources. Regional SZP expression in cartilage obtained from the femoral condyles was quantified by enzyme-linked immunosorbent assay (ELISA) and visualized by immunohistochemistry. Friction coefficient measurements of cartilage plugs slid in the boundary lubrication system were obtained. OA severity was graded using histochemical analyses. The concentrations of SZP and proinflammatory cytokines in synovial fluid were determined by ELISA. RESULTS: A pattern of SZP localization in knee cartilage was identified, with load-bearing regions exhibiting high SZP expression. SZP expression patterns were correlated with friction coefficient and OA severity; however, SZP expression was observed in all samples at the articular surface, regardless of OA severity. SZP expression and aspirate volume of synovial fluid were higher in OA patients than in normal controls. Expression of cytokines was elevated in the synovial fluid of some patients. CONCLUSION: Our findings indicate a mechanochemical coupling in which physical forces regulate OA severity and joint lubrication. The findings of this study also suggest that SZP may be ineffective in reducing joint friction in the boundary lubrication mode at an advanced stage of OA, where other mechanisms may dominate the observed tribological behavior.

Atomic force microscope investigation of the boundary-lubricant layer in articular cartilage.

OBJECTIVE: To determine the roles of superficial zone protein (SZP), hyaluronan (HA), and surface-active phospholipids (SAPL) in boundary lubrication of articular cartilage through systematic enzyme digestion using trypsin, hyaluronidase, and phospolipase-C (PLC) surface treatments. METHODS: The friction coefficient of articular cartilage surfaces was measured with an atomic force microscope (AFM) before and after enzyme digestion. Surface roughness, adhesion, and stiffness of the articular surface were also measured to determine the mechanism of friction in the boundary lubrication regime. Histology and transmission electron microscopy were used to visualize the surface changes of treatment groups that showed significant friction changes after enzyme digestion. RESULTS: A significant increase in the friction coefficient of both load-bearing and non load-bearing regions of the joint was observed after proteolysis by trypsin. Treatment with trypsin, hyaluronidase, or PLC did not affect the surface roughness. However, trypsin treatment decreased the adhesion significantly. Results indicate that the protein component at the articular cartilage surface is the main boundary lubricant, with SZP being a primary candidate. The prevailing nanoscale deformation processes are likely plastic and/or viscoelastic in nature, suggesting that plowing is the dominant friction mechanism. CONCLUSIONS: The findings of this study indicate that SZP plays an intrinsic and critical role in boundary lubrication at the articular surface of cartilage, whereas the effects of HA and SAPL on the tribological behavior are marginal.

Direct-current cathodic vacuum arc system with magnetic-field mechanism for plasma stabilization.

Filtered cathodic vacuum arc (FCVA) deposition is characterized by plasma beam directionality, plasma energy adjustment via substrate biasing, macroparticle filtering, and independent substrate temperature control. Between the two modes of FCVA deposition, namely, direct current (dc) and pulsed arc, the dc mode yields higher deposition rates than the pulsed mode. However, maintaining the dc arc discharge is challenging because of its inherent plasma instabilities. A system generating a special configuration of magnetic field that stabilizes the dc arc discharge during film deposition is presented. This magnetic field is also part of the out-of-plane magnetic filter used to focus the plasma beam and prevent macroparticle film contamination. The efficiency of the plasma-stabilizing magnetic-field mechanism is demonstrated by the deposition of amorphous carbon (a-C) films exhibiting significantly high hardness and tetrahedral carbon hybridization (sp3) contents higher than 70%. Such high-quality films cannot be produced by dc arc deposition without the plasma-stabilizing mechanism presented in this study.

Differential regulation of endothelial cell adhesion, spreading, and cytoskeleton on low-density polyethylene by nanotopography and surface chemistry modification induced by argon plasma treatment.

Plasma treatment of polymer surfaces can modify the nanoscale roughness, wettability, and oxygen surface functionalities. However, how these modifications regulate cell behavior is not well understood. The objective of this investigation was to examine adhesion, spreading, and cytoskeleton of vascular endothelial cells seeded on low-density polyethylene surfaces modified by Ar plasma. In the absence of serum, adhesion and spreading of the cells and actin filament assembly were enhanced by high-energy Ar plasma-induced hydrophilicity and formation of C-O groups at the surface. Although serum increased cell adhesion and spreading on untreated surfaces for a relatively short period, this behavior was not stable for a long time. In contrast to the untreated polymer surfaces, serum suppressed cell adhesion and spreading on the plasma-treated surfaces. The preadsorption of albumin from the bovine serum on the polymer surfaces inhibited cell adhesion and spreading. Results demonstrate the differential effects of Ar plasma-induced surface modifications on endothelial cell behavior and provide insight into complex interactions among polymer surfaces, adsorbed proteins, and cells. The findings of this study have significant implications in surface engineering for vascular repair.

Microdevice for measuring friction and adhesion properties of sidewall contact interfaces of microelectromechanical systems.

A microdevice was specifically designed to characterize the static and dynamic friction and adhesion characteristics of sidewall contact interfaces of microelectromechanical systems (MEMS). The microdevice was fabricated by surface micromachining and tested under conditions that accurately mimic those of typical MEMS contacts. The developed experimental scheme enables the direct measurement of the critical normal force at the instant of surface separation and the friction force at the onset of sliding. Additional capabilities include evaluation of the dynamic friction behavior, measurement of the electrical characteristics across the contact interface, and characterization of the tribological response under impact contact loading. The microdevice can operate over a wide range of normal forces and different environmental conditions. Because the design is independent of process environment, the microdevice can be used to study the effects of different surface treatments and variations in fabrication process steps on the tribological properties of MEMS contact interfaces. Characteristic results of static and dynamic friction behaviors, electrical contact resistance, and response to dynamic impact loading illustrate the experimental capabilities and versatility of the designed microdevice.

Carbon monoxide adsorption and oxidation on monolayer films of cubic platinum nanoparticles investigated by infrared-visible sum frequency generation vibrational spectroscopy.

The adsorption and oxidation of CO on monolayer films of cubic Pt nanoparticles synthesized by a modified solution-phase polyol process were examined by sum frequency generation (SFG) vibrational spectroscopy in total internal reflection (TIR) geometry. Extremely low incident laser power (approximately 5 microJ/pulse of infrared) yields sufficient SFG intensity in TIR geometry and reduces destructive interference. Because TIR-SFG spectroscopy does not require correction for bulk gas absorption, CO spectra can be collected over a wide pressure range (<1 mTorr up to 700 Torr). Poly(vinylpyrrolidone)-capped Pt nanoparticles deposited on single-crystal sapphire were monitored under high-pressure reaction conditions in a combined spectroscopy-catalytic reactor cell. The effect of the capping polymer on the position and intensity of the CO peak was studied before and after low-temperature calcination. The polymer decreased the amount of CO adsorption and caused a slight red-shift of the atop CO band relative to a surface treated in oxygen at 373 K. Oxidation rates were determined by measuring the intensity of the atop CO peak as a function of time in the presence of flowing oxygen. The activation energy (approximately 19.8 kcal/mol) determined from the SFG data is close to that obtained from gas chromatography (GC) measurements of CO oxidation rates at different temperatures. The SFG and GC results are in good agreement with published data for Pt(100) surfaces.

Entropically mediated polyolefin blend segregation at buried sapphire and air interfaces investigated by infrared-visible sum frequency generation vibrational spectroscopy.

The segregation behavior of binary polymer blends at hydrophilic solid sapphire and air interfaces was investigated by infrared-visible sum frequency generation (SFG) vibrational spectroscopy. SFG spectra were collected from a bulk miscible blend consisting of identical molecular weight (approximately 54,000) and similar surface free energy (29-35 dyn/cm) components of atactic polypropylene (aPP) and aspecific poly(ethylene-co-propylene) rubber (aEPR). Characteristic CH resonances of the blend were contrasted with those of the individual components at both buried (sapphire/polymer) and free (air/polymer) interfaces. Preferential segregation of the aPP component was observed after annealing at both air/polymer and sapphire/polymer interfaces. SFG spectra revealed ordering of the polymer backbone segments with the methylene (CH2) groups perpendicular to the surface at the sapphire interface and the methyl (CH3) groups upright at the air interface. The SFG results indicate that the surface composition can be determined from the peak intensities that are characteristic of each component and that conformational entropy played a likely role in surface segregation. aPP occupied a smaller free volume at the surface because of a statistically smaller segment length (aPP is more flexible and has a shorter length). In addition, the high density of the ordered CH3 side branches enhanced the surface activity by allowing the long-chain backbone segments of aPP to order at the surface.

Molecular restructuring at poly(n-butyl methacrylate) and poly(methyl methacrylate) surfaces due to compression by a sapphire prism studied by infrared-visible sum frequency generation vibrational spectroscopy.

Infrared-visible sum frequency generation (SFG) vibrational spectroscopy, performed in visible wavelength total internal reflection (TIR) geometry, was used to determine the molecular structures of poly(n-butyl methacrylate) (PBMA) and poly(methyl methacrylate) (PMMA) surfaces in air and in contact with a smooth sapphire surface with and without the application of pressure. C-H vibrational resonances were probed optically to nondestructively examine the buried polymer/sapphire interfaces and obtain information about the molecular orientation in situ. These findings are contrasted with those of the same polymers cast from a toluene solution directly on the sapphire prism surface and annealed. Compared to polymer surface conformation in air, the SFG spectra of the deformed (compressed) PBMA at the sapphire interface illustrate that the ester butyl side chain restructures and tilts away from the surface normal. However, the molecular conformation in the similarly deformed PMMA at the sapphire interface is identical to that obtained in air, which is dominated by the upright-oriented ester methyl side chains. For PBMA and PMMA spin cast on sapphire and annealed, the surface structure of the undeformed PBMA at the sapphire interface is identical to that of the deformed PBMA at the sapphire interface, while the PMMA conformation is different and shows alpha-methyl group ordering. Since the glass transition temperature of PBMA is below room temperature, the rubbery state of PBMA demonstrates a melt-like behavior, evidenced by the fact that PBMA is in conformation chemical equilibrium at the sapphire surface even under compression. Due to the high glass transition temperature of PMMA, compression freezes PMMA in a metastable state, revealed by the restructured molecular conformation when annealed against the sapphire surface. The results of this study demonstrate that structural changes at buried polymer surfaces due to the application of contact pressure can be detected in situ by TIR-SFG vibrational spectroscopy.

Surface modification of low-density polyethylene by inductively coupled argon plasma.

The surface chemistry and nanotopography of low-density polyethylene (LDPE) were modified by downstream, inductively coupled, radio frequency (rf) Ar plasma without inducing surface damage. The extent of surface modification was controlled by the applied ion energy fluence, determined from the plasma ion density measured with a Langmuir probe. The treated LDPE surfaces were characterized by atomic force microscope (AFM) imaging, contact angle measurements, and X-ray photoelectron spectroscopy (XPS). Analysis of AFM surface images confirmed that topography changes occurred at the nanoscale and that surface damage was insignificant. Contact angle measurements demonstrated an enhancement of the surface hydrophilicity with the increase of the plasma power. XPS results showed surface chemistry changes involving the development of different carbon-oxygen functionalities that increased the surface hydrophilicity. Physical and chemical surface modification was achieved under conditions conducive to high-density inductively coupled rf plasma.

Chemical and biological characteristics of low-temperature plasma treated ultra-high molecular weight polyethylene for biomedical applications.

Several low-temperature radio-frequency (RF) plasma surface treatments were performed on ultra-high molecular weight polyethylene (UHMWPE) used in biomedical applications. Process gases included Ar, C3F6, CH4, hexamethyldisiloxane (HMDSO), and NH4. These treatments were carried out at pressures in the range of 64-400 mTorr, RF powers of 240-1200 W, and temperatures well below the melting point of UHMWPE. X-ray photoelectron spectroscopy (XPS) was used to obtain information about the surface characteristics of UHMWPE treated with the HMDSO, C3F6, and CH4 gases as a function of treatment conditions. XPS spectra of UHMWPE treated with C3F6 and CH4 and exposed to a laboratory environment for different time periods were examined in order to assess the stability of these treatments. It was found that for the C3F6 process gas the amount of fluorine at the surface decreased over time, whereas the oxygen content of the CH4 treated samples increased as a function of time. In vitro cytotoxicity of Ar, C3F6, CH4, and NH4 plasma treated samples was studied in light of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) test results. The hemolytic nature of the various plasma treatments was evaluated using standard hemolysis tests. All of the samples tested in this study exhibited no cytotoxic and negligible hemolytic effects. The process parameters for several low-temperature plasma treatments demonstrating chemical and structural stability and good biocompatibility are discussed in conjunction with the broad applicability to other biomedical polymers.