Black Inkjet Research Articles

Forensic classification of black inkjet prints using Fourier transform near-infrared spectroscopy and Linear Discriminant Analysis

This work presents a study regarding the forensic discrimination of black inkjet-printed documents in question. Nondestructive Fourier transform near-infrared (FT-NIR) spectroscopy in combination with supervised classification method Discriminant Analysis (DA); Linear Discriminant Analysis (LDA) and Quadratic Discriminant Analysis (QDA) were utilized to investigate 22 different prints of the three most sold office printer brands. The spectra were acquired using the FT-NIR spectrometer NIRFlex N-500 (Büchi Labortechnik AG, Flawil, Switzerland) with the Fiber Optic Solids measuring cell in the spectral region of 10,000–4000 cm−1. Each sample was printed on the same type of office paper. The spectra were 45 times acquired on 3 separate printed squares of each sample. It results in 990 acquired spectra for the presented experiment. The FT-NIR spectra of the printed squares were split into calibration and test sets with which the Classification accuracy (CA) value of unknown samples was evaluated. In order to increase the significance, three different compilations of calibration and test sets were realized. The performance of three different Discriminant model methods; LDA (Euclidean and Mahalanobis algorithm) and QDA were compared to each other. Furthermore, the CA of each DA method was examined using 1–5 principal components (PCs) in the construction of the respective DA model. Two groups of models, according to the ink subset (Carbon black and Black colorant), were performed in raw and Standard Normal Variate (SNV) correction spectra alternations. The results showed that the Euclidean method yielded the highest accuracy in predicting independent test samples and thus clearly outperformed the QDA and Mahalanobis algorithm DA method. It was also determined that the ink type Carbon black had higher CA values than the ink type Black colorant. This work demonstrated the special ability of FT-NIR spectroscopy in combination with DA to examine inkjet-printed documents in a fast and non-destructive fashion.

The Capability of Raman Microspectroscopy to Differentiate Printing Inks.

This study applies Raman microspectroscopy to differentiate the chemical components in printing inks of different brands, colors, and type using the 532 nm and 785 nm excitation wavelengths. Spectra were collected from 319 inks (78 inkjet, 76 toner, 79 offset, and 86 intaglio) representing various colors. Comparisons were performed to calculate discrimination capability percentages for each ink type. Overall, Raman microspectroscopy differentiates according to the following hierarchy: intaglio (96%), inkjet (92%), offset (90%), and toner (61%). The ability of Raman microspectroscopy to differentiate between same-colored inks from different brands was dependent on the color and ink analyzed. Based on ink color, the discrimination capability ranged from 75 to 94% (inkjet), 0 to 86% (toner), and 0 to 77% (offset). Copper phthalocyanine was detected in cyan inks and various intaglio inks, while carbon black was identified in black inkjet, offset, and intaglio inks.

Study of surface-enhanced infrared absorption spectroscopy (SEIRAS) of black inkjet prints using silver colloid

Abstract Only black inkjet prints were studied with regard to forensic examination of documents. We analysed twenty-one inkjet prints using surface-enhanced infrared absorption spectroscopy (SEIRAS). The present paper deals with micro-destructive document analysis based on silver nanoparticles (AgNPs) use to obtain surface enhanced ATR-FTIR (attenuated total reflection - Fourier transform infrared) spectra directly from the document. For this experiment, AgNPs in colloid form was applied. AgNPs for SEIRAS analyses were synthesised and afterwards analysed by scanning electron microscopy (SEM). The purpose of the enhancement of colloids was to improve the resolution of the absorption signal of the analysed samples from noise. In the experiment, the obtained ink ATR-FTIR spectra, with and without silver treatment, were significantly affected by the paper base.

Study of Vis-NIR and NIR spectral data of black inkjet prints using principal component analysis for forensic discrimination

The aim of this work was to prepare spectral data for principal component analysis and to examine 19 samples of six different brands. Samples consisted of the same type of office paper with black areas printed in black ink only. The spectral data were acquired by fibre optics reflection spectroscopy in Vis-NIR and only NIR (Vis-NIR FORS) directly on paper. The black inkjet-printed samples were analysed with regard to the forensic analysis of documents. The method used is based on the combination of molecular spectroscopy in the visible (Vis) and near infrared region (NIR) combined with a chemometric method, – principal component analysis (PCA). The PCA method divides the inkjet inks sample into clusters. It was found out that by a combination of spectrum pre-processing methods and principal component analysis, it is possible to separate inks containing carbon black from the other inks using other organic colourants. This method appears to be a useful tool for forensic examination of printed documents containing inkjet inks. Spectra of inkjet inks were acquired without any destructive or invasive procedure, for example cutting sample or for extraction with the possibility to measure out of the laboratory.

Direct analyte-probed nanoextraction (DAPNe) coupled to matrix-assisted laser desorption ionization (MALDI) for examination of the ink chemistry on documents

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has been coupled to direct analyte-probed nanoextraction (DAPNe) through use of nanomanipulation for the analysis of ink chemistry on documents. DAPNe is first used to extract ink from the document and then deposits the sample on the MALDI plate. Through this method, cutting the document for MALDI-MS analysis is avoided. DAPNe extracts ink from documents with minimal to no visible destruction. Specific dyes and binding agents in the extracted ink are monitored with mass spectrometry. Different matrices, 1, 5-diaminonapthalene (DAN), 2, 5-dihydroxybenzoic acid (DHB), and silver nanoparticles, were tested to compare intensity enhancement of the mass spectra signals. The advantages of using MALDI-MS coupled to DAPNe are shown by characterizing Crystal Violet, Basic Yellow 2, Rhodamine B, and polyethylene glycol from red and blue pens, black pen, and a black inkjet printer cartridge.

Principal component analysis for the forensic discrimination of black inkjet inks based on the Vis–NIR fibre optics reflection spectra

Nineteen black inkjet inks of six different brands were examined by fibre optics reflection spectroscopy in Visible and Near Infrared Region (Vis–NIR FORS) directly on paper with a view to achieving good resolution between them. These different inks were tested on nineteen different inkjet printers from three brands. Samples were obtained from prints by reflection probe. Processed reflection spectra in the range 500–1000nm were used as samples in principal component analysis. Variability between spectra of the same ink obtained from different prints, as well as between spectra of square areas and lines was examined. For both spectra obtained from square areas and lines reference, Principal Component Analysis (PCA) models were created. According to these models, the inkjet inks were divided into clusters. PCA method is able to separate inks containing carbon black as main colorant from the other inks using other colorants. Some spectra were recorded from another piece of printer and used as validation samples. Spectra of validation samples were projected onto reference PCA models. According to position of validation samples in score plots it can be concluded that PCA based on Vis–NIR FORS can reliably differentiate inkjet inks which are included in the reference database. The presented method appears to be a suitable tool for forensic examination of questioned documents containing inkjet inks. Inkjet inks spectra were obtained without extraction or cutting sample with possibility to measure out of the laboratory

Forensic application of laser-induced breakdown spectroscopy for the discrimination of questioned documents

Document examination is an important forensic discipline and the legal system regularly needs the knowledge and skills of the scientific expert when questioned documents are involved in criminal or civil matters. Amongst the many aspects of the scientific examination of documents, elemental analysis can provide useful results. In this study, the evaluation of the analytical performance of a commercially available laser-induced breakdown spectroscopy (LIBS) instrument was conducted on office papers, writing inks, inkjet inks and laser printer toners. The paper sample set analysed consisted of 33 Australian paper specimens originating from the same production plant but representing different brands and/or batches. In addition, a total of 131 ink or toner samples were examined that included black and blue ballpoint inks, black inkjet inks, and black laser printer toners originating from several manufacturing sources, models and/or batches. Results from the LIBS method were compared against those obtained using more established elemental profiling method such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). LIBS demonstrated detectable and significant differences between different batches of the same brand as well as between different brands of paper, ink and toner samples. The LIBS method provided comparable discrimination powers for the selected sample sets when compared to those obtained using LA-ICP-MS (discrimination from 99.8 and 100% of the sample pairs, depending on the sample subset under examination). LIBS is a suitable technique for the determination of elemental composition as part of a protocol for the examination of questioned documents.

Application of CE-MS to examination of black inkjet printing inks for forensic purposes

The potential of capillary electrophoresis coupled to mass spectrometry with electrospray ion source and time of flight analyser (CE-ESI-TOF-MS) in the analysis of inkjet inks was investigated. The developed and validated method allowed reliable and repeatable analysis of black inkjet inks extracted from printouts. Over a dozen inkjet printouts printed on various printer models from different manufacturers were analysed under selected conditions to determine the variation of chemical composition of inks between different brands and types. It was ascertained that the developed method is capable of revealing qualitative differences between ink samples. For most of the investigated inks, the studies showed the presence of a characteristic mass spectrum originating from the surfactant or polymer. The mass distribution of the additive is distinctive for some inkjet ink producers, and allows for group identification of inks. The results showed the strength of the CE-ESI-TOF-MS method as an effective technique for forensic purposes, requiring a small amount of inkjet ink samples and giving analytical information that is useful in the identification of compounds.

Characterization of toners and inkjets by laser ablation spectrochemical methods and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy

Detection and sourcing of counterfeit currency, examination of counterfeit security documents and determination of authenticity of medical records are examples of common forensic document investigations. In these cases, the physical and chemical composition of the ink entries can provide important information for the assessment of the authenticity of the document or for making inferences about common source. Previous results reported by our group have demonstrated that elemental analysis, using either Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) or Laser Ablation Induced Breakdown Spectroscopy (LIBS), provides an effective, practical and robust technique for the discrimination of document substrates and writing inks with minimal damage to the document. In this study, laser-based methods and Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) methods were developed, optimized and validated for the forensic analysis of more complex inks such as toners and inkjets, to determine if their elemental composition can differentiate documents printed from different sources and to associate documents that originated from the same printing source. Comparison of the performance of each of these methods is presented, including the analytical figures of merit, discrimination capability and error rates. Different calibration strategies resulting in semi-quantitative and qualitative analysis, comparison methods (match criteria) and data analysis and interpretation tools were also developed. A total of 27 black laser toners originating from different manufacturing sources and/or batches were examined to evaluate the discrimination capability of each method. The results suggest that SEM-EDS offers relatively poor discrimination capability for this set (~70.7% discrimination of all the possible comparison pairs or a 29.3% type II error rate). Nonetheless, SEM-EDS can still be used as a complementary method of analysis since it has the advantage of being non-destructive to the sample in addition to providing imaging capabilities to further characterize toner samples by their particle morphology. Laser sampling methods resulted in an improvement of the discrimination between different sources with LIBS producing 89% discrimination and LA-ICP-MS resulting in 100% discrimination. In addition, a set of 21 black inkjet samples was examined by each method. The results show that SEM-EDS is not appropriate for inkjet examinations since their elemental composition is typically below the detection capabilities with only sulfur detected in this set, providing only 47.4% discrimination between possible comparison pairs. Laser sampling methods were shown to provide discrimination greater than 94% for this same inkjet set with false exclusion and false inclusion rates lower than 4.1% and 5.7%, for LA-ICP-MS and LIBS respectively. Overall these results confirmed the utility of the examination of printed documents by laser-based micro-spectrochemical methods. SEM-EDS analysis of toners produced a limited utility for discrimination within sources but was not an effective tool for inkjet ink discrimination. Both LA-ICP-MS and LIBS can be used in forensic laboratories to chemically characterize inks on documents and to complement the information obtained by conventional methods and enhance their evidential value.

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.

Surface-enhanced resonance Raman scattering of black inkjet dyes in solution and in situ printed onto paper.

Understanding the changes that occur when dyes are absorbed onto paper is crucial for the design of new inkjet dyes. This problem is particularly difficult for black dyes that have complex chromophores, and as a result, spectroscopic information on electronic and structural changes can be of importance. Surface-enhanced resonance Raman scattering (SERRS) and electronic structure calculations were used to probe in situ changes in the chromophore in black di-azo dyes printed onto paper. The data indicate that the low-energy chromophore is due mainly to the hydrazone group and the high-energy chromophore to both the azo and hydrazone groups. A comparison of SERRS from the dyes adsorbed onto silver particles in suspension and from the dyes on paper demonstrated a broadening of the chromophore into the red for both dyes and evidence of a structural change in one dye.

Carbon Black Dispersions For High Optical Density on Plain Paper

As a result of the inherent advantage of pigment based inks over dye based inks, carbon black is now the colorant of choice for black inks in the SOHO market. There is a need for black ink jet inks which give high optical density and excellent print quality on plain paper of varying quality. In this work, a series of self dispersed carbon black dispersions were made using commercially available carbon blacks spanning a broad range of particle morphology. Inks made with these dispersions were printed on a series of 7 plain paper types of varying quality and optical densities were determined. A strong correlation was observed between carbon black particle morphology and optical density.