Ballpoint Inks Research Articles

Spectroscopic techniques and chemometrics for ink analysis: Document analysis application

This study represents a methodology to determine the falsified documents via a combined method of spectroscopic techniques and chemometrics. The techniques of UV–Vis and FTIR-ATR spectroscopies and principal component analysis methods have been applied to black, blue, and red ballpoint pens available in the Türkiye market. The analysis results of the applied spectroscopic techniques were found to be consistent with each other for the examined eleven ink samples from three different brands, and it was observed that FTIR-ATR spectroscopy had higher discriminative power. A dried sample preparation technique developed for small amounts of samples for FTIR-ATR measurements and the increased the sensitivity of FTIR-ATR technique was associated with this sample preparation method. Statistical techniques showed that the UV–Vis technique proves useful outcomes in distinguishing inks according to their colors, whereas the FTIR-ATR technique is valuable for identifying ink brands. Additional analysis of the sub-brand of black inks and falsified old-dated check sample analysis validated that our methodology has the potential to classify and identify ballpoint inks in forensic applications. Due to the limited sample quantity available for analysis in real samples, only FTIR-ATR analysis was possible, and the results demonstrated that document forgery could be detected from small parts of samples in the document. When we look at the overall outcome of this study, a comprehensive methodology enriched with statistical calculations has been proposed that can be applied even in a laboratory with limited resources, having only UV–Vis and FTIR-ATR capabilities.

Application of Raman spectroscopy in relative blue ballpoint pen ink dating for forensic document analysis – a case report

In this case report, blue ballpoint ink on a questioned document was investigated using a newly developed Raman model devoted for dating of documents via writing inks. The majority of blue ballpoint pen inks contain crystal violet - a triarylmethane dye which displays a typical “molecular fingerprint” type of Raman spectrum, of which most intense peaks at 749 cm−1 and 1542 cm−1 (under 785 nm laser excitation) represents the least and the most stable bonds of crystal violet molecules, respectively. The ratios of peak intensities at above mentioned Raman shifts are utilized to estimate the relative dating of the questioned blue ballpoint pen ink in practice, results of which agreed with estimations using other traditional relative dating methods. ® 2023 Journal of Science and Technology - NTTU

Application of Raman spectroscopy in relative blue ballpoint pen ink dating for forensic document analysis – a case report

In this case report, blue ballpoint ink on a questioned document was investigated using a newly developed Raman model devoted for dating of documents via writing inks. The majority of blue ballpoint pen inks contain crystal violet - a triarylmethane dye which displays a typical “molecular fingerprint” type of Raman spectrum, of which most intense peaks at 749 cm−1 and 1542 cm−1 (under 785 nm laser excitation) represents the least and the most stable bonds of crystal violet molecules, respectively. The ratios of peak intensities at above mentioned Raman shifts are utilized to estimate the relative dating of the questioned blue ballpoint pen ink in practice, results of which agreed with estimations using other traditional relative dating methods.
 ® 2023 Journal of Science and Technology - NTTU

The Use of Crystal Violet Degradation Products for Ballpoint Pen Ink Manuscript Dating.

Determining the approximate dates that written documents were drawn up based on the chemical composition of the ink is not a simple process. It is very demanding in terms of legal requirements. Various studies have succeeded in dating manuscripts by analyzing the temporal evolutions of the concentrations of dyes and solvents in documents based on the original formulations of the ink pens. These analyses were carried out simultaneously by HPLC-DAD for dyes and by GC-MS for solvents. This study aims, for the first time, to evaluate novel ink compounds and the temporal evolution of the concentrations of the degradation products of the dyes used by most suppliers and which are present in almost all types of ballpoint inks, i.e., Crystal Violet (CV). CV degrades through two parallel pathways: on the one hand, it undergoes progressive demethylation until it becomes pararosaniline, and on the other, it undergoes a breakdown of the molecule obtaining, among other by-products, the compound N,N'-Dimethyl-4-aminophenol (NNAPH), that was experimentally verified using four different inks (e.g., Inoxcrom® and Sigma® brands, in blue and black). For the NNAPH compound, we observed that four of the inks under analysis displayed the same temporary behavior despite having different initial chemical compositions. These initial results show the high potential for both CV and NNAPH, together with the rest of the pararosaniline family, as age tracers for dated/old documents. These techniques may potentially open up new avenues for universal dating tools, regardless of the brands of ink employed for use in different ballpoint pen types.

Testing Ink Resistance on Ballpoint and Stamp Based on Regulation of The National Archives of The Republic of Indonesia No. 7 Year 2018

The use of ballpoint ink and stamp ink is particularly important in the future condition of archives. The ink on the paper is degradable due to natural aging during conservation. It cannot be stopped but must be maintained. This paper aims to examine the durability of ink on ballpoint pens and stamps based on the Republic of Indonesia's National Archives Regulations. Ink samples were soaked in deionized water and soap solution (1% v/v) for 1 hour to identify faded ink on the surface of the paper. Chemical composition of ballpoint ink and stamp ink were analysed using Gas Chromatography Mass Spectrometry (GC-MS) and physical characterization using Video Spectral Comparator (VSC). The results of this study are the ballpoint pens commonly used in ANRI for handwriting and signatures that fade easily. Ballpoint pen inks that do not fade are Standard Lexion LX-105 and Pilot Super GP while ink that does not fade is the Archives Section stamp. The results of the GCMS analysis found 15 chemical compounds with the main compounds being long fatty acid esters. The result of VSC analysis is that each ink has distinct colour characteristics when exposed to Infrared at 645nm.

Deep-Learning-Based Character Recognition from Handwriting Motion Data Captured Using IMU and Force Sensors.

Digitizing handwriting is mostly performed using either image-based methods, such as optical character recognition, or utilizing two or more devices, such as a special stylus and a smart pad. The high-cost nature of this approach necessitates a cheaper and standalone smart pen. Therefore, in this paper, a deep-learning-based compact smart digital pen that recognizes 36 alphanumeric characters was developed. Unlike common methods, which employ only inertial data, handwriting recognition is achieved from hand motion data captured using an inertial force sensor. The developed prototype smart pen comprises an ordinary ballpoint ink chamber, three force sensors, a six-channel inertial sensor, a microcomputer, and a plastic barrel structure. Handwritten data of the characters were recorded from six volunteers. After the data was properly trimmed and restructured, it was used to train four neural networks using deep-learning methods. These included Vision transformer (ViT), DNN (deep neural network), CNN (convolutional neural network), and LSTM (long short-term memory). The ViT network outperformed the others to achieve a validation accuracy of 99.05%. The trained model was further validated in real-time where it showed promising performance. These results will be used as a foundation to extend this investigation to include more characters and subjects.

Comparative analysis of aged documents by desorption electrospray ionization-Mass spectrometry (DESI-MS) imaging.

Document dating is an important and challenging task in the field of forensic science. With the development of analytical techniques, related methods are emerging for document dating studies. Desorption electrospray ionization-mass spectrometry (DESI-MS) is an ambient ionization-MS technique that has been applied in the forensic discrimination of inks. This study focused on utilizing DESI-MS to distinguish between ink entries of different ages. Blue ballpoint ink and black gel ink samples were artificially aged by heat and light exposure and then screened by DESI-MS in the positive ion mode, with a methanol-water-formic acid solution (90:10:0.1%, v/v/v) as the desorption solvent. As a result, the artificially aged ink samples were directly differentiated from the reference ones in the chemical images of age-dependent compounds such as basic dyes or polyethylene glycol derivatives. The amount of ethoxylated fatty amine surfactants in copy paper was also found to decrease after artificial aging. Moreover, this method enabled us to visualize the differences between the composition of naturally aged and fresh ink samples. It has been proven to cause no apparent destruction of the samples. The identification of chronological changes in document materials suggests that the DESI-MS method is a promising approach for relative document dating.

The discrimination potential of VSC, TLC and HPLC for ballpoint inks

The Sri Lanka Journal of Forensic Medicine, Science & Law (SLJFMSL) is a peer-reviewed, open-access journal published biannually in May and December each year by the Department of Forensic Medicine, Faculty of Medicine, University of Peradeniya, Sri Lanka.The mission of the SLJFMSL is to stimulate, encourage and empower researchers to publish high quality research in order to promote evidence based practice and provide a platform for researchers to share experiences and knowledge in the fields of forensic medicine, forensic sciences, medical ethics and relevant law. This journal publishes original research papers, reviews, points of view, case reports, technical notes and letters to the editor. The SLJFMSL is committed to maintaining and conforming to the editorial and ethical standards recommended by the International Committee of Medical Journal Editors.SLJFMSL was assessed by the Journal Publishing Practices and Standards framework and was placed at level four (of six) and is currently listed in SLJOL, DOAJ, IMSER, NLM Catalogue.

Determination of Sequence of Strokes-Conventional & Non-Conventional Techniques - A Review Study

The most important tool for a document examiner is his or her own vision, but in this section and the laboratory tour section we will consider the external tools which enable the examiner to see, evaluates and record more than is apparent to the unaided eye. The number of papers outlines the basic necessity of photographic illustrations for demonstrating the data offer clinching evidence, strong enough to with stand legal scrutiny on which opinions of the document examiner are based, hence play a very vital role in the examination of forensic documents. For the purpose of examination in the laboratory as well as the use of photographs becomes indispensible in cases involving traced or simulated forgery, built-up documents, forgery over genuine signatures and forgery by substitution, interpolations, differences in the tint of ink etc. The authors have solved a case in resolving the sequence of strokes with same ball point ink in an actual case received in the laboratory.

Determining Intersecting Ball-Point Ink Strokes with Different Aging

The order of laying down homogeneous intersecting strokes of ball-point inks has been assessed using a range of different spectroscopic and analytical techniques for recent inks and for inks with a time difference of 4 years. These techniques are infrared reflectance photography with luminescence, fluorescence micro-spectrophotometry, Fourier transform infrared spectrometry, high resolution liquid chromatography and gas chromatography with mass spectrometry. This paper presents a combined method applicable to forensic cases aimed at resolving homogenous intersecting strokes of ball-point ink to determine whether they were made at the same time or, on the contrary, they were intersecting strokes laid down with an acute time difference, taking four years as an age reference.

ToF-SIMS evaluation of markings made by the same black ballpoint pens at different times

The differentiation and relative dating of ink lines in questioned documents are important tasks in forensic science. Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) is a surface-sensitive mass spectrometry technique with potential to distinguish inks based on chemical differences such as those caused by differences in the age of ink markings from the same pen. In this work, both positive and negative polarity ToF-SIMS spectra were evaluated for three commercial black ballpoint pen inks over an analysis time of 4 to 671 days. Changes in the spectra included demethylation of triarylmethane dyes such as crystal violet, and loss of the anionic dye metanil yellow. ToF-SIMS spectra of the black ballpoint inks continued to change up to 6 months for all inks and up to 22 months in some cases. Samples with 1-day, 1-week and 1-month drying times were also evaluated using several data processing approaches. Markings from the same pen were most likely to be distinguished by ToF-SIMS if the age difference between the markings was 1 month or longer, although some samples were distinguished with smaller differences in writing times. Furthermore, the results indicated that ToF-SIMS imaging is best performed within 3–6 months after sample preparation as differentiation becomes more difficult after longer analysis delays. This is the first systematic ToF-SIMS study of ink aging, which provides valuable information about the characteristic ions and data analysis approaches for future forensic analyses.

Application of chemometric methods for the determination of fading and age determination of blue ballpoint inks

AbstractThis study presents preliminary results for applicability of micro‐Raman and VIS–NIR reflectance spectroscopy in age determination of blue ballpoints inks containing phthalocyanine and crystal violet. Based on chemometric methods, 74 different random blue pens were classified to various types of inks. Then handwritten samples stored in different light conditions were subjected to the analysis. The first set of samples was stored for 7 years at room temperature in an envelope without direct exposure to the light, whereas the second set of samples was aged by exposing them to natural light cycle for 85 days. The L, a, b values were determined on the basis of recorded Raman and VIS–NIR spectra and then used for chemometric calculation. Based on those values, partial least squares models were built, allowing to obtain correlations between ∆E and Raman and reflectance spectra. Relative standard errors of prediction RSEP(%) for obtained models were calculated in the range 1.97–5.13 and 1.20–2.27 for Raman and VIS–NIR spectra, respectively. The proposed nondestructive method allows to estimate the age of daylight exposed samples.

Sequence determination between blue ballpoint pens and toner using MikrosilTM casting of the intersection

A technique was developed and assessed for use in the determination of line crossing sequence. This technique takes advantage of the transfer of both substrate topography and ink chemistry, at the line crossing intersection, to a Mikrosil™ casting compound. An initial pilot involving intersections between blue ballpoint inks and toner was constructed and blind tested using Forensic Document Examiners at the Canada Border Services Agency. Following this initial pilot, a more extensive trial was constructed to assess the technique’s application with a larger population of blue ballpoint pens and a larger number of document examiners.

In situ examination of handwritten blue ballpoint inks using video spectral comparison with chemometrics

Video spectral comparator (VSC®) workstations are routinely used for visual examinations of pen inks on handwritten documents. Current VSC® models also permit spectral acquisition, which can be combined with chemometric techniques to statistically determine ink similarity. However, there is a lack of research comparing such an approach to typical examinations by forensic experts. This preliminary study compares the analysis of handwritten blue ballpoint inks using visual and spectroscopic analysis. Both approaches were successful in detecting simulated additions or alterations on paper documents. These approaches could thus complement each other as an integrated workflow; providing quantitative data to support expert opinions.

Blue and Black Ballpoint Pen Inks: a Systematic Review for Ink Characterization and Dating Analysis

Documents are frequent targets of fraud and adulteration. Sometimes it is not enough to determine the document’s authenticity or authorship, but it is also necessary to demonstrate when the document was signed or written. Determining the age of a document, also known as ink dating analysis, is still a challenge for the forensic examiners. There are two main approaches for the dating of ballpoint pen inks: the static method, which is based on the characterization and identification of the ink composition and comparison to a reference collection, and the dynamic method, which involves the study of ink’s processes and alterations that occur with time, considering environmental aging factors such as light and humidity. This article aims to provide a comprehensive systematic review of the studies regarding ballpoint ink characterization and dating, in the last ten years. There are several methods, destructive and non-destructive, which are capable of characterizing and differentiating blue and black ballpoint pens that have shown applicability to the static approach. Regarding the dynamic dating methods, most studies quantified the loss of 2-phenoxyethanol (2-PE) solvent over time using GC-MS, or studied the dyes degradation through different methods. Although ink dating approaches offer relatively good accuracy, there is still more research to be done, such as the documents’ storage conditions evaluation, the influence of initial ink quantity variation between different pen brands and writing fists, and the type of paper.

Using the Physical and Chemical Characterization for the Ink of Laser Printer and Ballpoint Pen in Determination the Sequence of Their Intersection

In the forensic document examination, the determination of the chronological order of intersection strokes of the toner and ballpoint inks is a paramount challenge issue. Two types of intersection are prepared on three different types of paper. A digital microscope and Raman spectroscopy are two nondestructive techniques used to determine these sequences via cross lines. Four physical characteristics observed at intersection point under the digital microscope were a specular reflection, the ink gloss, the ink spreading and gap. The results of the digital microscope determined the two types of intersections strokes except the red color of ink over toner. The results of Raman spectroscopy showed that the spectrum results at the intersection point similar to the pure ink executed later. The complementary technique of Raman spectroscopy and the digital microscope were necessary to achieve a complete determination of the sequences intersection strokes of the toner and ballpoint ink.

Painting a high-output triboelectric nanogenerator on paper for harvesting energy from human body motion

Paper-based triboelectric nanogenerators (TENGs) represent an affordable, green, and eco-friendly energy harvesting methodology. In this work, we propose a novel X-shaped paper TENG (XP-TENG) formed from a ballpoint ink layer coated by painting with a commercial brush pen. The paper and Teflon tape serve as the triboelectric pairs, with the paper serving as the supporting component. Moreover, the XP-TENG is capable of providing two working patterns that can yield an expanded scope of practical applications. A stacked XP-TENG was proposed for increasing the output performance and harvesting the mechanical energy generated by motion of the human body. This staked XP-TENG can directly light up 101 blue high-power LEDs with working voltage of 3.4 V. The fabricated XP-TENG can be used for harvesting mechanical energy from human walking.

Migration behavior of organic dyes based on physicochemical properties of solvents as background electrolytes in non-aqueous capillary electrophoresis

The migration behavior of organic fluorescent dyes (i.e., crystal violet, methyl violet base, methyl violet B base, rhodamine 6G, and rhodamine B base) in non-aqueous capillary electrophoresis (NACE) was investigated by focusing on the physicochemical properties of various organic solvents [ethanol, methanol, 2-propanol, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO)] in background electrolyte (BGE). Laser-induced fluorescence (LIF) and UV/Vis detectors were employed to observe both the migration time of organic dyes and the electroosmotic flow (EOF) in NACE, respectively. As seen in conventional aqueous BGE, the mobility of EOF in organic solvents tended to rise when the ratio between the dielectric constant and the solvent’s viscosity (ε/η) increased in accordance with Smoluchowski’s equation. However, unlike the ε/η of pure organic solvents, the migration order of dyes changed as follows: methanol (60.0) > DMF (45.8) > ethanol (22.8) > DMSO (23.4) > 2-propanol (9.8). Since the amount of acetic acid added to balance the pH depends on the pKa of each solvent, EOF changed when the difference in the ε/η value was small. This resulted from the inhibition of mobility, and its difference was dependent on the ε/η of BGEs with high ionic strength. In particular, the actual mobility of dyes in DMF showed excellent compliance with the Debye–Hückel–Onsager (DHO) theory extended by Falkenhagen and Pitts, which enabled us to analyze all dyes within 15 min with excellent resolution (Rs > 2.5) under optimum NACE conditions (10 mM sodium borate and 4661 mM acetic acid in 100% DMF, pH 4.5). In addition, the NACE method was successfully applied for analyzing commercially available ballpoint ink pens. Thus, these results could be used to anticipate the migration order of organic dyes in a 100% NACE separation system.

Extended stribeck curves for food samples

Stribeck curves have long been used for understanding the lubricating behaviour of oils and greases, and in the recent years for applications ranging from ball point inks to synovial fluids. In the current work, an attempt is made to show as to what one can read from Stribeck curves of food samples such as chocolate spread, sauce etc. Additionally, the effect of saliva – human and artificial – on the frictional behaviour has also been studied. The tests were carried out on an MCR Tribometer with a ball-on-three-pin configuration. Polydimethylsiloxane and glass were used to simulate soft contact conditions that exist in the human mouth. Results from the tribological tests are plotted in the form of extended Stribeck curves, wherein, the friction coefficient is plotted as a function of rotational speed. Since the tribometer is capable of speeds as low as a few nanometres per second, it is also possible to observe the build-up of static friction and its transition into the kinetic regime of friction. Results indicate that certain aspects of the Stribeck curve can offer an insight into the correlation between the frictional behaviour of food to their sensory feel.

Direct and comprehensive analysis of dyes based on integrated molecular and structural information via laser desorption laser postionization mass spectrometry

Laser desorption laser postionization time-of-flight mass spectrometry (LDPI-TOFMS) was employed for direct analysis and determination of typical basic dyes. It was also used for the analysis and comprehensive understanding of complex materials such as blue ballpoint pen inks. Simultaneous emergences of fragmental and molecular information largely simplify and facilitate unambiguous identification of dyes via variable energy of 266nm postionization laser. More specifically, by optimizing postionization laser energy with the same energy of desorption laser, the structurally significant results show definite differences in the fragmentation patterns, which offer opportunities for discrimination of isomeric species with identical molecular weight. Moreover, relatively high spectra resolution can be acquired without the expense of sensitivity. In contrast to laser desorption/ionization mass spectrometry (LDI-MS), LDPI-MS simultaneously offers valuable molecular information about dyes in traces, solvents and additives about inks, thereby offering direct determination and comprehensive understanding of blue ballpoint inks and giving a high level of confidence to discriminate the complicated evidentiary samples. In addition, direct analysis of the inks not only allows the avoidance of the tedious sample preparation processes, significantly shortening the overall analysis time and improving throughput, but allows minimized sample consumption which is important for rare and precious samples.