双溶剂提取法的优化

目的建立一种稳定的双溶剂提取圆珠笔油墨的实验体系,达到相对准确判断圆珠笔字迹书写时间的目的。方法依次用弱溶剂(氯苯)、强溶剂(N-N二甲基甲酰胺)溶解提取纸张上的圆珠笔油墨,点样在硅胶板上,薄层扫描得到吸收峰高值,而后根据吸收峰高值测算其相对提取率和标准偏差。结果找到了弱溶剂量10μl、取样量10~15片、弱溶剂溶解时间60s以及强溶剂量10μl的最佳实验条件。结论优化了双溶剂提取法,提高了该方法在检验鉴定中的准确度和可靠性。     

溶剂蒸溶法对书写时间判定的初步尝试

本文针对圆珠笔字迹相对书写时间的鉴定,参照溶剂提取法,提出一种新的实验技术——溶剂蒸溶法.该方法以检样纸张作为展开板,以乙醇蒸气作为展开剂,通过测定圆珠笔油墨在纸张上的扩散程度来判定圆珠笔字迹的相对书写时间.     

定量转印技术确定圆珠笔字迹的相对书写时间

定量转印技术是将单溶剂提取法与转印技术相结合形成的方法,实验表明该方法在一定条件下可以判定圆珠笔字迹的相对书写时间.     

油性圆珠笔字迹书写时间鉴定的研究综述

本文追述了油性圆珠笔问世以来,字迹书写时间的检验发展过程;总结了静态法,如标准样品比对法和基准物标记法,动态法,如如溶剂萃取法、色谱法、质谱法和光谱法用于鉴定圆珠笔字迹书写时间的研究成果;展望了非破坏性方法在鉴定书写时间上的发展趋势。     

圆珠笔油墨字迹书写时间鉴别的研究

圆珠笔油墨字迹书写时间的鉴别是摆在文件鉴定人员面前的棘手问题.本文作者借鉴国外的检验方法,经过近十年的探索,考查了各种因素的影响,研究出了适合我国国情的通过圆珠笔字迹油墨被溶解能力测试来确定其书写时间的鉴定技术,并且进一步发展了国外的检验方法,研制出了专用的检验器材,发明了模拟低温操作程序,使这一技术的适用范围更广.在有合适比对样本的情况下,可以准确鉴别落款时间在一年以上、怀疑书写时间在半年以内的可疑文件的真伪.     

GC-HPLC法考察圆珠笔字迹油墨厚度对溶剂挥发速率的影响

目的考察圆珠笔字迹油墨厚度对溶剂挥发速率的影响。方法采用GC/HPLC联用技术对不同时间、不同字迹油墨厚度在同种纸张上的圆珠笔油墨字迹中的溶剂、染料成分的定量分析。结果字迹油墨较厚的苯甲醇、苯氧基乙醇的含量随时间的变化比字迹油墨较薄的慢。结论字迹油墨的厚度对溶剂的挥发速率影响较大。     

国产圆珠笔油墨字迹书写时间的鉴别

对国产圆珠笔油墨字迹书写时间的鉴别进行了实验研究,达到了检测速度快,实用性强,费用低的效果.     

多次测定法确定蓝色圆珠笔字迹形成时间

通过研究相隔一定时间的多次测定数据的变化规律与书写时间的内在关系，建立了部分近期书写的圆珠笔字迹形成时间的检验方法，确定了相隔一定时间的两次测定数据的变化规律与书写时间内在关系的判定阀值。形成了无需对照样本即可判定部分圆珠笔字迹是否近期书写的检验方法。     

双溶剂提取法判定印泥印文形成时间的初探

目的通过双溶剂提取法判定印泥印文的形成时间,为判定文件的真伪提供重要依据。方法选用6种不同品牌的印泥和4种纸张分别制作印泥印文的历时性样本,通过实验确定适用于双溶剂提取法判定印泥印文形成时间的弱提取剂和强提取剂;确定薄层扫描时狭缝的大小和扫描波长;绘制盖印时间与提取率的关系曲线。结果弱提取剂为50％的甲酸溶液,强提取剂为N,N-二甲基甲酰胺,狭缝大小为12．00mm×0．60mm,扫描波长为485nm,得到了盖印印文形成后半年内印泥提取率随印文形成时间变化的关系曲线。结论双溶剂提取法是判定印泥印文形成时间的一种有效方法。     

蓝色圆珠笔字迹色痕FT-IR光谱经时变化的研究

笔者曾用FT-IR光谱法对108种不同蓝色圆珠笔油墨进行了系统分析,确定了油墨组成成份,实现了种类认定.在此基础上,选取了二种不同种类的蓝色圆珠笔油墨字迹色痕,在紫外光下定时照射,根据各自光谱特征峰校正峰高的计算,确定相关峰的相对峰高比.根据相对峰高比值随时间变化的规律,进行了曲线拟合和计算机编程.同时,探讨了油墨组份之间随光照时间的变化,其目的是为了推断字迹色痕的“年龄”.     

书写材料的无损检验系统研究

本研究运用显微分光光度仪、文件检验仪和傅立叶变换拉曼光谱仪三种方法,分别对在中国市场上收集的不同厂家、牌号、型号的35种黑墨水、20种蓝黑墨水、22种蓝墨水、49种黑色墨水笔、30种蓝色墨水笔、45种黑色圆珠笔、和50种蓝色圆珠笔等七组样品进行非破坏检验。结果表明:(1三种非破坏检验方法都能单独对七组样品进行不同程度的鉴别,区分率在50%—94.4%之间;(2)三种方法联用后对黑墨水、蓝黑墨水、蓝墨水、黑色墨水笔、蓝色墨水笔、黑色圆珠笔和蓝色圆珠笔的区分率可分别提高到93.4%、97.3%、99.1%97.2%、97.2%、95.6%和91.8%。通过三种非破坏检验方法的联用,证明它们之间有较强的互补性,最大限度地提高了检验效应,可建立系统的非破坏检验方法。     

书写时间确定技术的国内现状与发展

综述了书写时间确定技术在国内的现状及最新发展,主要从三方面进行了介绍:水溶性书写时间确定技术;圆珠笔油墨书写时间确定技术;间接确定文件的书写时间方法。     

Identification and dating of the fountain pen ink entries on documents by ion-pairing high-performance liquid chromatography

A novel approach for the identification and dating of the fountain pen ink entries on paper has been established by ion-pairing high-performance liquid chromatography (IP-HPLC). Twelve black and six red fountain inks have been collected, and their ink entries have been prepared by drawing lines on paper. The chromatographic conditions for separation of their dye components after extraction with solvents were optimized. Under the optimized conditions, the 18 fountain pen inks were differentiated individually by comparing the number of detectable main or minor dye components, and the relative peak intensities of each component. The ink entries were artificially and naturally aged, and the analysis results showed that the ink dye components were significantly decomposed when exposed to UV or fluorescent light compare to those of inks stored under natural condition. The changes of the relative peak height for the dye components were linearly related to the aging time, especially under natural aging conditions. The degradation characteristics of the dye components under different aging conditions provide scientific evidences for dating of the suspicious fountain pen ink entries on document.     

墨水书写时间测定的进展

本文追述了从20世纪20年代初到90年代末书写墨水的时间测定的进展.这包括,介绍新检验方法建立所需遵循的基本要求;推荐目前案件检验的工作程序,即墨水种类的确定,可疑文件的外观检验,同牌号、同配方、同批号比对样本的寻找;评述目前已为办案使用的各种书写年代测定的方法,如扩散法,转印法,染料比值法,气相色谱法、溶剂萃取法,差示扫描量热法等;以及讨论了有望用于年代测定的一些新技术,如用于钢笔墨水的电化学法,光谱法和用于圆珠笔墨水的显微分光光度法,付里叶变换拉曼光谱法等.     

Dating of Inkpad Seals Using the Extraction Rate Method: Preliminary Findings

Inkpad seals are often placed on important documents, and determining the date when a seal was affixed can be important to assess the authenticity of a document. In this study, three different brands of inkpads and four different types of paper were used to make diachronic samples of the seals. A double‐solvent extraction method was employed to date the inkpad seals by comparing extraction rates with inks of known age. Cyclohexane was selected as a weak solvent, and chlorobenzene was selected as a strong solvent. After testing, curves were created to show the relationship between the extraction percentage of ink and the date of the seals. The experimental results showed that the extraction rate method was applicable for the relative dating of inkpad seals in some cases where the seal was placed on the document within 6 months.     

LC—MS／MS法测定蓝色圆珠笔油墨中的碱性染料

目的建立蓝色圆珠笔油墨中碱性染料的LC—MS／MS方法,为蓝色圆珠笔油墨的种类鉴别提供方法。方法用二级质谱寻找并确定结晶紫、甲基紫、维多利亚蓝B、碱性紫14、碱性蓝7和罗丹明B等碱性染料的特征性母离子／子离子对。收集50种蓝色圆珠笔．划线后对其笔道用0．5mm直径打孔器取样,乙腈超声提取。液相分离采用WatersXBridgeC18柱。流动相为0．1％甲酸缓冲液（A）-乙腈（B）,梯度程序洗脱。结果4个点的取样量足以满足检测需要,采用相对峰面积的定量方法．结果重现性好．RSD％≤2．3％。应用该方法对50种蓝色圆珠笔油墨中的碱性染料进行检测,区分率为94．4％。结论所建LC—MS／MS方法定性准确,定量可靠,为蓝色圆珠笔油墨的种类鉴别提供了方法。     

A lifting process for determining the writing sequence of two intersecting ball-point pen strokes

The authors describe a technique for determining the order in which two intersecting ball-point pen strokes were made by means of lifting part of the ink with KromeKote paper. The KromeKote paper is applied to the intersection with the glossy side against the writing. The back of the lifting paper is rubbed with a blunt pointed instrument using moderate pressure. Study of the lift under low magnification discloses a pattern of edge markings with those from the last written line dominating the intersection. Results show a high percentage of accuracy.     

In situ luminescence spectroscopy with multivariate analysis for the discrimination of black ballpoint pen ink-lines on paper

A novel approach to the non-destructive discrimination of black, ball-point pen ink-lines on paper, has been developed which uses a standard luminescence spectrometer coupled with multivariate statistical analysis. The application of Principal Component Analysis (PCA) to these data-sets, followed by linear regression of the loadings, not only facilitates separation of the ink luminescence from that of the paper, but also allows a direct comparison between two ink lines on documents. This data reduction means that such a comparison can be done on an effectively univariate basis whereby a straightforward statistical comparison is made between two numbers, each characteristic of an ink. Thus the question, in the forensic context, of whether two ink-lines are indistinguishable may be answered with a particular statistical confidence and the method shows significantly better discrimination, for the pens studied, than conventional forensic investigative techniques involving the luminescence imaging of writing using filtered light.     

Dynamic of the ageing of ballpoint pen inks: quantification of phenoxyethanol by GC-MS.

The ageing process of some inks were studied to evaluate whether it is possible to date them. We used gas chromatography coupled with mass spectrometry to measure the evaporation of volatile components. The selected approach thus follows the disappearance of one ink volatile component (phenoxyethanol) as a function of time. The ink ageing curve represents the ratio of an evaporating compound to a stable compound of ink according to time. The results obtained are thus independent of the quantity of ink sampled for analysis. We obtained for two pens, containing two different inks, a curve highlighting an exponential decrease of the evaporating compound. By fitting these curves we determined the limitations of dating a ballpoint pen ink. Two distinct behaviours were observed in two distinct modes, the first called 'fast mode' and the second called 'slow mode'. In order to try to explain the phenomenon, the studies were based on solvent diffusion theory in complex matrix (such as polymer on varnish). Calculations from certain parameters showed an extremely fast evaporation of ink solvents, as well as varying behaviour depending on the paper used. The results showed that it is not possible to date ballpoint pen inks with this method in document examination casework.