Analysis Of Inks Research Articles

Comparison of the discriminating power of Raman and surface‐enhanced Raman spectroscopy with established techniques for the examination of liquid and gel inks

The ability to discriminate between inks is important for forensic document analysis. Here, Raman spectroscopy (RS) and surface‐enhanced RS have been compared to the traditional document examination techniques of video spectral comparison and thin layer chromatography on a population of blue and black‐coloured liquid and gel inks. It was found that in most cases, the Raman techniques provided a similar or better discriminating power than the conventional methods. Importantly, this study allowed us to determine whether the same underlying changes in composition were being exploited by the different methods to discriminate between samples. It was found that there was indeed a high degree of commonality in the sample pairs being discriminated by the various techniques. This work can therefore underpin introduction of Raman methods into standard operating procedures for ink analysis since it not only measures the extent of discrimination between samples but can also explain the origin of the spectral changes that are used to distinguish between them. © 2013 John Wiley & Sons Ltd and Crown copyright

The Classification of Inkjet Inks Using AccuTOF™DART™ (Direct Analysis in Real Time) Mass Spectrometry—A Preliminary Study

A novel approach for the analysis of inkjet inks is being reported. A time-of-flight mass spectrometer, coupled with a Direct Analysis in Real Time (DART™) ion source (AccuTOF™ DART™), was used to determine if inkjet inks from various manufacturers and models of printers could be reliably differentiated, characterized, and identified. A total of 217 ink standards were analyzed. As inkjet printing often involves the use of multiple colors (e.g., cyan, magenta, yellow, and black) to form an image or text, two different approaches to creating a library of standards and sampling methods were evaluated for implementation in a standard operating procedure. This research will show that a microscopic examination of the region of interest is requisite to identify what colors were utilized during the printing process, prior to comparing with known standards. Finally, blind testing was administered with 10 unknown samples to assess the validity and accuracy of the methodology.

Non-destructive spectroscopic investigation on historic Yemenite scriptorial fragments: evidence of different degradation and recipes for iron tannic inks

Six fragments of different Yemenite manuscripts (three on parchment and three on paper) were analyzed by means of attenuated total reflectance Fourier transform infrared, micro-Raman and X-ray fluorescence spectroscopies. The combination of molecular and elemental techniques allowed the characterization of the conservation state of all the fragments, the identification of sizing agents and salts on the supports and the identification of the composition all red and black writing media. In particular, analysis of black inks provided interesting insights: independent of the substrate, all inks seemed to have identical composition, corresponding to rather well preserved high-quality iron tannic inks to which carbon black had not been added. However, in some samples, the most intense Raman peak of the ink was clearly shifted with respect to the typical bands of iron gall ink. Starting from the hypothesis that the shift could have been produced by the use of sources of tannin other than gallnuts, research was undertaken by preparing and characterizing seven different tannic inks. The experimental results confirmed the hypothesis of different tannin sources.

From Ptolemaic to modern inked linen via Laser Induced Breakdown Spectroscopy (LIBS)

Laser Induced Breakdown Spectroscopy (LIBS) has been applied to inked linen textile that belongs to a mummy's linen wrapping dated back to the Ptolemaic period (330 BC: 30 AD). The rarity of the ancient archeological piece introduced in this study has suggested the use of a model sample of currently manufactured linen for comparison purposes and optimization of the experimental conditions. The Nd:YAG laser operating at both wavelengths 532 and 1064 nm as our excitation source along with an Echelle spectrometer with an intensified charge-coupled device detector has been employed. Under the experimental conditions adopted throughout this work, the use of the visible 532 nm laser produced poorer S/B when compared to that produced by a 1064 nm laser which suggests the production of colder plasma leading to less atomization of the ablated material. Additionally, the 532 nm wavelength shows a negative behavior in ablating ink writings which was visually clear. Although, LIBS qualitative results are so comparable to that of SEM-EDX, some elements were detected only by LIBS which could be attributed to the irregularity of ink on linen. Thus, the capabilities of LIBS should be extensively exploited to the in situ measurements and analysis of archeological ink and fabrics.

Micro‐Raman spectroscopic analysis of inks and pigments in illuminated medieval old‐Slavonic manuscripts

Micro‐Raman spectroscopy was applied in characterisation of inks and pigments used in the text, illuminations and miniatures of two old‐Slavonic manuscripts: Vrutok four gospels (13th–14th centuries) and Benche four gospels (16th century). They were written in old‐Slavonic language with old Cyrillic alphabet. Both were decorated with ornaments in so called Balkan style characterised with intertwined rings and floral motifs. Only four colours/pigments were used in the simple miniature and ornaments in Vrutok book: orpiment, vermilion, organo‐copper complex and mixed ink. Much richer palette of pigments was revealed in the Benche book: calcite, gypsum, lead white, yellow ochre, pararealgar/realgar, vermilion, red lead, red ocra, organo‐copper complex, malachite, indigo, iron gall ink, carbon black and pure metallic gold. The use of pigments in ornaments compared with miniatures is somewhat different in Benche book, suggesting that either handwriting and ornamenting on one side and miniatures, on the other, were done by different persons/painters or depiction of sacral themes of the miniatures canonically required the use of more expensive/elaborate pigments.Micro‐Raman spectroscopy allowed in situ, non‐destructive, rapid and unambiguous identification of the majority of pigments used in the text, ornamentations and miniatures in the Vrutok and Benche four gospels. In case of uncertainty in identification of pigments, scanning electron microscopy–energy dispersive X‐ray analysis was applied. Copyright © 2012 John Wiley & Sons, Ltd.

Optical analysis of ink and other contaminants in process waters

Analysis methods developed specifically to determine the presence of ink and other optically active components in paper machine white waters or other process effluents are not available. It is generally more interest¬ing to quantify the effect of circulation water contaminants on end products. This study compares optical techniques to quantify the dirt in process water by two methods for test media preparation and measurement: direct process water filtration on a membrane foil and low-grammage sheet formation. The results show that ink content values obtained from various analyses cannot be directly compared because of fundamental issues involving test media preparation and the varied methodologies used to formulate the results, which may be based on different sets of assumptions. The use of brightness, luminosity, and reflectance and the role of scattering measurements as a part of ink content analysis are discussed, along with fine materials retention and measurement media selection. The study concludes with practical tips for case-dependent measurement methodology selection.

Multi-element analysis by ArF laser excited atomic fluorescence of laser ablated plumes: Mechanism and applications

A new multi-element analysis technique based on laser-excited atomic fluorescence was reviewed. However, the one-wavelength-one-transition constraint was overcome. Numerous elements were induced to fluoresce at a single excitation wavelength of 193 nm. This was possible provided that the analytes were imbedded in dense plumes, such as those produced by pulsed laser ablation. The underlying mechanism of the technique was explained and corroborated. Analytical applications to metals, plastics, ceramics and their composites were discribed. Detection limits in the ng/g range and mass limits of atto moles were demonstrated. Several real-world problems, including the analysis of paint coating for trace lead, the non-destructive analysis of potteries and ink, the chemical profiling of electrode-plastic interfaces, and the analysis of ingestible lead colloids were discussed.

Analysis of the Chemical Composition of Red Pigments and Inks for the Characterization and Differentiation of Contemporary Prints

Prints are one of the most popular artistic forms. They consist of an original matrix that is printed on a paper support. The stamps are part of a series, and each series is composed of a particular number of prints. Many contemporary prints are made using oil inks and synthetic pigments (reds and yellows). Inks are mainly composed of pigments (organic or inorganic) and a binding medium. The analysis of inks has the potential to facilitate and complement the identification of stamps of different origins. Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDX) are techniques that are typically available in museums and centers related to the study of works of art. Both can be classified as micro-destructive and provide complementary information about the organic and some inorganic compounds (FTIR), and the elemental composition (SEM-EDX). In this article, the two techniques were used to analyze the composition of red ink in prints. As a result of these analyses, it was possible to distinguish among nearly all of the pigments and inks, indicating that the composition of the red ink can be reliably used to differentiate between stamps of different origins in a series of prints.

고대 먹의 특성 분석

In this work, scientific and systematic analysis was conducted for finding out the methods and techniques of ancient ink stick making. Analysis the ancient ink stick on ancient documents and wooden writing as letter or painting, we concluded as followings. From the analysis of ancient wood by dendrochronology, wood was cut at 1899, which provided the information on the year of ink stick`s made on writing on ancient wood. Single particle size for soot of ancient ink stick was 107 nm for ink on the roof-filling timber in Sinsunwonjeon of Changdeok Palace, compared to 38 to 86 nm on the letter on ancient 12 paper document. Aggregate particle size was 370 nm for ink on the roof-filling timber in Sinsunwonjeon of Changdeok Palace, but 206 to 318 nm for aggregate particle size on 12 paper documents. There was similar pattern between single particle size and aggregate particle size of soot, which might provide the information of raw material for ancient ink. From infra-red and Raman spectroscopic analysis of sheet of writing on paper or wood, there was severe interference from background material (paper or wood). From Raman spectroscopic analysis of ancient ink carefully separated from ancient wood, spectrum pattern was closer to ink stick made by the soot from pine burning.

Development and Testing of a New Computerized Link Analysis System

AbstractLink analysis (LA) is a popular ergonomic tool for studying and improving the layout of workspaces. It uses a data (event) recording method to input interactions of human behavior with their environment. The traditional “pen and paper'' method of LA is cumbersome, time consuming, and gives limited outputs. To address these limitations, the computerized link analysis (CLA) system was developed and tested in laboratory and real‐world environments. CLA offers an integrated task analysis tool, including traditional LA functions (layout, event recording) with more detail for operator activities, time‐motion functions, and multioperator data recording. As well as the conventional LA results (link diagrams and link tables), there are additional outputs for time‐event lists (start/end time, duration, chronology, additional notes, importance, and operator ID), and processed link diagrams with the link direction and frequency. © 2012 Wiley Periodicals, Inc.

Non-invasive methods for characterisation of printed cultural heritage

Abstract The quality of a book reprint depends on several factors, e.g. paper, typesetting, reproduction of illustrations, printing and bookbinding. The quality of the 1958 and 1988 reprints of the fairytale edition from 1944 designed by the Slovenian architect Jože Plecnik was studied using standard and other non-invasive testing methods, e.g. microscopic and spectroscopic techniques, sonic velocity, Young's modulus of elasticity, surface topography and image analysis. The chemical, physical and colorimetric properties of papers and typographic tonal density were analysed. The results showed that the reprints do not correspond to the originals. Some of the differences in the reprints, if compared with the original (e.g. typographic tonal density), could have been easily avoided, while others (e.g. structural and optical properties of paper) remain unavoidable, mainly due to the influence of internal and external factors on the ageing. The ageing process influences paper properties, since optical properties deteriorate in time. It has been concluded that a precise and systematic study of the properties of an old book should be performed before the preparation of a reprint. The results of the research have shown that the applied methods are useful and satisfactory for the characterisation of the paper properties and typography, and can be of use at the analysis of printing ink and illustration reproduction.

Dating of Historical Manuscripts Using Spectrometric Methods: A Mini-Review

An overview is provided of spectrometric methods useful for age estimation of historical manuscripts (medieval ones in particular), in order to confirm their authenticity. Individual methods (infrared and Raman spectroscopy, mass spectrometry, atomic emission spectroscopy, X-ray spectroscopy, and electron scanning microscopy) are discussed and examples of their application described. The following general strategy can be recommended for dating and/or authenticating of historical manuscripts. First of all, the pigment analysis should be carried out using Raman spectroscopy (distinguishing the period and modern pigments), followed by PIXE ink analysis (solving the question of ink homogeneity). Finally, the radiocarbon dating of the writing support, potentially supplemented by the ink dating using scanning Auger microscopy should be performed.

Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents

Inkjet ink analysis is the best way to discriminate between printed documents, or even though more difficult, to connect an inkjet printed document with a brand or model of printers. Raman spectroscopy and laser desorption mass spectrometry (LDMS) have been demonstrated as powerful tools for dyes and pigments analysis, which are ink components. The aim of this work is to evaluate the aforementioned techniques for inkjet inks analysis in terms of discriminating power, information quality, and nondestructive capability. So, we investigated 10 different inkjet ink cartridges (primary colors and black), 7 from the HP manufacturer and one each from Epson, Canon and Lexmark. This paper demonstrates the capabilities of three methods: Raman spectroscopy, LDMS and MALDI-MS. Raman spectroscopy, as it is preferable to try the nondestructive approach first, is successfully adapted to the analysis of color printed documents in most cases. For analysis of color inkjet inks by LDMS, we show that a MALDI matrix (9-aminoacridine, 9AA) is needed to desorb and to ionize dyes from most inkjet inks (except Epson inks). Therefore, a method was developed to apply the 9AA MALDI matrix directly onto the piece of paper while avoiding analyte spreading. The obtained mass spectra are very discriminating and lead to information about ink additives and paper compositions. Discrimination of black inkjet printed documents is more difficult because of the common use of carbon black as the principal pigment. We show for the first time the possibility to discriminate between two black-printed documents coming from different, as well as from the same, manufacturers. Mass spectra recorded from black inks in positive ion mode LDMS detect polyethylene glycol polymers which have characteristic mass distributions and end groups. Moreover, software has been developed for rapid and objective comparison of the low mass range of these positive mode LDMS spectra which have characteristic unknown peaks.

Examination of black inkjet printing inks by capillary electrophoresis

Counterfeiting of documents is a common phenomenon in the modern world. A large proportion of forgeries relates to inkjet printed documents. Hence there is an evident need to develop an effective and reliable method for the differentiation and identification of inkjet inks on questioned documents. The aim of the presented study was to investigate the possibility of applying micellar electrokinetic capillary chromatography (MECC) to forensic analysis of inkjet inks extracted from black and white printouts.In order to achieve the above aim, a capillary electrophoresis system equipped with a diode array detector was used. The separation was performed using a fused silica capillary (60/50cm total/effective length, 75μm i.d.) with a background electrolyte composed of 40mM sodium borate, 20mM SDS and 10% (v/v) acetonitrile (pH 9.5) at 25°C and 30kV. Ink samples were extracted from black inkjet printouts with the use of dimethyl sulphoxide (DMSO).Differentiation of inks was based on the number of significant peaks at different wavelengths, the relative migration times and the characteristic UV–Vis spectra. The electropherograms of the inks extracted from paper showed patterns which in most cases were distinctly different from each other. The greatest diversity of electrophoretic profiles was revealed for documents printed by Hewlett-Packard inkjet technology. A database of electrophoretic separation results of inks has been constructed for further forensic use.

Development of Semi-Quantitative Analytical System for Metal Nanoparticle Ink Using Laser-Induced Breakdown Spectroscopy

Abstract This paper describes the semi-quantitative analysis of metal nanoparticle ink using laser-induced breakdown spectroscopy (LIBS). LIBS can be used to obtain information about the density and chemical composition of silver particles or copper particles, even ultrafine particles. Metal particles have been attracting much attention because of their increased use in new micro-nano technologies. In this work, LIBS was used as a fine metal particle measurement system for nanometallic materials used in printing. Good spectral peak resolutions were obtained when the Ag spectra were recorded at wavelengths of 328.068 nm and 338.289 nm and Cu spectra at 324.754 nm and 327.396 nm.

Comparison of test medium preparation methods for residual ink analysis

ERIC (950 nm) and residual ink (700 nm) are commonly employed in paper recycling for estimating the amount of ink in pulp. Determination of ERIC and residual ink are assessed from the measured near-infrared (NIR) reflectance and scattering coefficient. Pads and sheets can be used for the determination, but when the opacity of measurement media exceeds 97%, the scattering coefficient cannot be measured and a constant value has to be used instead. This paper studies the feasibility of various test medium preparation methods for residual ink analysis. Studied methods consisted of an opaque pad filtered on paper, low grammage sheet filtered on wire screen, and low gram¬mage sheet filtered on high-retention filter paper (the most novel method). The comparison is based on measured retention, NIR scattering coefficient, reflectance, and residual ink values. Results showed that higher retention, scat¬tering, and residual ink values can be obtained when filter paper is used during sheet preparation. However, the opaque pad from which the measurement of scattering coefficient is prevented gives the lowest reflectance. A method involving sheet preparation on paper is seen as a good compromise for high retention of ink and fine materi¬al, while also enabling the measurement of scattering coefficient.

Application of capillary electrophoresis to examination of color inkjet printing inks for forensic purposes

In the process of questioned document examination, the discrimination of inkjet printing inks is becoming more necessary due to increasingly frequent counterfeiting of documents printed by inkjet printers. Therefore, a method based on micellar electrophoretic capillary chromatography (MECC) has been developed and applied to analysis of such inks extracted from paper. With the use of an optimized and validated analytical procedure, multielectropherograms of inks taken from various models of printers made by various producers (Hewlett-Packard, Epson, Brother, Lexmark and Canon) were created. It was shown that effective differentiation of individual inks was possible in terms of migration time, order and specific shapes of characteristic peaks. By comparison of recorded UV-Vis spectra, the identification of main dyes was also achievable. The usefulness of the method was confirmed by an intralaboratory test of utility, in which several forged printouts were successfully examined. The obtained results proved that the proposed procedure is a useful tool that could be applied to ink discrimination and group identification of dyes originating from inkjet printing inks. Consequently, the developed method can be applied in the forensic field, including investigation of the authenticity of documents.

The analysis of dyes in ball point pen inks on single paper fibres using laser desorption ionisation time of flight mass spectrometry (LDI-TOFMS)

An important requisite for the forensic analysis of inks on documents is that damage to the document is avoided or minimised. This paper describes a technique for dye identification in ballpoint pen inks using LDI-TOFMS on single ink bearing paper fibres and its application to a case. A single ink bearing paper fibre can be prised from the surface of the document under a stereo microscope and presented to the instrument for analysis without further treatment. This sampling process causes imperceptible damage to the surface of the document. Clear mass spectrometric identification of the ink dyes is obtained. A case example is provided to illustrate the practical application of the technique.

Analysis of Gravure Ink: Its Adhesion Strength and Thermo-elastic Behavior

In the packaging industry, the use of gravure ink has a major influence on the product contained in the package in terms of protection and communication. Another purpose of the film of gravure ink is to prevent heat transfer either from outside or from inside of the container or pack. However, the adherent film is not always long lasting. In this work, the mechanical and thermal properties of gravure ink films were measured. The mechanical properties measured, included the density, modulus of elasticity and the Poisson's ratio. The thermal measurements were confined to thermal conductivity, specific heat, heat diffusivity and the coefficient of linear expansion. If taken into account, these findings may be helpful in applying these films for the better protection of packaged products and in improving the adhesion of the films to different metallic and non-metallic substrates.

Multi-element analysis of ceramic and polymeric samples by ArF laser excited atomic fluorescence of ablated plumes

Laser-excited-atomic-fluorescence at the single excitation wavelength of the ArF laser was demonstrated for numerous analytes. These analytes were present in the material plumes produced by pulsed laser ablation of ceramic and polymeric targets. Under minimally destructive conditions, the fluorescence spectra were orders of magnitude brighter than the corresponding laser-induced breakdown spectra. Simultaneous emissions from Al, Ca, Co, Cr, Cu, Fe, In, Mg, Mn, Na, Pb, Sn, and Si were observed. The technique was applied to four analytical problems: the analysis of dried paint for trace lead when μg g−1 detection limits were achieved; the analysis of valuable potteries when two look-alike specimens were differentiated based on practically non-destructive single-shot analysis; the elemental analysis of ink when lines written with different pens could be discriminated without discernable sample destruction even under the microscope; and the analysis of electrode-plastic interfaces when the detection sensitivity was comparable to SIMS. The fluorescence intensity varied with the fluence and the timing of the ArF laser pulse in ways suggestive of particulates in the plume.