Carbon-based Ink Research Articles

Analysis of PEG oligomers in black gel inks: Discrimination and ink dating

Carbon-based black gel inks are common samples in forensic practice of questioned document examination in China, but there are few analytical methods for this type of ink. In this study, a liquid chromatography–.high resolution mass spectrometry (LC–HRMS) method was established for the analysis of PEG oligomers in carbon-based black gel ink entries. The coupled instruments achieve both the identification and quantification of PEG oligomers in ink entries with reproducible results. Twenty carbon-based black gel inks, whose Raman spectra appeared identical, were analyzed using the LC–HRMS method. As a result, the twenty gel inks were classified into four groups according to the distribution of PEG oligomers. Artificially aging of PEG 400 and a gel ink showed that as PEG degraded, the relative amounts of low molecular weight PEG oligomers increased, while those of high molecular weight decreased. The degradation of PEG oligomers in a naturally aged gel ink was consistent with those in the artificially aged samples, but occurred more slowly. This study not only provided a new method for discriminating carbon-based black gel ink entries, but also offered a new approach for studying the relative ink dating of carbon-based black gel ink entries.

Raman spectroscopic analysis of an important Visigothic historiated manuscript.

Raman spectroscopy has been used to study fragments of early Visigothic historiated manuscripts from the important mediaeval library at Santo Domingo de Silos which were a part of a Beato dating from the tenth to the mid-eleventh centuries. These fragments are from some of the oldest manuscripts in the scriptorium of the monastery. In this study, a comparison is made between the pigments and inks used on these manuscripts and those used in a previous study of the unique Visigothic Beato de Valcavado in Santa Cruz, Valladolid, completed in the year 970, which is noted for its quality of execution as well as its content and is remarkable eschatologically in being identifiable as the complete work of only a single scribe. For comparative purposes, the pigments and inks used in the Silos Monastery Beato and a series of historiated early manuscripts from mediaeval times through to the Renaissance also held in the monastic library were analysed. Raman spectroscopy identified a range of mineral and organic pigments such as cinnabar, orpiment, minium, azurite and indigo. In addition, a number of admixtures were found, for example, indigo and orpiment to produce vergaut (green) and a mixture of cinnabar with iron-gall ink and cerussite to produce darker and lighter shades of red. Some interesting conclusions were drawn about the use of iron-gall and carbon-based inks.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

Carbon-Based Flexible and All-Solid-State Micro-supercapacitors Fabricated by Inkjet Printing with Enhanced Performance

By means of inkjet printing technique, flexible and all-solid-state micro-supercapacitors (MSCs) were fabricated with carbon-based hybrid ink composed of graphene oxide (GO, 98.0 vol.%) ink and commercial pen ink (2.0 vol.%). A small amount of commercial pen ink was added to effectively reduce the agglomeration of the GO sheets during solvent evaporation and the following reduction processes in which the presence of graphite carbon nanoparticles served as nano-spacer to separate GO sheets. The printed device fabricated using the hybrid ink, combined with the binder-free microelectrodes and interdigital microelectrode configuration, exhibits nearly 780% enhancement in areal capacitance compared with that of pure GO ink. It also shows excellent flexibility and cycling stability with nearly 100% retention of the areal capacitance after 10,000 cycles. The all-solid-state device can be optionally connected in series or in parallel to meet the voltage and capacity requirements for a given application. This work demonstrates a promising future of the carbon-based hybrid ink for directly large-scale inkjet printing MSCs for disposable energy storage devices.Graphical

Design and fabrication of flexible supercapacitor devices by using mesoporous carbon/polyaniline ink

In this work, mesoporous carbon materials were synthesized by soft template method. In this strategy, poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) block co-polymers (F127) were used as the template while fructose were employed as the carbon precursor. After hydrothermal treatment, the soft templates could be easily removed by pyrolysis of the as-prepared carbon materials in argon. The resultant mesoporous carbon (MC) materials exhibit a specific surface area of ~422m2g−1. In addition, the as-prepared MC was incorporated together with polyaniline (PANI) to form the carbon-based ink. By using the screen printing method, the as-prepared ink was printed on the flexible substrate of polyethylene glycol terephthalate (PET) with silver layer. The as-fabricated flexible supercapacitor electrode was evaluated by galvanostatic charge-discharge and cyclic voltammetry (CV). By creating more storage space of electrons generated by the redox reaction of PANI, it is noticed that the specific capacitance of the supercapacitor of MC/PANI is about 2.5 times of the supercapacitor of PANI. The method of carbon-based ink synthesis and flexible supercapacitor fabrication could give a potential guidance for the flexible energy storage device fabrication.

Focus on materials, semiconductors, vacuum, and cryogenics

Focus on materials, semiconductors, vacuum, and cryogenics

Biosensor/Biofuel Cell System for Lactate Detection in Sweat, Targeted Towards Human Performance

Non-invasive monitoring of biomarkers in biological fluids through the use of wearable sensors gained significant interest in the past several decades [1]. Research efforts have been focused on the development of chemical and biochemical sensors for a range of metabolites, including glucose, lactate, ethanol, trace metals and various ions, targeting several bodily fluids such as tears, saliva, and sweat [2]. Work presented here will discuss the development of a sensor system, capable of real-time monitoring of lactate levels in sweat. Such a device is desired in order to correlate increasing levels of lactate to fatigue levels of a person performing physically demanding activities [3]. Most existing systems employ traditional batteries as power sources for sensors. The system described here utilizes a light weight biofuel cell as the power source giving a complete bio-friendly sensor system. The system is comprised of three main elements: a biosensor, a biofuel cell, and electronics interface. The biosensor detects lactate levels in sweat via enzymatic reaction of Lactate Dehydrogenase (LDH). Sensor patch features a three electrode design assembled onto generic athletic tape and covered with medical gauze, providing both flexibility and sweat collection capability. LDH is immobilized at the working electrode via conductive carbon-based ink. The electrode surface is then further modified by vapor-deposited tetramethyl orthosilicate (TMOS) coating in order to provide greater stability to the sensor against temperature and pH fluctuations. Sensor calibration time period was relatively quick (5 minutes) and response was immediate with addition of lactate. Test results for the sensor patch showed an open circuit potential of ~0.06V vs. Ag/AgCl and an equilibrated current of approximately 30µA when held at 0.3V vs. Ag/AgCl. The patch also demonstrated a sensitivity of 0.2µA/mM lactate when tested in a range of 5-100mM lactate. A glucose-based biofuel cell provides the power to operate the biosensor. The anode, driving glucose oxidation, is comprised of immobilized Glucose Dehydrogenase (GDH) on a high surface area carbon felt (CF) electrode. Prior to enzyme immobilization, CF electrode surface was modified with electrochemically deposited polymethylene green (PMG) as well as chemically tethered Nicotinamide Adenine Dinucleotide (NAD). An oxygen-reducing cathode was employed as counter electrode. The biofuel cell generated an open circuit potential of 0.7V vs. Ag/AgCl, a total current of 81.0mA, and total power of 16.7mW. The patch sensor is coupled to the biofuel cell via external electrical components: an energy harvester and a micropotentiostat. The energy harvester component is connected to the biofuel cell. Its primary function is to continuously provide stable output voltage to the micropotentiostat. Thus it is constantly drawing power from the biofuel cell and up-converting the voltage from 0.7 to 3V. The patch sensor is connected to the micropotentiostat. A constant potential of 0.3V vs. Ag/AgCl is needed to operate the sensor, which is supplied by the micropotentiostat. Additionally, it is used to provide a read-out of an electrical signal, i.e. current, generated during sensor operation. System performance was demonstrated, employing artificial sweat. Results showed linear sensor response with increasing lactate content of the artificial sweat solution. [1] A. J. Bandodkar and J. Wang, "Non-Invasive Wearable Electrochemical sensors: A Review," Trends in Biotechnology, vol. 32, no. 7, pp. 363-371, 2014. [2] J. Kim, W. R. de Araujo, I. A. Samek, A. J. Bandodkar, W. Jia, B. Brunetti, T. R. Paixao and J. Wang, "Wearable temporary tattoo sensor for real-time trace metal monitoring in human sweat," Electrochemistry Communications, vol. 51, pp. 41-45, 2015. [3] S. Jadoon, S. Karim, M. R. Akram, A. K. Khan, M. A. Zia, A. R. Siddqi and G. Murtaza, "recent Developments in Sweat Analysis and Its Applications," International Journal of Analytical Chemistry, pp. 1-7, 2015. Figure 1

A holistic multimodal approach to the non-invasive analysis of watercolour paintings

A holistic approach using non-invasive multimodal imaging and spectroscopic techniques to study the materials (pigments, drawing materials and paper) and painting techniques of watercolour paintings is presented. The non-invasive imaging and spectroscopic techniques include VIS–NIR reflectance spectroscopy and multispectral imaging, micro-Raman spectroscopy, X-ray fluorescence spectroscopy (XRF) and optical coherence tomography (OCT). The three spectroscopic techniques complement each other in pigment identification. Multispectral imaging (near-infrared bands), OCT and micro-Raman complement each other in the visualisation and identification of the drawing material. OCT probes the micro-structure and light scattering properties of the substrate, while XRF detects the elemental composition that indicates the sizing methods and the filler content. The multiple techniques were applied in a study of forty-six nineteenth-century Chinese export watercolours from the Victoria and Albert Museum (V&A) and the Royal Horticultural Society (RHS) to examine to what extent the non-invasive analysis techniques employed complement each other and how much useful information about the paintings can be extracted to address art conservation and history questions. A micro-destructive technique of micro-fade spectrometry was used to assess the vulnerability of the paintings to light exposure. Most of the paint and paper substrates were found to be more stable than ISO Blue Wool 3. The palette was found to be composed of mostly traditional Chinese pigments. While the synthetic pigment, Prussian blue, made in Europe, was found on some of the paintings, none was found on the RHS paintings accurately recorded as being between 1817 and 1831 even though it is known that Prussian blue was imported to China during this period. The scale insect dyes, lac and cochineal, were detected on nearly every painting including those that fall within the identified date range. Cochineal is known to have been imported to China in the same period. While carbon-based ink was used for the drawings in the V&A paintings, graphite pencil was used in most of the RHS paintings. The majority of RHS paintings were on Western papers, but nearly all of the V&A paintings were on Chinese papers. Nearly all of the V&A painting substrates and hardly any of the RHS paintings were sized with alum. Elements such as Cu, Zn, Ti and Pb were detected on nearly all of the RHS papers regardless of whether they were Chinese or Western papers. These elements were largely absent from the V&A papers. The differences between the two collections reflect their discrete origins and intended purposes.

Revealing letters in rolled Herculaneum papyri by X-ray phase-contrast imaging.

Hundreds of papyrus rolls, buried by the eruption of Mount Vesuvius in 79 AD and belonging to the only library passed on from Antiquity, were discovered 260 years ago at Herculaneum. These carbonized papyri are extremely fragile and are inevitably damaged or destroyed in the process of trying to open them to read their contents. In recent years, new imaging techniques have been developed to read the texts without unwrapping the rolls. Until now, specialists have been unable to view the carbon-based ink of these papyri, even when they could penetrate the different layers of their spiral structure. Here for the first time, we show that X-ray phase-contrast tomography can reveal various letters hidden inside the precious papyri without unrolling them. This attempt opens up new opportunities to read many Herculaneum papyri, which are still rolled up, thus enhancing our knowledge of ancient Greek literature and philosophy.

A perceptual approach to the fusion of visible and NIR images in the examination of ancient documents

Abstract Imaging techniques are commonly used to improve the legibility of text in ancient or degraded documents. Infrared reflectography is one of the best methods for examining documents written in a carbon-based ink since the contrast between the ink and the support is usually much greater in that band. In these cases, for archival and study purposes, the visible and the corresponding infrared images are usually shown next to one another. In other cases, like e.g. papyri, this separation between text and background is not easily achievable, and therefore, a more sophisticated elaboration is needed. Moreover, in these cases, the background is a relevant source of information on the original document, and thus its integration with the extracted text could represent an effective solution for scholars. In this paper, we present a new method to improve the legibility of the text in visible light reflectance images without altering the appearance of the support. The method is based on the fusion of the text extracted from the infrared image with the visible image. The contrast of the text in the infrared image is first enhanced with the Automatic Color Equalization algorithm, a perceptual-based enhancement technique, and then extracted with a thresholding process. The proposed method allows to visualize different information (text, background, alterations, etc.) on a single image, and can be also used for an efficient archival approach.

Nanomanipulation-coupled to nanospray mass spectrometry applied to document and ink analysis

A method for the extraction and analysis of ink samples was developed using microscopy with direct analyte probe nanoextraction coupled to nanospray ionization mass spectrometry (DAPNe-NSI-MS) for localized chemical analysis of document inks. Nanomanipulation can be effectively coupled to nanospray ionization mass spectrometry providing picomolar sensitivity, and the capability to analyze ultra-trace amounts of material and reduce the required sample volume to as low as 300nL. This new and innovative technique does not leave destructive footprints on the surface of a document. To demonstrate the breadth of this technique, analysis of inks from various eras were tested, iron gall ink and modern inks, as well as the capability to detect the oxidative products of polyethylene glycol (PEG), a common binding agent. The experimental results showed that DAPNe-NSI-MS was able to chelate iron(II) and manganese(II) ions of iron gall ink and organic components of modern and carbon-based inks. Regardless of whether the ink composition is modern or ancient, organic or inorganic, this new instrumental approach is able to identify and characterize the ingredients by modifying the extraction solvent, illustrating the potential diversity of the DAPNe technique.

Efficacy and safety of a topical carbon suspension photoenhancer adjunctive to intense pulsed light treatment for pigmented lesions in Japanese patients: A pilot study.

Pigmented lesions, e.g., senile lentigo and seborrheic keratosis are commonly seen in photodamaged skin in the Japanese general population. The use of the laser to treat such lesions is often painful, and intense pulsed light (IPL) systems have become widely used. Clearly demarcated pigmented lesions may be identified easily and treated with IPL. Less well demarcated lesions, however, which are very difficult to identify or thick melanogesic lesions like seborrheic keratosis represent one of the most challenging conditions to be treated using IPL. This pilot study evaluated carbon suspension-assisted IPL treatment of such lesions. Three female Japanese patients, Fitzpatrick skin type III-IV, comprised the subjects, aged 58, 78 and 85, with indistinct senile lentigines or thick seborrheic keratoses. The lesions were painted or demarcated with a carbon-based ink from a commercially-available Japanese writing instrument (Fude-pen™, Pentel, Japan) consisting of a brush-like pen nib with a refillable or replaceable ink reservoir, and then treated with a broadband (560 - 1200 nm) IPL system. The poorly-demarcated lesions were quickly and easily marked with the pen, and the IPL treatments were well-tolerated. All patients had good improvement in their painted pigmented lesions based on the overall evaluation, compared with unpainted ones. Side effects after treatment, such as hyperpigmentation, persistent erythema, and scarring, were minimal. Topical carbon suspension-assisted IPL treatment could be a good option for patients with indistinct pigmented or thick melanogenesic lesions. Adverse reactions to this treatment were minimal and the results acceptable, though appropriate lesions need to be chosen carefully.

Effect of rheology controller agent addition to Micro-Porous Layers on PEMFC performances

Formulations of carbon-based inks for doctor blade applications were considered and the use of Carboxymethylcellulose (CMC) as rheology modifier and suspension stabilizer was proposed. Rheological measurement evidenced that CMC addition guarantees a good dispersion of the carbon powder which results in a higher stability of the ink. The electrical performances of Gas Diffusion Layer (GDL) coated with Micro-Porous Layers (MPLs) prepared with and without CMC were compared. A single PEMFC was used to assess the properties of these GDLs: electrochemical performances were tested in terms of I–V curves and of AC Electrochemical Impedance Spectroscopy (EIS) of the running cell. CMC-containing GDLs showed improved performances when the cell was operated at 80°C and RH 80–60. Analysis of the EIS spectra demonstrated that, at high Current Density (CD), the CMC-based GDLs suffer for water management. Such a behavior was ascribed to a hydrophilic character of the GDL due to residual amounts of CMC in MPL coating.

Maximizing the Use of Platinum Catalyst by Ultrasonic Spray Application

The following discusses the method and advantages of ultrasonic deposition of carbon-based platinum ink solution onto catalytic membranes in the manufacture of platinum-based fuel cells, doubling industry standard performances. Using patented ultrasonic atomization technology (Ultrasonic atomization technology provided by Sono-Tek) conductive properties are compared to those of films created with hydraulic deposition and paste printing methods, using comprehensive analysis of morphology characteristics, deposition density, and distribution of platinum particles throughout the thickness and surface area of the coating. Results indicate significant increase in uniform distribution of platinum particles using the ultrasonic deposition method. Measured electrochemically active Pt surface area using ultrasonic atomization was recorded as high as 71% of the total Pt particle surface area.

A multi-analytical approach for the characterization of powders from the Pompeii archaeological site

Nine black powders found in Pompeii houses in three different types of bronze vessels (cylindrical theca atramentaria, unguentaries, and aryballoi) were characterized in order to assess a correspondence between the composition and the type of vessel and, possibly, to verify if these powders were inks or not. For the compositional characterization, a multi-analytical approach was adopted, which involved the use of scanning electron microscopy-energy dispersive X-ray, Fourier-transformed infrared spectroscopy, Raman, X-ray diffraction, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, gas chromatography coupled with mass spectrometry (GC/MS), and pyrolysis GC/MS. Powders contained in cylindrical theca atramentaria form a homogeneous group, and their organic and inorganic compositions suggest that they were writing inks, while powders contained in unguentaries and aryballoi could have had several different uses, including writing inks and cosmetics. Furthermore, the composition profile of the powders found in cylindrical cases shows that, at 79 AD: , in Pompeii, carbon-based inks were still used for writing, and iron gall inks had not been introduced yet.

The Artemidorus Papyrus: Solving An Ancient Puzzle with Radiocarbon and Ion Beam Analysis Measurements

Ancient papyrus manuscripts are one of the most fascinating sources for reconstructing not only ancient life habits but also past literature. Recently, an amazing document has come to the fore due to the heated debates it raised: the so-called Artemidorus papyrus. It is a very long scroll (about 2.5 m) composed of several fragments of different sizes, with inscriptions and drawings on both sides. On the recto of the document, a text about geography and some drawings of heads, feet, and hands are present, while on the verso there are many sketches of animals, both real and fantastic. Its importance in classical studies comes from the fact that some scholars claim that it is the first known transcription of a relatively large fragment by the Greek geographer Artemidorus. However, other scholars think that the papyrus is a fake, drawn in the 19th century AD by a well-known forger. In order to overcome all possible ambiguities, the papyrus has been studied not only on the basis of historical and paleographic criteria but also by scientific techniques. We have contributed to the knowledge about the papyrus by radiocarbon dating the document and by analyzing the composition of the ink using ion beam analysis (IBA). Results are compatible with the scroll being an ancient manuscript: accelerator mass spectrometry (AMS) 14C measurements have dated the papyrus to a period between the 1st century BC and 1st century AD, while IBA measurements have pointed out the use of an organic (carbon-based) ink, which was typical of ancient Roman and Greek times. Details of the measurements are presented to emphasize the importance of combining AMS and IBA results.

Intraperitoneal India ink deposits appearing as endometriosis in a patient with chronic pelvic pain.

Visualization and biopsy of suspicious peritoneum can confirm endometriosis. Endoscopic India ink tattooing can lead to peritoneum that visually mimics endometriosis. A woman with chronic pelvic pain and a history of treated endometriosis underwent diagnostic laparoscopy. Previously, a small bowel endoscopy had been performed to evaluate the pain. At laparoscopy, black peritoneal lesions were seen and biopsied due to concern for endometriosis. Pathology concluded the lesions to be carbon-based ink. Investigation revealed that tattoos placed during the small bowel endoscopy used India ink. Endoscopic India ink tattooing used to demarcate an area of bowel for later identification can stain peritoneal surfaces and mimic endometriotic implants.

The Grolier Codex: A Non Destructive Study of a Possible Maya Document using Imaging and Ion Beam Techniques

AbstractThe Grolier Codex has been a controversial document ever since its late discovery in 1965. Because of its rare iconographical content and its unknown origin, specialists are not keen to assure its authenticity that would set it amongst the other tree known Maya codes in the world (Dresden, Paris Codex and Madrid Codex).The document that has been kept in the Museo Nacional de Antropología in Mexico City, after its exposure in 1971 at the Grolier Club of New York, has been analyzed by a set of non-destructive techniques in order to characterize its materials including paper fibers, preparation layer and colors composition. The methodology included UV imaging, IR reflectography and optic microscopy examinations as well as Particle Induced X-ray Emission (PIXE) and Rutherford Backscattering Spectrometry (RBS) using an external beam setup for elemental analysis. All the measurements were carried out at 3MV Pelletron Accelerator of the Instituto de Física, UNAM. The aim of this work is to verify if the materials in the Grolier Codex match those found for other pre-Hispanic documents.From the elemental composition we concluded that the preparation layer shows the presence of gypsum (CaSO4), color red is due to red hematite (Fe2O3) and black is a carbon-based ink. These results agree with previous analyses carried out by Scanning Electron Microscopy (SEM-EDX) on few samples. However, the presence of Maya Blue in the blue pigment cannot be assured. The examination using UV and IR lights shows homogeneity in the inks and red color but dark areas that contain higher amounts of K in the preparation layer. This paper discusses the results obtained for the UV-IR examinations and the elemental analysis. A comparison with other studies on pre-Hispanic and early colonial codex is presented.

Science and Fiction: James Nasmyth's Photographic Images of the Moon

aving made his fortune as an industrialist and inventor with his Bridgewater Foundry in Manchester, the mechanical engineerJames Nasmyth was able to retire in his late forties, in 1856, in order to devote himself to his longstanding passion for astronomy (Nasmyth, Autobiography 329). His main astronomical project, from 1842, had been a sustained series of lunar observations, culminating in his publication The Moon: Considered as a Planet, a World, and a Satellite (Nasmyth and Carpenter).' Among the reasons Nasmyth's book is noteworthy is that it was one of the first books to be illustrated by photo-mechanical prints. This new technique allowed photographs to be published through standard industrial print processes using permanent carbonbased inks (Jussim 52), and represented a significant improvement upon the more laborious and fugitive silver-chemistry darkroom processes used in the earliest books with photographic illustrations (Gernsheim). In photo-mechanical printing, light is used to prepare printing surfaces: because the process can be applied to both photographic and line originals (Woodbury 363), it provided the technical basis for mass-produced illustrated publication from the late nineteenth century until the advent of digital print technology. Nasmyth produced twenty-four photographs consciously designed for publication in this innovative medium, with the intention of using his visual evidence to carry some of the argument of his book. Although some successful photographic images of the moon had already been shown in public exhibitions--such as the 1851 daguerrotype byJohn Adams Whipple, or photographs on paper by Warren de la Rue, Henry Draper, and Lewis Rutherford in the 1850s and 1860s-they had not been directly disseminated in print. Such images were rare, for they required exceptional technical dexterity, luck, and long observational knowledge on the part of the photographic astronomer; furthermore, they

Development of disposable low density screen-printed electrode arrays for simultaneous electrochemical measurements of the hybridisation reaction

Abstract This paper deals with the development of different formats of screen-printed array of electrodes. The arrays consist of a silver pseudo-reference electrode surrounded by four or eight radially distributed working electrodes. Two different commercially available inks were used to fabricate the working electrode (WE) surfaces: a carbon-based ink and a gold-based ink. Due to their low curing temperature, the inks were screen-printed onto an inert plastic substrate. The electrochemical characterisation of these arrays is shown; reproducibility of the arrays as well as the batch-to-batch reproducibility were also assessed. As model case, the four WE array was used as platform to develop an electrochemical genosensor. Analytical parameters such as linearity range, reproducibility and detection limit of the genosensor were evaluated. Preliminary results on real samples were also reported.

REAL OR FAKE?

A NEW CHAPTER HAS BEEN WRITten in a long-standing controversy about whether a document at Yale University called the Map is real or fake. Researchers in England have just reported that black ink on the map is carbon-based and note that a yellow border on the ink lines, which appears to stem from pigment breakdown, could not have been produced by a carbon-based ink [ Anal. Chem. , 74, 3658 (2002)}. So they conclude that the map is a 20th-century forgery But whether this represents the final chapter in the Map saga remains to be seen. The Map is held at the Beinecke Rare Book & Manuscript Library Yale University's principal repository for literary papers, early manuscripts, and rare books. The map primarily depicts Europe, Asia, and part of Africa. But it also shows an island in the western Atlantic Ocean labeled Vinilanda Insula, and an inscription above the island describes its discovery by Viking explorers. Vinland ...