激光显微共聚焦拉曼光谱仪对红色墨迹的研究

目的利用激光显微共聚焦拉曼光谱仪对文书中常见的红色墨迹材料进行表征,研究该方法对红色墨迹材料的区分能力。方法在785nm激发波长,50倍物镜条件下,对49种红色印文,以及9种彩色喷墨打印和13种彩色激光打印的红色墨迹材料进行拉曼光谱表征。结果通过对71种墨迹样品的谱图进行分析,可以发现,红色印文墨迹、喷墨打印红色墨迹及激光打印红色墨迹的拉曼光谱间均存在差异,同时,拉曼光谱可将这三种墨迹材料分别进一步区分。结论显微共聚焦激光拉曼光谱可对红色墨迹材料进行有效表征和区分。这一方法可对红色印文墨迹进行识别,并且可实现对伪造印文文件的鉴别。     

黑色墨迹的拉曼光谱分析

目的对常见的黑色墨迹进行初步筛选,为墨迹的进一步检验提供依据。方法依据黑色墨迹的同色异谱特征,利用显微共焦激光拉曼光谱仪对19种黑色墨迹进行分析检验。结果根据不同墨迹的拉曼谱图,19种黑色墨迹可以分为3大类,即:未检出拉曼峰的墨迹,只检出碳物质的墨迹,以及主体色料为染料的墨迹。结论拉曼光谱可用于区分不同种类黑色墨迹,从而为选择合适的方法对黑色墨迹进一步进行检验奠定基础。     

线聚焦显微激光拉曼光谱技术区分激光打印墨粉

目的利用Renishaw InVia激光显微拉曼光谱仪对打印墨粉进行区分。方法用785nm激发波长,采取线聚焦模式,50倍物镜条件下,测定了惠普等8个品牌25种硒鼓型号的30份激光打印机打印墨迹样品的拉曼光谱。结果 30种样品墨迹的谱图进行了分析,根据拉曼的异同,可将30种样品分为5大类。结论线聚焦显微激光拉曼光谱可用于区分不同种类激光打印墨粉。     

显微激光拉曼光谱技术区分喷墨打印墨迹研究

目的运用激光显微共聚焦拉曼光谱仪对打印墨水的墨迹样品进行检验。方法采用514nm激发波长,测得EPSON、HP、CANON等3个品牌21种型号墨迹样品的拉曼光谱。结果根据拉曼峰位的异同,可将21种型号墨迹样品分为8大类。结论该方法可以快速区分常见不同种类打印墨水墨迹,为印刷文件的检验鉴定提供方法参考。     

利用彩色文件上的图文特征鉴别喷墨打印机品牌

目的通过彩色文件上的图文特征鉴别喷墨打印机的品牌。方法在体视显微镜下观察采用不同喷墨机理的惠普、佳能和爱普生三大品牌喷墨打印机打印的彩色图文。结果通过对彩色图文上六种墨迹形态特征的比较,发现三大品牌喷墨打印机打印的彩色图文存在明显差异。结论依据这六种特征对三大品牌的喷墨打印机进行鉴别。     

显微共焦拉曼光谱法在添改文件检验中的应用

随着经济犯罪和民事纠纷案件的日益增多,针对合同、票据、文件中的某些文字是否添改形成的检验给司法工作者造成一定的麻烦,因此如何快速、准确、无损进行检验显得尤为关键。文献报道过用色谱法对签字笔墨迹进行鉴别,但都破坏了样品,无法满足物证的无损检验要求。显微共焦拉曼光谱法分析速度快,对样品无需处理就可直接进行无损检测,     

喷墨打印文书的检验方法

随着计算机技术的进一步发展，办公自动化日益普及，打印机打印输出的经济合同、文本协议等文书在人们的社会生活中被广泛使用。在涉及经济领域的刑事犯罪中此类文书作为证据已愈现突出，需要司法部门检验鉴定文书来源、打印方式及其真伪性的工作量也不断增多。本文着重探讨喷墨打印文书的检验鉴定技术。喷墨打印技术是在９０年代中期迅猛发展起来的，市场占有率高，是目前企业和家庭办公自动化的主流机种。喷墨打印机是非击打式打印机。它通过向打印纸的相应位置喷射墨点实现图像和文字的输出。喷墨打印机分为固态喷墨和液态喷墨两种打印方…     

基于过程解析法的同机添加打印文件鉴别方法

利用喷墨打印机二次添加打印,特别是同机添加打印变造文件,是文件检验工作中的难题。喷墨打印机采用串行接字方式,内部结构复杂,喷嘴数目多,同一型号打印机又有多种质量模式。因此,在打印图文上往往留有较多的打印特征,如对接重叠线、对接错位线、横向白线、卫星墨点、墨点错位等。分析爱普生、惠普、佳能三个品牌的20台喷墨打印机不同质量模式的打印文件,发现这些特征重复再现频率较高,不同台打印机打印文件特征差异较大,同一台打印机在不同质量模式下特征出现的位置也不尽相同。通过提取打印文件上的打印特征,分析字车运行方向和打印图文pass数值,分解打印过程并制作检验图谱,判断打印文件的可疑区域是否符合打印规律,为确定二次添加打印提供帮助,提升检验过程的规范性、检验意见的准确性和结果依据的可读性。     

基于银胶表面增强拉曼光谱检验蓝色书写字迹初探

目的用基于银胶的表面增强拉曼光谱技术检验蓝色签字笔字迹。方法取4种常见不同牌号的蓝色签字笔在其字迹上滴加微量银胶,用显微共焦拉曼光谱仪进行检验。结果不同品牌的蓝色签字笔字迹的表面增强拉曼光谱不同。结论基于银胶的表面增强拉曼光谱技术可用于纸张上蓝色签字笔字迹的检验。     

显微共焦激光拉曼光谱仪分析激光打印黑色墨粉字迹

激光打印机是常用办公设备,案件中经常会涉及到激光打印文件的检验,运用显微共焦激光拉曼光谱仪检验激光打印黑色墨粉字迹是一种快速、无损、灵敏度高的检验方法,可以对墨粉成分进行定性分析,在司法实践中,此种方法对激光打印黑色墨粉具有较好的检验效果,应用前景广阔。     

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.     

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.     

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 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.     

Evaluation of the Forensic Utility of Scanning Electron Microscopy‐Energy Dispersive Spectroscopy and Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry for Printing Ink Examinations

Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis and comparisons. In this study, 319 printing inks (toner, inkjet, offset, and Intaglio) were analyzed directly on the paper substrate using scanning electron microscopy‐energy dispersive spectroscopy (SEM‐EDS) and Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS). As anticipated, the high sensitivity of LA‐ICP‐MS pairwise comparisons resulted in excellent discrimination (average of ~ 99.6%) between different ink samples from each of the four ink types and almost 100% correct associations between ink samples known to originate from the same source. SEM‐EDS analysis also resulted in very good discrimination for different toner and intaglio inks (>97%) and 100% correct association for samples from the same source. SEM‐EDS provided complementary information to LA‐ICP‐MS for certain ink types but showed limited utility for the discrimination of inkjet and offset inks.     

Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks

Stamp pad inks from different manufacturers across India have been analyzed to investigate the feasibility of Raman scattering as a tool for forensic analysis of questioned documents involving stamp inks. Nine different stamping inks were analyzed by both Raman spectroscopic and HPTLC methods. The results demonstrate the effectiveness of these methods in classifying the investigated stamping inks based on their spectral pattern and HPTLC chromatogram. Raman scattering tool was able to determine the sequence of heterogeneous intersection strokes involving a blue stamp pad ink and other writing instruments, such as ballpoint pen ink (red and black), pencil and laser printer toner. However, this method was unable to resolve the exact sequencing for the intersection strokes involving investigated stamp ink and blue ballpoint ink or gel pen ink (all colors).     

Experimental Research on Class Identification with a New Type of Erasable Gel Pens

A new type of erasable gel pen ink is becoming increasingly popular because of the modifiable characteristics for writing on documents. This study attempts to distinguish 12 types of blue and black erasable gel pens produced by mainstream stationery manufacturers using infrared (IR) visual analysis, Fourier transform infrared (FTIR) analysis, fluorescence analysis, and microspectrophotometry. The results demonstrate that IR visual, FTIR, and fluorescence analysis can be used to help distinguish each type of erasable gel ink. While microspectrophotometry can be used to effectively differentiate the blue gel inks in this study, there are limitations with respect to distinguishing black erasable gel pens. When these four optical analyses methods were used in combination, the gel inks could be accurately distinguished.     

A Novel Forensic Tool for the Characterization and Comparison of Printing Ink Evidence: Development and Evaluation of a Searchable Database Using Data Fusion of Spectrochemical Methods

A searchable printing ink database was designed and validated as a tool to improve the chemical information gathered from the analysis of ink evidence. The database contains 319 samples from printing sources that represent some of the global diversity in toner, inkjet, offset, and intaglio inks. Five analytical methods were used to generate data to populate the searchable database including FTIR, SEM‐EDS, LA‐ICP‐MS, DART‐MS, and Py‐GC‐MS. The search algorithm based on partial least‐squares discriminant analysis generates a similarity “score” used for the association between similar samples. The performance of a particular analytical method to associate similar inks was found to be dependent on the ink type with LA‐ICP‐MS performing best, followed by SEM‐EDS and DART‐MS methods, while FTIR and Py‐GC‐MS were less useful in association but were still useful for classification purposes. Data fusion of data collected from two complementary methods (i.e., LA‐ICP‐MS and DART‐MS) improves the classification and association of similar inks.     

Preliminary Study on Determining the Sequence of Intersecting Lines by Fluorescence Technique

The determination of the sequence of intersecting lines is an important part of questioned document examinations. A fluorescence technique was used to determine the sequence of heterogeneous intersecting lines produced using inkpad ink, stamp‐pad ink, ballpoint pens, gel pens, fountain pens, colorants of carbon paper, photocopiers, laser printers, and inkjet printers. A SteREO Discovery.V20 equipped with the ZEN Blue Lite software was chosen to perform the tests.As the results obtained from the study were positive under most conditions, the fluorescence technique was found to be very successful in determining the sequence of intersecting lines from ballpoint pen, gel pen, fountain pen, photocopier, laser and inkjet printers, and inkpad inks. The method was also successful in determining the sequence of intersecting lines from ballpoint pen, photocopier, laser printer, and stamp‐pad inks under most conditions. The technique was not successful in determining the order of crossing lines blending together.     

How Much Can a Forensic Laboratory Do to Discriminate Questioned Ink Entries?

Questioned document examiners are frequently required to determine whether the questioned ink entries on a document are written with the same ink, either for forged document identification or relative ink dating. How many methods are sufficient to discriminate potentially different inks? In this paper, 18 blue ballpoint inks were first nondestructively examined with a video spectral comparator. The ink entries were subsequently extracted with organic solvents for analysis of the volatile solvents and dyes by GC/MS, TLC, and LC‐MS/MS. The 18 ink samples were divided into 10, 9, 12, and 14 categories by these four methods, respectively. With the combined results, there were only two inks that remained indistinguishable, but they were further differentiated by microscopy. Therefore, to achieve effective discrimination of ballpoint ink entries, the authors suggest that a complete examination should include an analysis of their optical features, volatile solvents, and dyes as well as the ink quality.