Fifth Italian-Australian Workshop on Synchrotron Radiation X-ray Imaging for Life Sciences and Cultural Heritage

Italian and Australian synchrotron scientists came together May 14–15, 2012, at the International Centre for Theoretical Physics in Trieste, Italy, for the latest of a series of topical workshops, the Fifth Italian-Australian Workshop on Synchrotron Radiation X-ray Imaging for Life Sciences and Cultural Heritage. Both scientific communities are interested in applying synchrotron light to solve problems in medicine, zoology, archaeology, art conservation and analysis, palaeontology, and musical instruments.     

Subsurface analysis of painted sculptures and plasters using micrometre‐scale spatially offset Raman spectroscopy (micro‐SORS)

A recently developed variant of spatially offset Raman spectroscopy (SORS) for the non‐invasive analysis of thin painted layers, micro‐SORS, has been applied, for the first time, to real objects of Cultural Heritage – namely painted sculptures and plasters. Thin layers of paint originating from multiple restoration processes often applied over many centuries have been analysed non‐destructively using micro‐SORS to depths inaccessible to, or unresolvable into separate layers, by conventional confocal Raman microscopy. The concept has been demonstrated on several artistic artefacts of historical significance originating from Italy and dating from the medieval to the 18th century. The technique extends the depth applicability of Raman spectroscopy and with its inherently high chemical specificity that expands the portfolio of existing non‐destructive analytical tools in Cultural Heritage permitting to avoid cross‐sectional analysis often necessitated with this type of samples with conventional Raman microscopy. Currently, the method is non‐invasive only for artworks that can be placed under Raman microscope although there is a prospect for its use in a mobile system with largely removed restrictions on sample dimensions. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd.     

Analysis of process parameters of laser structuring with Taguchi method

In this study the usefulness of micro-Computed Tomography (μ-CT) for the in-depth analysis of enamelled metal objects was tested. Usually investigations of enamelled metal artefacts are restricted to non-destructive surface analysis or analysis of cross sections after destructive sampling. Radiography, a commonly used technique in the field of cultural heritage studies, is limited to providing two-dimensional information about a three-dimensional object (Lang and Middleton, Radiography of Cultural Material, pp. 60–61, Elsevier-Butterworth-Heinemann, Amsterdam-Stoneham-London, 2005). Obtaining virtual slices and information about the internal structure of these objects was made possible by CT analysis. With this technique the underlying metal work was studied without removing the decorative enamel layer. Moreover visible defects such as cracks were measured in both width and depth and as of yet invisible defects and weaker areas are visualised. All these features are of great interest to restorers and conservators as they allow a view inside these objects without so much as touching them.     

1999 chess users' meeting

Archeometry and conservation science are two emergent fields in materials science with an increasing demand of access to SR-based techniques such as X-ray fluorescence, X-ray diffraction, X-ray imaging and IR spectroscopy. These two fields deal with the investigation of the exact nature of art and archeological objects, the provenance of the materials, their dating, and also their alteration processes and preservation procedures. Materials concerned are as various as metals, minerals, pigments, glasses, ceramics, biomaterials, and organic materials. Characteristic features of the materials are often trace elements or minor phases. In addition, art and archeological objects are very complex and often composed of heterogeneous materials. Organic and inorganic materials can be intimately mixed from the macro- to the nanoscale. Surface layers formed by complex degradation processes show a different chemical composition and structure with respect to the bulk of the objects. Conservators and archeologists obviously prefer non-destructive or at least micro-destructive methods for the analysis of their materials and objects. Therefore, the analysis of art and archaeological objects represents a real challenge for materials science. Synchrotron radiation techniques, especially those with microbeams, provide powerful new tools to interrogate the records of our physical and cultural past.     

Quasar microlensing

Quasar microlensing deals with the effect of compact objects along the line of sight on the apparent brightness of the background quasars. Due to the relative motion between quasar, lenses and observer, the microlensing magnification changes with time which results in uncorrelated brightness variations in the various images of multiple quasar systems. The amplitudes of the signal can be more than a magnitude with time scales of weeks to months to years. The effect is due to the “granular” nature of the gravitational microlenses—stars or other compact objects in the stellar mass range. Quasar microlensing allows to study the quasar accretion disk with a resolution of tens of microarcseconds, hence quasar microlensing can be used to explore an astrophysical field that is hardly accessible by any other means. Quasar microlensing can also be used to study the lensing objects in a statistical sense, their nature (compact or smoothly distributed, normal stars or dark matter) as well as transverse velocities. Quasar microlensing light curves are now being obtained from monitoring programs across the electromagnetic spectrum from the radio through the infrared and optical range to the X-ray regime. Recently, spectroscopic microlensing was successfully applied, it provides quantitative comparisons with quasar/accretion disk models. There are now more than a handful of systems with several-year long light curves and significant microlensing signal, lending to detailed analysis. This review summarizes the current state of the art of quasar microlensing and shows that at this point in time, observational monitoring programs and complementary intense simulations provide a scenario where some of the early promises of quasar microlensing can be quantitatively applied. It has been shown, e.g., that smaller sources display more violent microlensing variability, first quantitative comparison with accretion disk models has been achieved, and quasar microlensing has been used to determine the fraction of dark matter in a lensing galaxy for the first time. This is the quantitative beginning. The future of quasar microlensing is bright.     

Practical issues in laser cleaning of stone and painted artefacts: optimisation procedures and side effects

In the last twenty years lasers have acquired an important role in the study and the preservation of Cultural Heritage (CH) objects and Monuments, as they have effectively illuminated a number of complex diagnostic and restoration problems. Their unique properties have enabled their use in a wide range of conservation applications, since they ensure interventions with precise control, material selectivity and immediate feedback.     

Limitations of portable XRF implementations in evaluating depth information: an archaeometric perspective

Portable instruments that can perform non-destructive analysis techniques are of great importance due to their high applicability, which can extend beyond the controlled laboratory environment. Their importance has long been recognised in the archaeometric field where art historians, conservators and restorers perform analyses on art works without causing any damage and without the need to move the objects to specialized laboratories. The X-ray fluorescence (XRF) technique is a popular choice in the archaeometric field for in situ investigations with portable instrumentations. This enables qualitative (elemental analysis) and quantitative (chemical composition) information retrieval from the objects of interest. Quantitative analyses can be performed under the assumption that the sample is homogeneous and its surface material is the same as in the rest of the object. This work aims to expose various details, including the strengths and the weaknesses of typical XRF analyses in the case of surface alterations, focusing on portable implementations. The chosen approach will be in line with certain issues considered important in archaeometry; nevertheless the presented findings are valid beyond this. We will focus our discussion on two kinds of objects that can be found in the cultural heritage field: artefacts that had their surface material altered due to prolonged exposure to the environment and artefacts that have been gilded. Our work also includes a critically examined overview of relevant information available in the literature. The core of our analysis focuses on two main distinct cases, that of multilayer objects and that of bronzes. PACS 78.66.Bz; 78.70.En; 33.20.Rm     

Recent applications and current trends in Cultural Heritage Science using synchrotron-based Fourier transform infrared micro-spectroscopy

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-FTIR) is one of the emerging techniques increasingly employed for Cultural Heritage analytical science. Such a technique combines the assets of FTIR spectroscopy (namely, the identification of molecular groups in various environments: organic/inorganic, crystallized/amorphous, solid/liquid/gas), with the extra potential of chemical imaging (localization of components + easier data treatment thanks to geographical correlations) and the properties of the synchrotron source (namely, high brightness, offering high data quality even with reduced dwell time and reduced spot size).This technique can be applied to nearly all kind of materials found in museum objects, going from hard materials, like metals, to soft materials, like paper, and passing through hybrid materials such as paintings and bones. The purpose is usually the identification of complex compositions in tiny, heterogeneous samples.Recent applications are reviewed in this article, together with the fundamental aspects of the infrared synchrotron source which are leading to such improvements in analytical capabilities. A recent example from the ancient Buddhist paintings from Bamiyan is detailed. Emphasis is made on the true potential offered at such large scale facilities in combining SR-FTIR microscopy with other synchrotron-based micro-imaging techniques. To cite this article: M. Cotte et al., C. R. Physique 10 (2009).     

Non-destructive imaging of fragments of historical beeswax seals using high-contrast X-ray micro-radiography and micro-tomography with large area photon-counting detector array

Historical beeswax seals are unique cultural heritage objects. Unfortunately, a number of historical sealing waxes show a porous structure with a strong tendency to stratification and embrittlement, which makes these objects extremely prone to mechanical damage. The understanding of beeswax degradation processes therefore plays an important role in the preservation and consequent treatment of these objects. Conventional methods applied for the investigation of beeswax materials (e.g. gas chromatography) are of a destructive nature or bring only limited information about the sample surface (microscopic techniques). Considering practical limitations of conventional methods and ethical difficulties connected with the sampling of the historical material, radiation imaging methods such as X-ray micro-tomography presents a promising non-destructive tool for the onward scientific research in this field. In this contribution, we present the application of high-contrast X-ray micro-radiography and micro-tomography for the investigation of beeswax seal fragments. The method is based on the application of the large area photon-counting detector recently developed at our institute. The detector combines the advantages of single-photon counting technology with a large field of view. The method, consequently, enables imaging of relatively large objects with high geometrical magnification. In the reconstructed micro-tomographies of investigated historical beeswax seals, we are able to reveal morphological structures such as stratification, micro-cavities and micro-fractures with spatial resolution down to 5 μm non-destructively and with high imaging quality. The presented work therefore demonstrates that a combination of state-of-the-art hybrid pixel semiconductor detectors and currently available micro-focus x-ray sources makes it possible to apply X-ray micro-radiography and micro-tomography as a valuable non-destructive tool for volumetric beeswax seal morphological studies.     

Soft X-ray microscopy in the spectral region of “carbon window” with the use of multilayer optics and a laser-plasma source

This paper reports on the fabrication and testing of multilayer mirrors for X-ray optical systems operating in the “carbon window” region (at wavelengths from 4.5 to 5.0 nm) and the results of their application in soft X-ray imaging of the internal structure of organic objects. The developed approaches to the fabrication and control of graded Co/C multilayer coatings have made it possible to create an X-ray multimirror system with a maximum known entrance aperture and throughput. The use of the developed high-spatial-resolution X-ray optics can significantly extend the field of practical application of soft X-ray absorption microscopy based on compact laser-plasma sources.     

Reconstruction of systems with delayed feedback: II. Application

We apply a recently proposed method for the analysis of time series from systems with delayed feedback to experimental data generated by a laser. The method allows estimating the delay time with an error of the order of the sampling interval, while an approach based on the peaks of either the autocorrelation function, or the time delayed mutual information would yield systematically larger values. We reconstruct rather accurately the equations of motion and, in turn, estimate the Lyapunov spectrum even for high dimensional attractors. By comparing models constructed for different “embedding dimensions” with the original data, we are able to find the minimal faithful model. For short delays, the results of our procedure have been cross-checked using a conventional Takens time-delay embedding. For large delays, the standard analysis is inapplicable since the dynamics becomes hyperchaotic. In such a regime we provide the first experimental evidence that the Lyapunov spectrum, rescaled according to the delay time, is independent of the delay time itself. This is in full analogy with the independence of the system size found in spatially extended systems. Received 17 December 1999     

Nanosciences: Evolution or revolution?

In miniaturized objects fabricated by modern technology the smallest linear size may be of a few nanometers. In the field of microelectronics, the advantages of such a miniaturization are huge (increased complexity and reliability, reduced costs). The technology is now approaching the limits where further size reduction will be impossible, except for very novel techniques such as molecular electronics. Miniaturization research has also led to the discovery of nanometric objects such as carbon nanotubes, which turn out to be particularly appropriate for inventing new materials. Miniaturization techniques have been progressively applied in other fields, with the hope of obtaining improvements similar to those encountered in microelectronics. Examples are biochips, which concentrate on a few cm² the recognition of ADN sequences, or ‘lab-on-a-chip’ devices, each of which constitutes a whole laboratory of chemical analysis, or MEMs (Micro Electro Mechanical Systems). New therapies will use miniaturized objects with multiple functions: For instance a nanoparticle can both recognize the target organ thanks to an appropriate protein, and deliver the therapeutic molecule to this target. These results have only been possible through new observation instruments, able to observe and manipulate nano objects. Is the observed evolution really a revolution of science and techniques? This is a point discussed in the conclusion, which also deals with risks associated to nanotechnologies, while the need for a social regulation is stressed.     

Transmission X-ray microscopy using X-ray magnetic circular dichroism

X-ray magnetic circular dichroism (X-MCD) was used as a large, element-specific and quantitative magnetic contrast mechanism in the soft X-ray microscopes at BESSY I (Berlin) and the ALS (Berkeley). The present state and potential of magnetic transmission X-ray microscopy (MTXM) is outlined. The possibility to record images in varying magnetic fields and the high spatial resolution down to 25 nm were used to image out-of-plane magnetized (4 ?Fe / 4 ?Gd)×75 systems. Magnetic domains could be studied in arrays of circular and square dots with lateral dimensions down to 180 nm. Hysteresis loops of individual dots were deduced using the direct proportionality of the X-MCD contrast to the sample magnetization. Images of a 3 nmCr / 50 nmFe / 6 nmCr film demonstrate for the first time that MTXM is also able to observe in-plane magnetized domains. In the future the possible applications of MTXM will be extended with regard to the strength of the external field, the available energy range and the sample conditions by building a dedicated transmission X-ray microscope for magnetic imaging at BESSY II. Received: 22 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

Synthesis of platinum and platinum–ruthenium-modified diamond nanoparticles

With the aim of developing dimensionally stable-supported catalysts for direct methanol fuel cell application, Pt and Pt–Ru catalyst nanoparticles were deposited onto undoped and boron-doped diamond nanoparticles (BDDNPs) through a chemical reduction route using sodium borohydride as a reducing agent. As-received commercial diamond nanoparticles (DNPs) were purified by refluxing in aqueous nitric acid solution. Prompt gamma neutron activation analysis and transmission electron microscopy (TEM) techniques were employed to characterize the as-received and purified DNPs. The purified diamond nanoparticulates, as well as the supported Pt and Pt–Ru catalyst systems, were subjected to various physicochemical characterizations, such as scanning electron microscopy, energy dispersive analysis, TEM, X-ray diffraction, inductively coupled plasma-mass spectrometry, X-ray photoelectron spectroscopy, and infrared spectroscopy. Physicochemical characterization showed that the sizes of Pt and Pt–Ru particles were only a few nanometers (2–5 nm), and they were homogeneously dispersed on the diamond surface (5–10 nm). The chemical reduction method offers a simple route to prepare the well-dispersed Pt and Pt–Ru catalyst nanoparticulates on undoped and BDDNPs for their possible employment as an advanced electrode material in direct methanol fuel cells.     

同轴X射线相位衬度计算机X射线断层摄影术研究

基于北京同步辐射装置(BSRF)开展了同轴X射线相位衬度计算机X射线断层摄影术(CT)研究.利用北京同步辐射的14 keV单色X射线作为光源,以高分辨能力的X射线胶片作为探测器,分别开展吸收衬度和同轴相位衬度成像的比较研究以及相位衬度计算机X射线断层摄影术研究.相位衬度计算机X射线断层摄影术重建采用Bronnikov提出的算法.结果显示,与传统的吸收衬度图像相比,相位衬度图像具有更好的衬度和更高的空间分辨力;实验获得人工样品和蝗虫的相位衬度计算机X射线断层摄影术重建图像.重建图像中可见样品的一些结构细节.实验结果表明,相位衬度X射线成像更适合于研究弱吸收或吸收差异很小的材料;利用北京同步辐射开展同轴X射线相位衬度计算机X射线断层摄影术研究是可行的.     

Clustered and integrated fluorescence spectra from single atmospheric aerosol particles excited by a 263- and 351-nm laser at New Haven,CT, and Adelphi,MD

Fluorescence spectra from individual micron-sized atmospheric aerosol particles were measured by a Dual-wavelength-excitation Particle Fluorescence Spectrometer (DPFS). Particles were drawn into our laboratory at Adelphi, MD, an urban site in the Washington, DC, metroplex and within the Yale University campus at New Haven, CT. Two fluorescence spectra were obtained for every individual particle as it was moving through the DPFS system and excited sequentially by single laser pulses at 263 and 351 nm. There were around ten to a few hundred particles detected per second and up to a few million per day within the 1–10 μm particle size range. The majority of the particles have weak fluorescence, but 10–50% of the particles have fluorescence signals above the noise level at both sites at different time period. For the first time, these Ultra Violet laser-induced-fluorescence (UV-LIF) spectra from individual particles were integrated every 10 min, which forms a group of about a few thousand to a few tens of thousand particles, to provide the averaged background atmospheric fluorescence spectral profiles which may be helpful in the development of bioaerosol detection systems, particularly those systems based on integrated fluorescence from a group of aerosol particles, such as Light Detection And Rangeing (LIDAR) remotor biosensor and the point sensor based on collected particles on substrate. These integrated spectral profiles had small variations from time to time and were distinguishable from that of the bacterial simulant B. subtilis. Also for the first time, the individual spectra excited by a 351 nm laser were grouped using unstructured hierarchical cluster analysis, with parameters chosen so that spectra clustered into 8 main categories. They showed less spectral variations than that excited by a 263-nm laser. Over 98% of the spectra were able to be grouped into 8 clusters, and over 90% of the fluorescent particles were in clusters 3–5 with a fluorescence emission peak around 420–470 nm; these were mostly from biological and organic carbon-containing compounds. Integrated fluorescence spectral profiles and averaged spectra for each cluster show high similarity between New Haven, CT and Adelphi, MD.     

Portable X-ray powder diffractometer for the analysis of art and archaeological materials

Phase identification based on nondestructive analytical techniques using portable equipment is ideal for the analysis of art and archaeological objects. Portable(p)-XRF and p-Raman are very widely used for this purpose, yet p-XRD is relatively rare despite its importance for the analysis of crystalline materials. This paper overviews 6 types of p-XRD systems developed for analysis of art and archaeological materials. The characteristics of each system are compared. One of the p-XRD systems developed by the authors was brought to many museums as well as many archeological sites in Egypt and Syria to characterize the cultural heritage artifacts, e.g., amulet made of Egyptian blue, blue painted pottery, and Islamic pottery from Egypt, jade from China, variscite from Syria, a Japanese classic painting drawn by Korin Ogata, and oil paintings drawn by Taro Okamoto. Practical application data are shown to demonstrate the potential ability of the method for analysis of various art and archaeological materials.     

一种利用小体积偏置探测器的新型锥束X射线CT系统

在传统的CT系统中, 系统的硬件成本和计算量都是非常巨大的. 提出了一种利用偏移放置的面阵探测器的锥束CT系统, 在这种系统中X射线束仅仅覆盖被扫描物体的一半体积, 投影数据在探测器方向上是截断的, 探测器尺寸和投影数据量都减少为传统CT系统的一半. 在这种新型扫描方式下, 现有的CT重建算法都不能处理. 因此, 提出了一种BPF形式的直接反投影重建方法. 该方法不需要对投影数据重排, 直接反投影滤波重建出最终的图像. 因此, 该算法在数学上更简洁, 计算速度更快. 最后, 数值模拟实验和真实CT系统实验结果均验证了该系统和重建算法能够获得高质量的CT图像.     

Lime-pastes with different kneading water: Pore structure and capillary porosity

Lime-mortars to be used in restoration works of Cultural Heritage are being more and more studied. The knowledge on the lime-pastes allows understanding the behaviour of the binder fraction. The aim of this work is to study the influence of the kneading water on two critical aspects of the lime-pastes: pore structure and capillary porosity, because both of them are related to the service life of the material, particularly with the moisture transport. Mercury intrusion porosimetry has been performed to establish the pore size distribution: one pore range has been checked in the different pastes tested, setting linear relationships between the pore diameter and the water/lime ratio.Fractal geometry has been used from the MIP results in order to evaluate the pore surface complexity, as a function of the kneading water. From the results, it can be concluded that kneading water is only responsible for a swelling of the structure, but it does not change the pore surface (keeping constant the surface fractal dimension). DIA analysis has been carried out, confirming the previous results. Finally, the correlation obtained between the capillary coefficient and the water/lime ratio confirms the postulated pore structure for the different amount of kneading water in lime-pastes.