Characterization of traditional Korean lacquers using surface analytical techniques

Traditional Korean lacquer films, such as Otchil and Hwangchil, are natural paints extracted from Rhus vernicifera and Dendropanax morbifera trees that grow in the eastern part and on the west and south coast of the Korean Peninsula, respectively. Rhus lacquer has a black color, and Hwangchil has a transparent gold color and a rich camphoric perfume (benzoin). These lacquers have been used since ancient times. In this study, analytical techniques, such as Fourier transform infrared (FT‐IR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), and time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), were used to study the traditional Rhus lacquer and Hwangchil films, avoiding time‐consuming and destructive extraction procedures. To compare the Rhus and Hwangchil lacquers, reference lacquer films were prepared using Rhus and Dendropanax saps. These films were then analyzed using FT‐IR, XPS, and TOF‐SIMS. After establishing the methodology using the reference lacquer films, surface analytical techniques were applied to two different plates painted by an artist. The results suggest that FT‐IR, XPS, and TOF‐SIMS are simple and complementary analytical techniques for the discrimination of old lacquer films. Copyright © 2015 John Wiley & Sons, Ltd.     

Direct patterning of copper on polyimide using ion exchangeable surface templates generated by site-selective surface modification

We demonstrate site-selective chemical surface modification by dispensing potassium hydroxide solution onto polyimide, which confines source metallic ions that can subsequently be used in resist- and mask-free fabrication of copper circuit patterns. Metallization can be achieved by a wet chemical method, providing control over metal/polymer interfacial structures. Because the approach is compatible with other existing printing technologies and much simpler than conventional lithography-based methods, we propose that the present surface template method may be of general application in fabrication of metallized polymers as well as in development of integrated circuits with a variety of electronic circuit elements.     

The application of surface analytical techniques to silicon technology

Summary Most modern semiconductor device engineering takes place in the top micron of the host wafer and involves the creation of regions whose composition varies over lateral dimensions which may be less than 0.5 m. Normal to the wafer surface, large changes in matrix and impurity composition may occur in the space of a single atomic plane. In future, the fabrication of quantum dots and wires will result in active device features a few nm in extent. Such material developments need to be supported by parallel development in surface analytical techniques with high spatial resolution. There are, however, fundamental limitations to what can be achieved directly. For a destructive technique such as secondary ion mass spectrometry (SIMS), the analytical sensitivity and spatial resolution are determined by the analyte volume which needs to be consumed to achieve the necessary statistical precision. Moreover, the type of information obtained depends on the details of the interaction between the primary probe and the sample surface. In order to combine high spatial resolution with high sensitivity, special sample structures and modified instruments are required. Techniques need to be developed for accurately compensating for the effects on the analysis of large localized changes in conductivity in the materials. A multi-technique approach to semiconductor analysis is required both to investigate the limitations of the techniques themselves, and to fully describe the material properties.     

可更新表面分析技术进展

概述了流动注射及顺序注射可更新表面分析技术及仪器的进展。介绍了该技术原理、仪器系统、流通池等方面的新发展以及在传感器、免疫分析、生物配位作用检测、酶反应检测、细胞功能检测等领域的应用。参考文献32篇。     

Miscibility of polyimide with polymeric primer and its influence on adhesion of polyimide to the primed copper metal: Effect of precursor origin

Poly(amic acid) (PAA) and poly(amic diethyl ester) (PAE) precursors of poly(4,4′-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA PI) were synthesized. Miscibility behaviors of these precursors with poly(arylene ether benzimidazole) (PAEBI), which is a good adhesion primer for copper metal, were investigated in N-methyl-2-pyrrolidone (NMP) as well as the condensed state and the imidized state. For the PAA/PAEBI blend over the whole range of compositions, no cloud point was measured either in the NMP solution, the condensed state, or the imidized state. Furthermore, no aggregation of PI chains in the blend films was detected by X-ray diffraction. These results indicate that the PAA and PAEBI are completely miscible at the molecular level, consequently leading to the miscible PI/PAEBI blend. This miscibility might result from the strong interaction via the complex formation of imidazole groups of the PAEBI and carboxylic acid groups of the PAA precursor. In contrast, the miscibility of PAE/PAEBI blend in NMP was limited up to a concentration of 13.5–36.3 wt %, leading to a phase separation in the soft-baked and imidized blend. The blend films rich with one component were optically transparent, which might be due to the phase-separated domains much smaller than 1 μm. The immiscibility might result from the relatively weak interactions of imidazole groups of PAEBI with both the ester and amide linkages in the PAE precursor. The difference in the miscibilities of PAEBI with the PAA and PAE precursors was reflected in the adhesion of PI/PAEBI/copper joints: higher miscibility gave higher adhesion strength. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2806–2814, 1999     

Ultra‐low modulus polyazomethines and enhanced adhesion strength with copper foils

Polyazomethines (PAzMs) were prepared from dialdehydes containing different lengths of alkylene groups (m = 2–12) and an ether‐containing common aromatic diamine. The main purpose of this work is to achieve an ultra‐low modulus and a considerably high adhesion strength with a smooth surface (S‐side) of electro‐deposited copper foils for applications as novel coating‐type protective layer materials of flexible printed circuit boards. The elongation at break of the PAzM films was drastically enhanced by increasing the annealing temperature (T_a). The results are probably attributed to a chain extension effect accompanied with solid‐state polymerization promoted at elevated temperatures. An increase in the alkylene chain length (m) led to a gradual decrease in the modulus of the PAzM films owing to an increase in the chain flexibility. It also drastically improved the adhesion strength (S‐side); 8.3 N cm^–1 at m = 12 in spite of the absence of anchoring effect. To further decrease the modulus, the PAzM (m = 12) was modified with another diamine comonomer containing a polybutylene oxide block. This approach was very effective for achieving the present target properties; the PAzM copolymer displayed ultra‐low tensile modulus (0.20 GPa) and a very high adhesion strength (9.8 N cm^–1) with the S‐side of copper foils. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of marine sediments using analytical techniques

This study deals with the characterization of a marine sediments profile from the Gulf of Tehuantepec, Mexico. Ten sediment samples obtained from a core of 18.3 m of length were analysed. Although there have been numerous marine sediments studies carried out in Mexico, more are needed to better understand the sea floor formation. Crystallographic, morphologic, physical, chemical and gamma ray activity analysis were carried out on the samples. The analysis results showed a decrease in organic matter content as a function of sea depth; this value is related to the specific surface area. Some hazardous materials as Cr, Mn, Ni, Sr and Hg were also identified by PIXE in some samples, probably due to anthropogenic activity. The presence of uranium a naturally occurring element was found in all the samples, suggesting a migration through all materials of strata, radioactive elements such as ²²⁶Ra, ²³⁵U, ²¹²Pb, ²¹⁴Pb, ²²⁸Ac, ²⁰⁸Ti, ²¹⁴Bi, ²²⁸Ac and ⁴⁰K were detected.     

Applications of surface analytical techniques for study of the interactions between mercury and fluorescent lamp materials

Several surface analytical techniques, including electron spectroscopy for chemical analysis (ESCA)(X-ray photoelectron spectroscopy) and sputtered neutral mass spectrometry (SNMS), were used to study the interaction between Hg and other components of fluorescent lamps, a very critical issue in lighting industries. Active sites, responsible for Hg interaction/deposition, can be successfully identified by comparing the x- y distribution (obtained by ESCA mapping) and depth distribution (available through SNMS) of respective lamp components with that of Hg. A correlation in both depth and x- y distribution is strong evidence of site preference for Hg interaction/deposition. A burial mechanism is, however, proposed when only depth distribution, not x- y, is correlated. Other modes of ESCA (high resolution, angle-resolved, etc.) were also helpful. Information about the valence states of the interacted Hg species would help to define the nature of the interaction.     

Integrated analytical techniques for the study of ancient Greek polychromy

The materials used in the decoration of three painted astragaloi (knucklebones) from the Koroneia cave (Greece) were investigated by means of sequential application of non-destructive and destructive techniques: optical microscopy, environmental scanning electron microscopy coupled with X-ray microanalysis (ESEM-EDX), Fourier transform infrared spectroscopy (FTIR) with micro-attenuated total reflection (μ-ATR) technique, high performance liquid chromatography (HPLC) coupled with UV-fluorescence and gas chromatography-mass spectrometry (GC-MS) were used.The main results highlighted that the three astragaloi were prepared with a ground of ochre or iron clay and painted with a proteinaceous matter such as binder egg tempera. Both FTIR and GC-MS agree in the detection of lipids that can be related to egg. Organic dyestuffs identified as madder lake and shellfish purple were used together with inorganic pigments.     

Separation and preconcentration of trace amounts of aluminum ions in surface water samples using different analytical techniques

A separation/preconcentration of aluminum (III) (Al³⁺) has been developed to overcome the problem of high matrix species, which may interfere with the determination of trace quantity of Al³⁺ in natural water samples. The separation of Al³⁺ in water samples was carried out from interfering cations by complexing them with 2-methyle 8-hyroxyquinoline (quinaldine) on activated silica. Whereas the separated trace amounts of Al³⁺ was preconcentrated by cloud point extraction (CPE), as prior step to its determination by spectrofluorimetry (SPF) and flame atomic absorption spectrometry (FAAS). The Al³⁺ react with 8-hydroxyquinoline (oxine) and then entrapped in non-ionic surfactant Triton X-114. The main factors affecting CPE efficiency, such as pH of sample solution, concentration of oxine and Triton X-114, equilibration temperature and time period for shaking were investigated in detail. The validity of separation/preconcentration of Al³⁺ was checked by certified reference material of water (SRM-1643e). After optimization of the complexation and extraction conditions, a preconcentration factor of 20 was obtained for Al³⁺ in 10 mL of natural water samples. The relative standard deviation for 6 replicates containing 100 μg L⁻¹ of Al³⁺ was 5.41 and 4.53% for SPF and FAAS, respectively. The proposed method has been applied for determination of trace amount of Al³⁺ in natural water samples with satisfactory results.     

Characterization of fossil Sequoioxylon wood using analytical instrumental techniques

In this study, fossil (Sequoioxylon) wood from the Oligocene–Miocene transition in İstanbul, Turkey was examined using non-destructive test methods to evaluate changes in anatomical and chemical structure. Molecular changes in the cell wall structure of the wood were determined using Fourier transform infrared (FTIR) and FT-Raman spectroscopy, along with the comparison to recent wood [Sequoiadendron giganteum (Lindl.)]. We found that the cell wall carbohydrates of the fossil wood were significantly more degraded compared with lignin; FT-Raman spectroscopy revealed the degradation in more detail compared with FTIR spectroscopy. FT-Raman spectra also demonstrated that hemicellulose and holocellulose were decreased in the fossil wood. Laser-induced breakdown spectroscopy (LIBS) analysis confirmed that the mass loss was due to the decreased H and O content of the fossil wood sample and was caused by decomposition. Light microscopy also showed that fossil and recent woods have similar anatomic structures, and that the micro-morphological structure of the fossil wood was well-preserved.     

Electrochemical and surface analytical study of the formation of oxide films on monel-400 and copper in alkaline media

The nature of the oxide films formed on monel-400 and copper in presence of NaOH and N-methylpyrrolidine (a volatile amine) at pH 9.5 and in 0.1 M KNO₃ medium were investigated. The oxide films were grown by applying an anodic potential of +0.4 V (vs saturated calomel electrode) for 30 min. The compositions of the surface oxide films were analysed by X-ray photoelectron spectroscopy. In the case of copper in NaOH medium, Cu(0) and a very small amount of copper hydroxide were observed. However, in amine medium, Cu(0) and Cu-amine complex were found. For monel in NaOH, the anodic film was found to contain hydroxides of both copper and nickel. After sputtering, this film showed a small amount of metal oxide below the hydroxide layer as confirmed by the oxygen peak. In amine medium the anodic film was found to contain only nickel hydroxide and metallic copper. The depth profile analysis of films showed that the film developed was very thin and the nickel hydroxide was sputtered very easily from the film. Received: 27 May 1997 / Accepted: 8 September 1997     

Structural colors and physical properties of elytra in the jewel beetle,Chrysochroa fulgidissima,using surface analytical techniques

Structural coloration frequently originates from the interaction of light with multilayers of thin films in living organisms. One example where structural colors are created by multilayers is the jewel beetle, Chrysochroa fulgidissima, which has highly iridescent green elytra with longitudinal red stripes. We examine the structure, chemical information, and physical properties of the epicuticle of the jewel beetle by using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nanoindentation, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). AFM and SEM were used to analyze the surface structures of the green elytra and red stripes of the jewel beetle's wing. SEM and TEM images obtained from the cross-sectioned cuticle samples of green and red areas indicated that the color arises from interference reflectors and reflectors consist of successive repeating layers of different electronic densities. Nanoindentation results showed that the green area of the elytron possesses a higher hardness and reduced modulus compared with the red area. To analyze the surface of the elytra and to compare multilayers of the green area with those of the red area, mass spectra and depth profiles were acquired by ToF-SIMS with C₆₀ and Ar cluster ion beams. The epicuticle consists of several layers with alternating high and low abundances of inorganic and organic fragment ions, with approximately 16 layers in the green and 12 layers in the red area. Therefore, ToF-SIMS combined with other analytical techniques indicate that multilayer reflection is a major mechanism of the jewel beetle's iridescence causing structural coloration.     

A study of solvent diffusion in thin polyimide films using laser interferometry

Using laser interferometry, we have determined in situ the thickness increase with time of thin supported polyimide films (4–8 μm in initial thickness) immersed in n-methyl-2-pyrrolidone (NMP) as a function of NMP temperature (22–120°C). Similar experiments were also performed in dimethyl sulfoxide (DMSO) at 22°C with polyimide films of 4.1 μm in thickness. For NMP, the equilibrium fractional thickness increase (about 20%) is independent of initial polyimide thickness and temperature. The time scale for reaching equilibrium sharply decreases with temperature from 2–3 days at 22°C to 30–60 min at 120°C. Compared with NMP, the rate of DMSO sorption is considerably faster, reaching equilibrium swelling of about 28% in about 5 h at 22°C. To describe the transport process, we applied a phenomenological model proposed by Astarita and Sarti¹ but reformulated in polymer fixed frame to enable straightforward comparison with the thickness data. Our analysis indicated that the transport of NMP is best described as anomalous, that is, intermediate between diffusion controlled and case II transport. The effective diffusion coefficient D_eff and the front velocity U₀ at 22°C were found to be 3–6 × 10^?12 cm²/s and 8 × 10^?9 cm/s, respectively. Our front velocity is in good accord with the value of 6 × 10^?9 cm/s obtained for a similar polyimide based on gravimetric measurements.² Both D_eff and U₀ show an activation energy of ～56 kJ/mol. For DMSO, however, the transport is clearly case II. The front velocity at 22°C was found to be about 6 × 10^?8 cm/s, which is about four times that obtained by Rutherford back-scattering spectrometry.³     

Enhanced adhesion of polypropylene to copper substrates

Varying concentrations of maleic anhydride (MAH) were grafted onto three types of polypropylene (PP) in the presence of dicumyl peroxide (DCP). Pull-off adhesive strength from a copper substrate, tensile Young's modulus, and tensile strain-at-break were determined and SEM observations made as a function of the MAH concentration for each PP. One of the PPs plus 3 wt% MAH provides a high value of the adhesive strength along with the Young modulus and the strain-at-break sufficient for the use as a coating for copper wires and cables.     

Probing the interaction at nano-bio interface using synchrotron radiation-based analytical techniques

Understanding the interactions of nanomaterials(NMs) with biomolecules, organelles, cells, and organic tissues at the nano-bio interface can offer important information for their uptake, distribution, translocation, metabolism and degradation in vitro and in vivo, which can help to precisely tune and design "smart" NMs for biomedical applications. However, probing the interactions at the nano-bio interface, which generally requires dedicated analytical methods and tools, is remarkably complicated due to the dynamically changed nature of the nano-bio interface. Because of the advantages of high spatial resolution, high sensitivity, excellent accuracy, low matrix effects and non-destructiveness, synchrotron radiation(SR)-based analytical techniques have become extremely valuable tools. Herein, we present a comprehensive overview of SR-based techniques for the visualized study of NMs at cellular and subcellular interfaces and their transformation in vitro; the exploration of biodistribution, translocation, metabolism and degradation of NMs in vivo; and clarification of the molecular mechanisms of NMs' reactions with biomolecules. Rapid development of advanced light source means that in situ, real-time analysis of NMs at the nano-bio interface will be achieved.     

A molecular dynamics simulation study of surface effects on gas permeation in free-standing polyimide membranes

A 141100-atom model of a glassy ODPA–ODA polyimide free-standing membrane, corresponding to a thickness of two average radii of gyration for the 40-mers chains, has been studied using molecular dynamics (MD) simulations. Due to the large-scale of the fully atomistic model, a parallelized particle-mesh technique using an iterative solution of the Poisson equation had to be implemented for the efficient evaluation of the electrostatic interactions. With flattened-chain configurations, the density was found to adjust itself naturally in the middle of the membrane to 95% of the ODPA–ODA experimental value. At the free-standing surfaces, the density profile became sigmoïdal, indicating surface roughness. For comparison, two isotropic bulk models, one at the “normal” density as obtained for ODPA–ODA under ambient conditions and the other one at 95% of the normal-density, were built. Small gas probes were inserted into all three models in order to investigate whether the interfacial structure of the glassy free-standing membrane can influence penetrant transport. Gas diffusion in the low-density part of the interface was found to be very fast. The limiting value for the gas diffusion coefficient D_membrane is only attained when the probes enter more dense regions in the membrane. Indeed, D_membrane compares well with D_bulk obtained for the 95%-density bulk system, i.e. about twice that in the normal-density bulk. Solubility is larger in the membrane than in both bulk models, thus suggesting an effect of chain flattening in addition to the density. Adsorption is particularly high at the free-standing interfaces.     

Analysis of ancient copper alloys using epithermal activation techniques

A method was developed for the analysis of ancient copper alloys. Over the past three years this method has been applied to a wide range of alloy types, ranging from nominally pure 5th millenium BC coppers to 9th century silver—brass stycas from Northumbria. The analysis of samples provides more analytical information than alternative non-desctructive or non sampling techniques.