应用现代仪器分析技术鉴定字迹形成时间的研究
发布时间：2018-08-06 14:17
【摘要】：文件形成时间的鉴定一直是国内外法庭科学研究领域的热点问题,其中书写字迹形成时间鉴定的研究最早可以追溯到1904年对钢笔墨水字迹的研究。1937年圆珠笔问世以后,法庭科学家们就开展了大量关于油墨种类及形成时间的研究工作。通过球珠的滚动带出书写介质的书写工具,统称为滚珠笔。按照书写介质的粘度由大到小,可分为圆珠笔、中性笔和水性笔,其中后两种又称为签字笔,是目前国际上流行的一种新型书写工具。近一个世纪以来,国内外的科学家一直在坚持不懈的探索,利用各种分析技术和方法,对圆珠笔油墨进行了大量的研究,由于干扰因素较多,字迹形成时间的鉴定一直是困扰国内外法庭科学工作者的一大难题。在各类经济案件中,作案人或当事人常常于事后,通过伪造或篡改文件时间来达到犯罪目的,如何对书写字迹的形成时间进行准确鉴定,就成为判定这类案件的关键依据。 本文主要通过现代仪器分析方法对圆珠笔油墨和签字笔墨水字迹中的溶剂和色料成分进行了分析,并研究了它们随字迹书写时间的变化规律以及加热、光照等因素对字迹老化规律的影响。 建立了气相色谱法鉴别圆珠笔和签字笔字迹油墨(水)分析方法,对圆珠笔字迹油墨中苯甲醇(苯氧基乙醇)溶剂与三芳甲烷染料的相对含量随字迹自然老化的变化规律进行了研究。圆珠笔字迹在纸张上形成之后,油墨中溶剂含量在20天内的递减最快,随着油墨树脂的固化成膜,油墨内的溶剂含量变化逐渐变缓,100天以后老化曲线的斜率趋近于零,字迹油墨中的溶剂成分很难再挥发出来。通过气相色谱和质谱联用技术确定了签字笔墨水中的溶剂成分主要乙二醇、二甘醇和甘油等多元醇,研究了利用二次溶剂提取字迹墨水,通过气相色谱分析所得的提取率对书写时间作图,绘制签字笔字迹的老化曲线,同时对不同签字笔墨水中相同的溶剂成分的老化规律进行了统计研究。通过分析加热前后,圆珠笔字迹油墨中溶剂相对含量和签字笔字迹墨水中溶剂成分提取率的变化阈值,来推断无比对样本字迹的形成时间。 研究了高效液相色谱法鉴别圆珠笔字迹油墨的分析方法,确定了蓝色圆珠笔油墨中的染料主要包括结晶紫5BN、碱性艳蓝B及它们的同系物,并根据所含染料种类和相对含量对蓝色圆珠笔进行分类。圆珠笔油墨中的染料成分变化相对缓慢,书写时间在6个月至1年的字迹油墨中的染料会发生脱甲基反应,染料同系物相对含量发生变化。通过优化电泳条件,建立了区带毛细管电泳法分析黑色水性笔字迹墨水的方法,对不同种类黑色水性笔字迹墨水提取液进行了分类研究。利用毛细管电泳二极管阵列检测器检测可见波长下黑色水性墨水中不同染料相对含量的变化关系,研究了字迹染料成分的老化,得出较好的变化规律,可以分析至少600天以内的黑色水性笔墨水字迹的相对形成时间。光照可以加速圆珠笔油墨和水性笔墨水中染料的分解。 中性笔是当前比较流行的一种书写工具,其墨水多采用颜料作为色料成分,很难用水和有机溶剂进行提取,故无法利用分析圆珠笔油墨和水性笔墨水所采用的气相色谱或高效液相色谱等方法进行检验。目前在法庭科学领域内还没有一种有效的方法用于分析中性笔字迹的书写墨水。采用裂解气相色谱法分析了蓝色中性笔字迹的书写墨水,根据色谱峰的个数和保留时间将收集的65种样品分成3大类,其中大部分样品属于具有铜酞菁颜料主要色谱峰的第二大类。色谱峰的保留时间和峰面积比值的分析结果表明所建立的分析方法重现性好且稳定。在此基础上,对蓝色中性笔墨迹随书写时间的变化规律进行了初步研究,得出了老化曲线。
[Abstract]:The identification of the time of the formation of documents has always been a hot issue in the field of forensic research at home and abroad. The research on the time identification of writing handwriting can be traced back to the study of pen ink handwriting in 1904. After the advent of the.1937 ballpoint pen, the tribunal scientists have carried out a large amount of research on the type of ink and the time of formation of the ink. As a writing tool, it is called ball pen. According to the viscosity of the writing medium, it can be divided into ballpoint pen, neutral pen and water pen. The latter two are also called the signature pen. It is a new writing tool in the world. A great deal of research on the ink of the ball point pen is carried out with various analytical techniques and methods. The identification of the time of the formation of the handwriting has been a difficult problem for the scientists at home and abroad. In all kinds of economic cases, the perpetrators or the parties are often forged or tampered with the post, by forgery or tampering. How to accurately identify the formation time of handwriting becomes the key basis for judging such cases.
In this paper, a modern instrument analysis method is used to analyze the solvent and color composition of the ink and ink handwriting of the ballpoint pen and the signature pen, and the influence of the changing rule of the writing time on the handwriting and the effect of heating and illumination on the rule of the handwriting aging is studied.
An analysis method for identifying the ballpoint pen and the signature ink (water) by gas chromatography is established. The relative content of benzyl alcohol (benzyl alcohol) and three aromatic methane dyes in the ink of the ball pen handwriting ink changes with the natural aging of the handwriting. After the handwriting of the ballpoint pen is formed on paper, the content of the solvent in the ink is 20 days. With the solidification of the ink resin, the change of the solvent content in the ink gradually slowed, and the slope of the aging curve approached to zero after 100 days, and the solvent components in the handwriting ink were difficult to evaporate. The main solvent components in the ink were determined by gas chromatograph and mass spectrometry, and the main ethylene glycol was two Gan. Polyols, such as alcohol and glycerol, have been studied by using two solvents to extract handwriting ink, drawing the writing time by gas chromatography, drawing the aging curve of the signature pen handwriting, and studying the aging law of the same solvent components in the ink of different signature pens. The threshold value of the relative solvent content in the ink and the solvent extraction rate in the ink of the signature pen can be used to infer the formation time of the sample handwriting.
The analysis method of high performance liquid chromatography (HPLC) to identify the ink of ballpoint pen handwriting is studied. The dyes in the blue ball pen ink are mainly composed of crystal violet 5BN, alkaline blue B and their homologues, and the blue ball pen is classified according to the type and relative content of the dyes. The change of the dye composition in the ball pen ink is relatively slow The dye in the handwriting ink with writing time from 6 months to 1 years will be demethylated and the relative content of the dye homologue changes. By optimizing the electrophoresis conditions, a method for the analysis of black water pen handwriting ink with capillary electrophoresis is established, and the extraction liquid of different kinds of black water pen handwriting ink is studied. The relationship between the relative contents of different dyes in black water-based ink at visible wavelength was detected by capillary electrophoresis diode array detector. The aging of the components of the handwriting dye was studied, and the good change law was obtained. The relative time of formation of the ink handwriting of the black waterborne pen within 600 days could be analyzed. The light can accelerate the ball pen. The decomposition of dyes in ink and water pen ink.
The neutral pen is one of the most popular writing tools at present. It is difficult to use the methods of gas chromatography or high performance liquid chromatography, such as gas chromatography or high performance liquid chromatography, to be used for the analysis of ballpoint ink and water pen ink. The effective method is used to analyze the writing ink of neutral handwriting. The blue neutral pen writing ink is analyzed by pyrolysis gas chromatography. According to the number of peaks and the retention time, the 65 samples are divided into 3 categories, and most of them belong to second major categories of the main chromatographic peaks of copper phthalocyanine. The analysis results of the retention time and peak area ratio show that the proposed method is reproducible and stable. On this basis, a preliminary study on the change law of the blue neutral ink mark with the writing time is carried out, and the aging curve is obtained.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2009
【分类号】：D918.2
本文编号：2167997
[Abstract]:The identification of the time of the formation of documents has always been a hot issue in the field of forensic research at home and abroad. The research on the time identification of writing handwriting can be traced back to the study of pen ink handwriting in 1904. After the advent of the.1937 ballpoint pen, the tribunal scientists have carried out a large amount of research on the type of ink and the time of formation of the ink. As a writing tool, it is called ball pen. According to the viscosity of the writing medium, it can be divided into ballpoint pen, neutral pen and water pen. The latter two are also called the signature pen. It is a new writing tool in the world. A great deal of research on the ink of the ball point pen is carried out with various analytical techniques and methods. The identification of the time of the formation of the handwriting has been a difficult problem for the scientists at home and abroad. In all kinds of economic cases, the perpetrators or the parties are often forged or tampered with the post, by forgery or tampering. How to accurately identify the formation time of handwriting becomes the key basis for judging such cases.
In this paper, a modern instrument analysis method is used to analyze the solvent and color composition of the ink and ink handwriting of the ballpoint pen and the signature pen, and the influence of the changing rule of the writing time on the handwriting and the effect of heating and illumination on the rule of the handwriting aging is studied.
An analysis method for identifying the ballpoint pen and the signature ink (water) by gas chromatography is established. The relative content of benzyl alcohol (benzyl alcohol) and three aromatic methane dyes in the ink of the ball pen handwriting ink changes with the natural aging of the handwriting. After the handwriting of the ballpoint pen is formed on paper, the content of the solvent in the ink is 20 days. With the solidification of the ink resin, the change of the solvent content in the ink gradually slowed, and the slope of the aging curve approached to zero after 100 days, and the solvent components in the handwriting ink were difficult to evaporate. The main solvent components in the ink were determined by gas chromatograph and mass spectrometry, and the main ethylene glycol was two Gan. Polyols, such as alcohol and glycerol, have been studied by using two solvents to extract handwriting ink, drawing the writing time by gas chromatography, drawing the aging curve of the signature pen handwriting, and studying the aging law of the same solvent components in the ink of different signature pens. The threshold value of the relative solvent content in the ink and the solvent extraction rate in the ink of the signature pen can be used to infer the formation time of the sample handwriting.
The analysis method of high performance liquid chromatography (HPLC) to identify the ink of ballpoint pen handwriting is studied. The dyes in the blue ball pen ink are mainly composed of crystal violet 5BN, alkaline blue B and their homologues, and the blue ball pen is classified according to the type and relative content of the dyes. The change of the dye composition in the ball pen ink is relatively slow The dye in the handwriting ink with writing time from 6 months to 1 years will be demethylated and the relative content of the dye homologue changes. By optimizing the electrophoresis conditions, a method for the analysis of black water pen handwriting ink with capillary electrophoresis is established, and the extraction liquid of different kinds of black water pen handwriting ink is studied. The relationship between the relative contents of different dyes in black water-based ink at visible wavelength was detected by capillary electrophoresis diode array detector. The aging of the components of the handwriting dye was studied, and the good change law was obtained. The relative time of formation of the ink handwriting of the black waterborne pen within 600 days could be analyzed. The light can accelerate the ball pen. The decomposition of dyes in ink and water pen ink.
The neutral pen is one of the most popular writing tools at present. It is difficult to use the methods of gas chromatography or high performance liquid chromatography, such as gas chromatography or high performance liquid chromatography, to be used for the analysis of ballpoint ink and water pen ink. The effective method is used to analyze the writing ink of neutral handwriting. The blue neutral pen writing ink is analyzed by pyrolysis gas chromatography. According to the number of peaks and the retention time, the 65 samples are divided into 3 categories, and most of them belong to second major categories of the main chromatographic peaks of copper phthalocyanine. The analysis results of the retention time and peak area ratio show that the proposed method is reproducible and stable. On this basis, a preliminary study on the change law of the blue neutral ink mark with the writing time is carried out, and the aging curve is obtained.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2009
【分类号】：D918.2
【引证文献】
相关硕士学位论文 前1条
1 章晴;水性印油印迹的主要成分分析与稳定性研究[D];北京化工大学;2011年
，本文编号：2167997
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