In the present work, a detailed spectroscopic investigation of carbon in different crystalline forms from diamond to graphite was carried out. The spectra of photoemission peak, plasmon losses and X-rays-excited C KLL were studied in order to characterize the carbon phase in different samples. In addition, a method for determination of sp 2 /sp 3 ratio from the first derivative of Auger C KLL spectrum was employed. The obtained results indicated that carbon photoemission peak for sp 2 and sp 3 configurations is characterized by the same value of binding energy. The peaks of plasmon losses and Auger KLL transition were more diagnostic than C 1s photoemission peak, permitting to distinguish the sp 2 and sp 3 configurations. For intermediate situation, which is present in diamond-like carbon (DLC), characterized by a mixture of sp 2 and sp 3 states, the spectra were very similar to the carbon-black, whereas single-wall carbon nanotubes (CNT) were containing about 50% sp 2 states.

Recently, carbon spectroscopy became very important due to the growing interest in the applications of new carbon allotropes, especially of 2D structures such as graphene and nanotubes. It is well known that the hybridization of carbon electrons defines most of the properties of these materials. Among the analytical techniques used for the identification of carbon allotropes is the spectroscopy of carbon Auger line, which involves the transitions of valence band electrons and can be excited by electron beam (AES) or X‐ray photons (XAES). From the shape of C KVV spectrum, it is possible not only to recognize the cases of pure sp2 and sp3 configurations but also to quantify their ratio in amorphous carbon films. In present work, an experimental study of three main allotropes of carbon: graphite, diamond, and graphene is reported. The average thickness of graphene was evaluated from the ratio of C 1s and substrate photoelectron peaks, registered at grazing angle. Carbon KVV spectra were investigated by using XAES and AES techniques. Obtained results were compared with the ones acquired for reference samples of graphite and monocrystalline diamond. In addition, some samples of hydrogenated diamond were analyzed. It was demonstrated that the comparison of C KVV spectra excited by electrons and X‐rays can be used for identification of graphene. Diamond‐like C KVV spectrum, observed in XAES experiments, is a very promising fingerprint of graphene. Obtained results are also compared with valence band spectra of graphene, diamonds and graphite that were acquired by using ultraviolet photoemission spectroscopy. Copyright © 2014 John Wiley & Sons, Ltd.

A stable and improved control of the wettability of textiles was obtained by using a coating of diamond like carbon (DLC) films on cotton by PECVD. By controlling different plasma pretreatments of argon, oxygen, and hydrogen on the cotton fibers' surface, we have shown that the pretreatments had a significant impact on wettability behavior resulting from an induced nanoscale roughness combined with an incorporation of selected functional groups. Upon subsequent deposition of diamond like carbon (DLC) films, the cotton fibers yield to a highly controlled chemical stability and hydrophobic state and could be used for self-cleaning applications. By controlling the nature of the plasma pretreatment we have shown that the oxygen plasma pretreatment was more effective than the argon and hydrogen for the superhydrophilic/ultra hydrophobic properties. The chemical and morphological changes of the cotton fibers under different treatments were characterized using X-ray photoelectron and Raman spectroscopy, AFM, and water contact angle measurements. The mechanism underlying the water-repellent properties of the cotton fibers provides a new and innovative pathway into the development of a range of advanced self-cleaning textiles.

No abstract

Fire gilding and silvering are age-old mercury-based processes used to coat thesurface of less precious substrates with thin layers of gold or silver. In ancient times, these methods were used to produce and decorate different types of artefacts, such as jewels, statues, amulets, and commonly-used objects. Gilders performed these processes not only to decorate objects but also to simulate the appearance of gold or silver, sometimes fraudulently. From a technological point of view, the aim of these workmen over 2000 years ago was to make the precious metal coatings as thin and adherent as possible. This was in order to save expensive metals and to improve the resistance to the wear caused by continued use and circulation. Without knowledge about the chemical-physical processes, the ancient crafts-men systematically manipulated these metals to create functional and decorative artistic objects. The mercury-based methods were also fraudulently used in ancient times to produce objects such as jewels and coins that looked like they were made of silver or gold but actually had a less precious core. These coins were minted by counterfeiters but also by the official issuing authorities. The latter was probably because of a lack of precious metals, reflecting periods of severe economic conditions. In this Account, we discuss some representative cases of gold- and silver-coatedobjects, focusing on unique and valuable Roman and Dark Ages period works of art, such as the St. Ambrogio's altar (825 AD), and commonly used objects. We carried out the investigations using surface analytical methods, such as selected area X-ray photoelectron spectroscopy and scanning electron microscopy combined with energy-dispersive spectroscopy. We used these methods to investigate the surface and subsurface chemical features of these important examples of art and technology, interpreting some aspects of the manufacturing methods and of disclosing degradation agents and mechanisms. These findings may contribute to cultural heritage preservation, thus extending the applicability of the surface analytical techniques.