Combined SERS and Raman analysis for the identification of red pigments in cross-sections from historic oil paintings

The Analyst ◽  
2014 ◽  
Vol 139 (24) ◽  
pp. 6450-6455 ◽  
Author(s):  
Kristen A. Frano ◽  
Hannah E. Mayhew ◽  
Shelley A. Svoboda ◽  
Kristin L. Wustholz

SERS and normal Raman approach to identify red pigments in cross-sections from historic oil paintings.

2011 ◽  
Vol 17 (5) ◽  
pp. 696-701 ◽  
Author(s):  
Katrien Keune ◽  
Annelies van Loon ◽  
Jaap J. Boon

AbstractScanning electron microscopy backscattered-electron images of paint cross sections show the compositional contrast within the paint system. They not only give valuable information about the pigment composition and layer structure but also about the aging processes in the paint. This article focuses on the reading of backscatter images of lead white-containing samples from traditional oil paintings (17th–19th centuries). In contrast to modern lead white, traditional stack process lead white is characterized by a wide particle size distribution. Changes in particle morphology and distribution are indications of chemical/physical reactivity in the paint. Lead white can be affected by free fatty acids to form lead soaps. The dissolution of lead white can be recognized in the backscatter image by gray (less scattering) peripheries around particles and gray amorphous areas as opposed to the well-defined, highly scattering intact lead white particles. The small particles react away first, while the larger particles/lumps can still be visible. Formed lead soaps appear to migrate or diffuse through the semipermeable paint system. Lead-rich bands around particles, at layer interfaces and in the paint medium, are indications of transport. The presence of lead-containing crystals at the paint surface or inside aggregates furthermore point to the migration and mineralization of lead soaps.


The Analyst ◽  
2021 ◽  
Vol 146 (7) ◽  
pp. 2374-2382
Author(s):  
Chang Hyun Bae ◽  
Si Won Song ◽  
Soo Yeong Lim ◽  
Seonyoung Yoo ◽  
Chang Sug Lee ◽  
...  

It has been reported that the scattering cross-sections of resonance Raman spectra strongly depend on the resonance between the laser's excitation energy and the electronic absorption band of pigments in solution.


MRS Advances ◽  
2017 ◽  
Vol 2 (33-34) ◽  
pp. 1801-1804
Author(s):  
Stephanie Spence ◽  
Takaaki Harada ◽  
Athanasios Margiolakis ◽  
Skylar Deckoff-Jones ◽  
Aaron N. Shugar ◽  
...  

ABSTRACTIssues in traditional cross-section sampling of paintings and other cultural artifacts with a scalpel, such as crumbling, delamination and paint compression, can deter conservators from sampling fragile paint layers. Often, such sampling carries the risk of causing further damage from a scalpel, which outweighs the benefits of scientific investigation. Here, we show that femtosecond lasers offer a viable alternative to obtaining cross-sections with minimal damage to the surrounding artwork. A Regenerative Ti:Sapphire amplifier system with a pulse duration of 70 femtoseconds, a few milliwatts of average power and a repetition rate of 1 kHz (1000 pulses/sec) was used for the study. Tests were performed on oil paintings ranging in age from the 19th century to late 20th century. Effective settings were determined to be 2 mW of power at a speed of 10mm/sec using an 800nm laser. Preliminary results suggest femtosecond lasers could be a viable alternative for obtaining paint cross-sections when traditional sampling methods cause unnecessary damage to fragile materials.


Author(s):  
S. Golladay

The theory of multiple scattering has been worked out by Groves and comparisons have been made between predicted and observed signals for thick specimens observed in a STEM under conditions where phase contrast effects are unimportant. Independent measurements of the collection efficiencies of the two STEM detectors, calculations of the ratio σe/σi = R, where σe, σi are the total cross sections for elastic and inelastic scattering respectively, and a model of the unknown mass distribution are needed for these comparisons. In this paper an extension of this work will be described which allows the determination of the required efficiencies, R, and the unknown mass distribution from the data without additional measurements or models. Essential to the analysis is the fact that in a STEM two or more signal measurements can be made simultaneously at each image point.


Author(s):  
R. W. Anderson ◽  
D. L. Senecal

A problem was presented to observe the packing densities of deposits of sub-micron corrosion product particles. The deposits were 5-100 mils thick and had formed on the inside surfaces of 3/8 inch diameter Zircaloy-2 heat exchanger tubes. The particles were iron oxides deposited from flowing water and consequently were only weakly bonded. Particular care was required during handling to preserve the original formations of the deposits. The specimen preparation method described below allowed direct observation of cross sections of the deposit layers by transmission electron microscopy.The specimens were short sections of the tubes (about 3 inches long) that were carefully cut from the systems. The insides of the tube sections were first coated with a thin layer of a fluid epoxy resin by dipping. This coating served to impregnate the deposit layer as well as to protect the layer if subsequent handling were required.


Author(s):  
Mihir Parikh

It is well known that the resolution of bio-molecules in a high resolution electron microscope depends not just on the physical resolving power of the instrument, but also on the stability of these molecules under the electron beam. Experimentally, the damage to the bio-molecules is commo ly monitored by the decrease in the intensity of the diffraction pattern, or more quantitatively by the decrease in the peaks of an energy loss spectrum. In the latter case the exposure, EC, to decrease the peak intensity from IO to I’O can be related to the molecular dissociation cross-section, σD, by EC = ℓn(IO /I’O) /ℓD. Qu ntitative data on damage cross-sections are just being reported, However, the microscopist needs to know the explicit dependence of damage on: (1) the molecular properties, (2) the density and characteristics of the molecular film and that of the support film, if any, (3) the temperature of the molecular film and (4) certain characteristics of the electron microscope used


Author(s):  
R.P. Apkarian ◽  
J.S. Sanfilippo

The synthetic androgen danazol, is an isoxazol derivative of ethisterone. It is utilized in the treatment of endometriosis, fibrocystic breast disease, and has a potential use as a contraceptive. A study was designed to evaluate the ultrastructural changes associated with danazol therapy in a rat model. The preliminary investigation of the distal segment of the rat uterine horn was undertaken as part of a larger study intended to elucidate the effects of danazol on the female reproductive tract.Cross-sections (2-3 mm in length) of the distal segment of the uterine horn from sixteen Sprague-Dawley rats were prepared for SEM. Ten rats in estrus served as controls and six danazol treated rats were noted to have alterations of the estrus cycle i.e. a lag in cycle phase or noncycling patterns. Specimens were fixed in 3% glutaraldehyde in 0.05M phosphate buffer containing CaCl2 at pH 7.0-7.4 and chilled to 4°C. After a brief wash in distilled water, specimens were passed through a graded series of ethanol, critical point dryed in CO2 from absolute ethanol, and coated with 6nm Au. Observations were made with an IS1-40 SEM operated at 15kV.


Author(s):  
J. P. Colson ◽  
D. H. Reneker

Polyoxymethylene (POM) crystals grow inside trioxane crystals which have been irradiated and heated to a temperature slightly below their melting point. Figure 1 shows a low magnification electron micrograph of a group of such POM crystals. Detailed examination at higher magnification showed that three distinct types of POM crystals grew in a typical sample. The three types of POM crystals were distinguished by the direction that the polymer chain axis in each crystal made with respect to the threefold axis of the trioxane crystal. These polyoxymethylene crystals were described previously.At low magnifications the three types of polymer crystals appeared as slender rods. One type had a hexagonal cross section and the other two types had rectangular cross sections, that is, they were ribbonlike.


Author(s):  
R.D. Leapman ◽  
P. Rez ◽  
D.F. Mayers

Microanalysis by EELS has been developing rapidly and though the general form of the spectrum is now understood there is a need to put the technique on a more quantitative basis (1,2). Certain aspects important for microanalysis include: (i) accurate determination of the partial cross sections, σx(α,ΔE) for core excitation when scattering lies inside collection angle a and energy range ΔE above the edge, (ii) behavior of the background intensity due to excitation of less strongly bound electrons, necessary for extrapolation beneath the signal of interest, (iii) departures from the simple hydrogenic K-edge seen in L and M losses, effecting σx and complicating microanalysis. Such problems might be approached empirically but here we describe how computation can elucidate the spectrum shape.The inelastic cross section differential with respect to energy transfer E and momentum transfer q for electrons of energy E0 and velocity v can be written as


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