【摘要】：文件形成時間的鑒定一直是國內外法庭科學研究領域的熱點問題,其中書寫字跡形成時間鑒定的研究最早可以追溯到1904年對鋼筆墨水字跡的研究。1937年圓珠筆問世以后,法庭科學家們就開展了大量關于油墨種類及形成時間的研究工作。通過球珠的滾動帶出書寫介質的書寫工具,統稱為滾珠筆。按照書寫介質的粘度由大到小,可分為圓珠筆、中性筆和水性筆,其中后兩種又稱為簽字筆,是目前國際上流行的一種新型書寫工具。近一個世紀以來,國內外的科學家一直在堅持不懈的探索,利用各種分析技術和方法,對圓珠筆油墨進行了大量的研究,由于干擾因素較多,字跡形成時間的鑒定一直是困擾國內外法庭科學工作者的一大難題。在各類經濟案件中,作案人或當事人常常于事后,通過偽造或篡改文件時間來達到犯罪目的,如何對書寫字跡的形成時間進行準確鑒定,就成為判定這類案件的關鍵依據。 本文主要通過現代儀器分析方法對圓珠筆油墨和簽字筆墨水字跡中的溶劑和色料成分進行了分析,并研究了它們隨字跡書寫時間的變化規(guī)律以及加熱、光照等因素對字跡老化規(guī)律的影響。 建立了氣相色譜法鑒別圓珠筆和簽字筆字跡油墨(水)分析方法,對圓珠筆字跡油墨中苯甲醇(苯氧基乙醇)溶劑與三芳甲烷染料的相對含量隨字跡自然老化的變化規(guī)律進行了研究。圓珠筆字跡在紙張上形成之后,油墨中溶劑含量在20天內的遞減最快,隨著油墨樹脂的固化成膜,油墨內的溶劑含量變化逐漸變緩,100天以后老化曲線的斜率趨近于零,字跡油墨中的溶劑成分很難再揮發(fā)出來。通過氣相色譜和質譜聯用技術確定了簽字筆墨水中的溶劑成分主要乙二醇、二甘醇和甘油等多元醇,研究了利用二次溶劑提取字跡墨水,通過氣相色譜分析所得的提取率對書寫時間作圖,繪制簽字筆字跡的老化曲線,同時對不同簽字筆墨水中相同的溶劑成分的老化規(guī)律進行了統計研究。通過分析加熱前后,圓珠筆字跡油墨中溶劑相對含量和簽字筆字跡墨水中溶劑成分提取率的變化閾值,來推斷無比對樣本字跡的形成時間。 研究了高效液相色譜法鑒別圓珠筆字跡油墨的分析方法,確定了藍色圓珠筆油墨中的染料主要包括結晶紫5BN、堿性艷藍B及它們的同系物,并根據所含染料種類和相對含量對藍色圓珠筆進行分類。圓珠筆油墨中的染料成分變化相對緩慢,書寫時間在6個月至1年的字跡油墨中的染料會發(fā)生脫甲基反應,染料同系物相對含量發(fā)生變化。通過優(yōu)化電泳條件,建立了區(qū)帶毛細管電泳法分析黑色水性筆字跡墨水的方法,對不同種類黑色水性筆字跡墨水提取液進行了分類研究。利用毛細管電泳二極管陣列檢測器檢測可見波長下黑色水性墨水中不同染料相對含量的變化關系,研究了字跡染料成分的老化,得出較好的變化規(guī)律,可以分析至少600天以內的黑色水性筆墨水字跡的相對形成時間。光照可以加速圓珠筆油墨和水性筆墨水中染料的分解。 中性筆是當前比較流行的一種書寫工具,其墨水多采用顏料作為色料成分,很難用水和有機溶劑進行提取,故無法利用分析圓珠筆油墨和水性筆墨水所采用的氣相色譜或高效液相色譜等方法進行檢驗。目前在法庭科學領域內還沒有一種有效的方法用于分析中性筆字跡的書寫墨水。采用裂解氣相色譜法分析了藍色中性筆字跡的書寫墨水,根據色譜峰的個數和保留時間將收集的65種樣品分成3大類,其中大部分樣品屬于具有銅酞菁顏料主要色譜峰的第二大類。色譜峰的保留時間和峰面積比值的分析結果表明所建立的分析方法重現性好且穩(wěn)定。在此基礎上,對藍色中性筆墨跡隨書寫時間的變化規(guī)律進行了初步研究,得出了老化曲線。
[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.
【學位授予單位】：東北師范大學
【學位級別】：博士
【學位授予年份】：2009
【分類號】：D918.2

【引證文獻】

相關碩士學位論文 前1條

1 章晴;水性印油印跡的主要成分分析與穩(wěn)定性研究[D];北京化工大學;2011年

，

本文編號：2167997