LDI-TOF-MS中性墨迹分析新方法及其侦查应用

LDI-TOF-MS Study of Gel Ink Analysis and Its Applications in Crime Investigation

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归属院系：

刑事侦查学院

作者：

杨溢

导师：

喻彦林

导师单位：

刑事侦查学院

学位：

硕士

语种：

中文

关键词：

LDI-TOF-MS, 黑色中性墨迹, PEG, 书写时间, 环境影响

摘要：

黑色中性笔因其书写流利性高、墨迹耐久性强等特点，已成为目前应用最广泛的书写工具。在诈骗、贪污及虚假诉讼等刑事案件中，对涉嫌伪造或变造文书中中性笔墨迹的检验已成为案件侦破与司法争议解决的关键环节。然而，现有分析方法（如薄层色谱法、高效液相色谱法等）存在前处理步骤复杂、耗时较长、样本需求量较大、灵敏度不足及区分能力有限等问题。此外，墨迹形成时间推断因成分复杂、老化机理不明、环境影响多样，仍是全球文件检验领域的难点。激光解吸电离飞行时间质谱（Laser Desorption/Ionization Time-of-Flight Mass Spectrometry，LDI-TOF-MS）具有前处理简便、样品需要量少、分析速度快、灵敏度高、可获得聚合物分子量分布信息等优势，为中性墨迹（主要成分为聚乙二醇（polyethylene glycol，PEG）等多元醇聚合物）分析提供了新工具。本研究旨在用LDI-TOF-MS技术解决中性墨迹种类快速鉴别与历时性规律探索两大核心问题，遵循“方法建立—分类应用—历时性研究—环境因素考察”逻辑主线展开研究。研究前期，优化了LDI-TOF-MS直接进样条件，实现了无基质下对墨迹中PEG等组分的快速灵敏检测。并在此基础上开展三项核心实验：1.种类鉴别研究。基于LDI-TOF-MS技术，对市售31支碳基中性笔墨水进行了种类鉴别，该类墨水在多光谱分析、拉曼光谱及溶解实验中均难以区分。实验结果表明，不同碳基墨水的LDI-TOF-MS谱图中特征峰丰富，多归属于PEG200、PEG400、PEG600、PEG1000等常见聚乙二醇成分。依据多元醇组成差异，31种碳基墨水可进一步划分为8类，其区分度DP达到81.5%。本研究证实，该方法无需复杂前处理，仅需微量样品即可实现墨迹种类的高效判别，具有较强的实用性与推广价值。2.历时性变化研究。本研究旨在基于LDI-TOF-MS技术探究中性墨迹的历时性变化规律，为墨迹形成时间判断提供实验依据和新思路。通过对4类含不同分子量聚乙二醇（PEG）的墨迹样本进行长达两年的追踪分析，发现不同PEG老化特性存在显著差异。结果表明：（1）PEG400、600、1000变化符合扩散挥发模型，特征峰下降先快后缓；（2）PEG400老化后信号强度高，在不同品牌中相似，具有长期研究价值；（3）PEG1000初始信号低，129天内几乎检测不出，可作为近期书写指标；（4）PEG系列特征峰变化具有较好的一致性；（5）新鲜墨迹均匀性好，老化后固化导致扩散不均，误差棒增大；（6）实际案例中，结合纸张特征和GC-MS分析，成功鉴定三份检材为同期形成，证实了该方法在司法鉴定中的应用潜力。3.环境因素影响研究。通过模拟紫外灯老化、高温以及咖啡/茶水污染等环境条件，本研究系统考察了这些因素对墨迹稳定性的影响。研究结果表明：（1）短期紫外照射对PEG系列特征峰的质谱信号响应影响较为有限；（2）在120℃-150℃时，温度对PEG的影响较为有限；而当温度超过170℃时，各分子量PEG组分发生显著挥发或分解，导致特征峰强度显著降低；（3）咖啡与茶渍污染对墨迹分析产生显著干扰，具体表现为墨迹相关峰信息大量丢失，PEG特征峰强度急剧下降，该现象可能与污染物对墨迹的稀释作用有关。上述研究结果可为实际案件中的墨迹分析结果解读及环境干扰评估提供重要的参考依据和数据支持。综上，本研究提出并验证了基于LDI-TOF-MS的中性墨迹分析新策略。结论如下：其一，该方法无需基质辅助，操作简便，能高灵敏揭示PEG等多元醇聚合物的分子量分布特征，可快速鉴别黑色中性笔墨迹种类，对31种常见墨迹实现有效分类；其二，探索墨迹中不同分子量的聚乙二醇特征峰随时间自然老化的强度衰减规律，展示了用该技术推断短期墨迹形成时间的可行性以及探索2年以上书写时间墨迹的检测潜力，为解决墨迹形成时间判定难题提供了新思路。其三，明确了紫外线、高温及常见液体污染对分析结果的影响模式，为实际应用与结果解释提供了科学依据。本研究为文件检验领域提供了具有良好前景的新方法，提升了墨迹种类鉴别的效率与能力，更为攻克墨迹形成时间检验难题提供了创新性技术途径和实验数据基础，具有重大理论意义和应用价值。

参考文献：

一、中文参考文献（一）著作类1.于湛.原位电离质谱技术与应用[M].北京: 科学出版社, 2017: 76-77.2.（德）于尔根H.格罗斯著；王昊阳、李博等译：基础质谱学，北京：化学工业出版社，2024年版。3.王跃：文件检验[M].北京:知识产权出版社有限责任公司,2022:09. 4.王彦吉,王景翰.字迹色痕分析与书写时间鉴定[M].北京:中国人民公安大学出版.社,2010:131-135.（二）论文类5.王晓青, 陈栓虎. 基质辅助激光解吸电离飞行时间质谱在聚合物表征中的应用[J]. 质谱学报, 2008(1): 51-596.王方丽, 洪敏, 许丽丹, 等. 基于纳米材料的表面辅助激光解吸离子化质谱研究[J]. 化学进展, 2015, 27(5): 571-584.7.王闯, 覃露媛, 李冬梅, 等. 纳米材料在激光解吸电离质谱技术中的应用进展[J]. 分析化学, 2023, 51(2): 172-187.8.叶卓龙,王长亮,崔岚.利用显微分光光度计鉴别黑色中性笔墨水[J].中国司法鉴定,2019(3):40-44.9.王晓宾, 马枭, 杨蕾, 等. 基于PLS-DA拉曼光谱特征提取的中性笔油墨MLP模式识别[J]. 激光与光电子学进展, 2021, 58(1): 329-335.10.许英健,史晓凡,王彦吉,等.高效液相色谱法鉴别黑色签字笔墨水字迹形成时间的研究[J].分析测试学报, 2006,(04): 52-54+58.11.连园园, 梁鲁宁.国产与进口黑色签字笔墨迹的拉曼光谱比较分析[J].光散射学报,2016,28(03):245-251.12.赵鹏程, 柳林, 贾铠, 等. 中性笔字迹色度差值递变规律初探[J]. 中国刑警学院学报, 2018(6): 108-111.13.葛千红.中性笔的开发及其发展[J].中国制笔,2001,(1):38-39.14.姜东.中性墨水用炭黑色浆的制备与研究[D].上海:东华大学,2015.15.张祉悦, 赵鹏程, 叶祯, 等. 基于油墨色料成分判鉴文件色痕来源与形成时间的研究进展[J].应用化学, 2025, 42(9).16.宁倩.中性笔及其书写字迹档案研究现状调研[J].中国档案,2021,(09):70-71.17.史金.黑色中性笔书写字迹耐久性实验分析[J].档案学通讯,2020,(02):104-108.18.周勇强, 饶建顺, 郑成,等. 分散剂对中性墨水性能的影响[J]. 日用化学工业, 2012, 42(5).19.徐捷,张红鸣.中性墨水的消泡和消泡剂[J].中国制笔,2017(1)：18-3220.张瑞东. 黑色颜料型中性墨水配方设计[D]. 太原: 太原理工大学, 2011.21.牛凡. 基于光谱法和色谱法对蓝色圆珠笔墨迹添改文件的模式识别新方法研究[D]. 北京: 中国人民公安大学, 2018.22.何海洋, 赵鹏程, 何宁, 等. 基于气相色谱技术研究黑色中性笔字迹中3种溶剂随书写时间的变化规律[J]. 理化检验(化学分册), 2021, 57(9): 769-775.23.赵鹏程, 王彦吉, 赵彦军, 等. 裂解气相色谱法分析蓝色中性笔字迹的书写墨水种类及墨迹随书写时间的变化规律[J]. 色谱, 2007(5): 762-765.24.陈明星, 潘伟, 苏佳利, 等. 圆珠笔油墨中三苯甲烷类染料老化规律的研究[J]. 实验室研究与探索, 2015, 34(4): 30-33.25.陈明星, 苏佳利, 潘伟, 等. 圆珠笔墨水中染料成分在不同条件下的老化研究[J]. 实验技术与管理, 2014, 31(4): 57-60.26.吴国萍, 赵瑜, 秦晋. 显微分光光度法与显微红外光谱综合方法在黑色中性笔字迹鉴定中的应用[J]. 分析测试学报, 2009, 28(9): 999-1003.27.韩伟, 李江春, 谭瑞国. 拉曼光谱与电阻测量技术联用鉴别签字笔墨水种类的研究[J]. 光散射学报, 2018, 30(4): 344-350.28.李路希,周文,成小林,等.基于DART-MS的纸质文物墨迹着色剂快速识别方法初探[J/OL].复旦学报(自然科学版), 1-12[2026-06-02].29.杨旭,施少培,徐彻,等.VSC文检仪在文件鉴定中的应用研究[J].中国司法鉴定,2007(6): 16-21.30.何海洋,赵鹏程,何宁,等.基于气相色谱技术研究黑色中性笔字迹中3种溶剂随书写时间的变化规律[J].理化检验(化学分册),2021,57(9):769-775.31.孙其然,沈敏,徐彻,等.书写时间鉴定方法研究进展[J].中国司法鉴定,2015(1):45-54.32.黄建同.鉴定书写时间的方法研究[J].中国人民公安大学学报(自然科学版),2004(3):16-19.33.孙其然,张清华,王雅晨,等.环境因素对黑色中性笔墨迹中PEG低聚物降解的影响研究[J].中国司法鉴定,2018(2):37-41.34.王伟超.碳黑中性墨水润滑性和流变学研究及红色中性墨水开发[D].华东理工大学,2014.35.李小娜,廖菊平,刘波,等.抑制聚乙二醇老化研究[C]//中国材料研究学会.中国材料大会2025论文汇编.（三）标准类36.GB/T37853-2019中性墨水圆珠笔和笔芯，2019.37.SF/ZJD0203004-2018，书写墨迹中9种挥发性溶剂的检测气相色谱-质谱法.38.SF/Z JD0203005—2018；书写墨迹中9种染料的检测 液相色谱-高分辨质谱法.二、外文参考文献（一）著作类39.Young-Jin Lee,Mass Spectrometry Imaging of Small Molecules,Humana Press,2007.（二）论文类40.Reed G, Savage K, Edwards D, et al. Hyperspectral imaging of gel pen inks: An emerging tool in document analysis[J]. Science & Justice, 2014, 54(1): 71-80.41. Biao Li, Peng Xie, Ying‐min Guo, et al. GC Analysis of Black Gel Pen Ink Stored under Different Conditions[J]. Journal of Forensic Sciences, 2014, 59(2): 543-549.42.Weyermann C, Bucher L, Majcherczyk P, et al. Statistical discrimination of black gel pen inks43.analyzed by laser desorption/ionization mass spectrometry[J]. Forensic Science International, 2012, 217(1-3): 127-133.44.Andrasko J. HPLC analysis of ballpoint pen inks stored at different light conditions[J]. Journal of Forensic Sciences, 2001, 46(1): 21-30.45.Ferrari A C, Robertson J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon[J]. Physical Review B, 2001, 64(7): 075414.46.Wu Y, Zhou C X, Yu J, et al. Differentiation and dating of gel pen ink entries on paper by laser desorption ionization- and quadruple-time of flight mass spectrometry[J]. Dyes and Pigments, 2012, 94(3): 525-532.47.Sisco E, Forbes T P. Forensic applications of DART-MS: A review of recent literature[J]. Forensic Chemistry, 2021, 22: 100294.48.Jones R W, McClelland J F. Analysis of writing inks on paper using direct analysis in real time mass spectrometry[J]. Forensic Science International, 2013.49.Sun Q, Luo Y, Xiang P, et al. Analysis of PEG oligomers in black gel inks: Discrimination and ink dating[J]. Forensic Science International, 2017, 277: 1-9.50.Siegel J, Allison J, Mohr D, Dunn J. The use of laser desorption/ionization mass spectrometry in the analysis of inks in questioned documents. Talanta. 2005 Aug 15;67(2):425-9.51.Young-Jin Lee,Mass Spectrometry Imaging of Small Molecules,Humana Press,2007.52.Wang XF, Zhang Y, Wu Y, Yu J, Xie MX. Identification and differentiation of the red ink entries of seals on document by laser desorption ionization mass spectrometry. Forensic Sci Int. 2014 Mar;236:99-108.53.Matthews B ,Walker S G ,Kobus H , et al.The analysis of dyes in ball point pen inks on single paper fibres using laser desorption ionisation time of flight mass spectrometry (LDI-TOFMS)[J].Forensic Science International,2011,209(1):e26-e30.54.Sun Q, Luo Y, Wang Y, et al. Comparative analysis of aged documents by desorption electrospray ionization-Mass spectrometry ( DESI-MS ) imaging[J]. Journal of Forensic Sciences, 2022, 67(5): 2062-2072.55.Smalldon KW, Moffat AC. The calculation of discriminating power for a series of correlated attributes. Journal - Forensic Science Society. 1973 Oct;13(4):291-295. 56.Ferrari A C, Robertson J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon[J]. Physical Review B, 2001, 64(7): 075414.57.Weyermann C, Bucher L, Majcherczyk P. A statistical methodology for the comparison of blue gel pen inks analyzed by laser desorption/ionization mass spectrometry[J]. Science & Justice, 2011, 51(3): 122-130.

学科：

侦查学

提交日期：

2026-08-28

引用参考：

杨溢. LDI-TOF-MS中性墨迹分析新方法及其侦查应用[D]. 西南政法大学,2026.

全文附件授权许可：

知识共享许可协议-署名

  • dc.title
  • LDI-TOF-MS中性墨迹分析新方法及其侦查应用
  • dc.title
  • LDI-TOF-MS Study of Gel Ink Analysis and Its Applications in Crime Investigation
  • dc.contributor.schoolno
  • 20230301Z31157
  • dc.contributor.author
  • 杨溢
  • dc.contributor.affiliation
  • 刑事侦查学院
  • dc.contributor.degree
  • 硕士
  • dc.contributor.childdegree
  • 法学硕士学位
  • dc.contributor.degreeConferringInstitution
  • 西南政法大学
  • dc.identifier.year
  • 2026
  • dc.contributor.direction
  • 物证技术
  • dc.contributor.advisor
  • 喻彦林
  • dc.contributor.advisorAffiliation
  • 刑事侦查学院
  • dc.language.iso
  • 中文
  • dc.subject
  • LDI-TOF-MS,黑色中性墨迹,PEG,书写时间,环境影响
  • dc.subject
  • DI-TOF-MS; Gel ink; PEG; Ink dating; Environmental impact
  • dc.description.abstract
  • 黑色中性笔因其书写流利性高、墨迹耐久性强等特点，已成为目前应用最广泛的书写工具。在诈骗、贪污及虚假诉讼等刑事案件中，对涉嫌伪造或变造文书中中性笔墨迹的检验已成为案件侦破与司法争议解决的关键环节。然而，现有分析方法（如薄层色谱法、高效液相色谱法等）存在前处理步骤复杂、耗时较长、样本需求量较大、灵敏度不足及区分能力有限等问题。此外，墨迹形成时间推断因成分复杂、老化机理不明、环境影响多样，仍是全球文件检验领域的难点。激光解吸电离飞行时间质谱（Laser Desorption/Ionization Time-of-Flight Mass Spectrometry，LDI-TOF-MS）具有前处理简便、样品需要量少、分析速度快、灵敏度高、可获得聚合物分子量分布信息等优势，为中性墨迹（主要成分为聚乙二醇（polyethylene glycol，PEG）等多元醇聚合物）分析提供了新工具。本研究旨在用LDI-TOF-MS技术解决中性墨迹种类快速鉴别与历时性规律探索两大核心问题，遵循“方法建立—分类应用—历时性研究—环境因素考察”逻辑主线展开研究。研究前期，优化了LDI-TOF-MS直接进样条件，实现了无基质下对墨迹中PEG等组分的快速灵敏检测。并在此基础上开展三项核心实验：1.种类鉴别研究。基于LDI-TOF-MS技术，对市售31支碳基中性笔墨水进行了种类鉴别，该类墨水在多光谱分析、拉曼光谱及溶解实验中均难以区分。实验结果表明，不同碳基墨水的LDI-TOF-MS谱图中特征峰丰富，多归属于PEG200、PEG400、PEG600、PEG1000等常见聚乙二醇成分。依据多元醇组成差异，31种碳基墨水可进一步划分为8类，其区分度DP达到81.5%。本研究证实，该方法无需复杂前处理，仅需微量样品即可实现墨迹种类的高效判别，具有较强的实用性与推广价值。2.历时性变化研究。本研究旨在基于LDI-TOF-MS技术探究中性墨迹的历时性变化规律，为墨迹形成时间判断提供实验依据和新思路。通过对4类含不同分子量聚乙二醇（PEG）的墨迹样本进行长达两年的追踪分析，发现不同PEG老化特性存在显著差异。结果表明：（1）PEG400、600、1000变化符合扩散挥发模型，特征峰下降先快后缓；（2）PEG400老化后信号强度高，在不同品牌中相似，具有长期研究价值；（3）PEG1000初始信号低，129天内几乎检测不出，可作为近期书写指标；（4）PEG系列特征峰变化具有较好的一致性；（5）新鲜墨迹均匀性好，老化后固化导致扩散不均，误差棒增大；（6）实际案例中，结合纸张特征和GC-MS分析，成功鉴定三份检材为同期形成，证实了该方法在司法鉴定中的应用潜力。3.环境因素影响研究。通过模拟紫外灯老化、高温以及咖啡/茶水污染等环境条件，本研究系统考察了这些因素对墨迹稳定性的影响。研究结果表明：（1）短期紫外照射对PEG系列特征峰的质谱信号响应影响较为有限；（2）在120℃-150℃时，温度对PEG的影响较为有限；而当温度超过170℃时，各分子量PEG组分发生显著挥发或分解，导致特征峰强度显著降低；（3）咖啡与茶渍污染对墨迹分析产生显著干扰，具体表现为墨迹相关峰信息大量丢失，PEG特征峰强度急剧下降，该现象可能与污染物对墨迹的稀释作用有关。上述研究结果可为实际案件中的墨迹分析结果解读及环境干扰评估提供重要的参考依据和数据支持。综上，本研究提出并验证了基于LDI-TOF-MS的中性墨迹分析新策略。结论如下：其一，该方法无需基质辅助，操作简便，能高灵敏揭示PEG等多元醇聚合物的分子量分布特征，可快速鉴别黑色中性笔墨迹种类，对31种常见墨迹实现有效分类；其二，探索墨迹中不同分子量的聚乙二醇特征峰随时间自然老化的强度衰减规律，展示了用该技术推断短期墨迹形成时间的可行性以及探索2年以上书写时间墨迹的检测潜力，为解决墨迹形成时间判定难题提供了新思路。其三，明确了紫外线、高温及常见液体污染对分析结果的影响模式，为实际应用与结果解释提供了科学依据。本研究为文件检验领域提供了具有良好前景的新方法，提升了墨迹种类鉴别的效率与能力，更为攻克墨迹形成时间检验难题提供了创新性技术途径和实验数据基础，具有重大理论意义和应用价值。
  • dc.description.abstract
  • Black gel ink pens have become the most widely used writing tools due to their exceptional writing fluidity and long-lasting ink properties. In criminal cases involving fraud, embezzlement, and fraudulent litigation, examining ink traces on documents suspected of forgery or alteration has emerged as a critical step in case investigation and judicial dispute resolution. However, existing analytical methods (such as thin-layer chromatography and high-performance liquid chromatography) suffer from drawbacks including complex pretreatment procedures, prolonged processing times, high sample requirements, insufficient sensitivity, and limited discrimination capabilities. Moreover, determining the formation time of ink traces remains a global challenge in document analysis due to complex chemical compositions, unclear aging mechanisms, and diverse environmental influences. Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (LDI-TOF-MS) offers significant advantages—including simplified pretreatment, reduced sample requirements, rapid analysis speed, high sensitivity, and capability to determine polymer molecular weight distributions—making it a novel tool for analyzing gel ink traces primarily composed of polyethylene glycol (PEG) and other polyol polymers. This study aims to employ LDI-TOF-MS technology to address two core challenges: rapid identification of gel ink types and exploration of temporal variation patterns, following a structured research approach encompassing method development, categorical application, temporal analysis, and environmental factor evaluation. During the preliminary research phase, the direct injection conditions of LDI-TOF-MS were optimized, enabling rapid and sensitive detection of components such as PEG in ink without requiring a matrix. Building on this foundation, three core experiments were conducted。1.Species identification study.：Utilizing LDI-TOF-MS technology, species differentiation was performed on 31 commercially available carbon-based ink pens; these inks proved difficult to distinguish through multispectral analysis, Raman spectroscopy, or dissolution tests. The results demonstrated that the LDI-TOF-MS spectra of different carbon-based inks exhibited abundant characteristic peaks, predominantly corresponding to common polyethylene glycol compounds such as PEG200, PEG400, PEG600, and PEG1000. Based on variations in polyol composition, the 31 ink samples could be further classified into eight categories, achieving a discrimination power (DP) of 81.5%. This study confirms that the method requires no complex pretreatment and can efficiently identify ink types using only trace amounts of samples, demonstrating strong practicality and broad applicability. 2.Study of ink aging：This study aims to investigate the diachronic variation patterns of neutral ink droplets using LDI-TOF-MS technology, providing experimental evidence and novel approaches for determining ink formation timing. Through a two-year longitudinal analysis of four ink samples containing polyethylene glycol (PEG) with varying molecular weights, significant differences in PEG aging characteristics were identified.the results show that ： (1) The behavior of PEG 400,600, and 1000 aligns with a diffusion-volatilization model, with characteristic peaks declining initially rapidly followed by a gradual slowdown; (2) PEG 400 exhibits high signal intensity after aging, consistent across different brands, indicating its value for long-term research; (3) PEG 1000 shows low initial signal intensity that becomes nearly undetectable within 129 days, making it suitable as an indicator for recent writing activity; (4) The characteristic peak profiles of PEG series exhibit consistent evolution; (5) Fresh ink has good uniformity, but after aging, solidification leads to uneven diffusion and increased error bars; (6) In practical applications, combined with paper characteristics and GC-MS analysis, three samples were successfully identified as contemporaneous products, confirming the method's potential for forensic application. 3. Environmental Factor Impact Study. By simulating environmental conditions such as UV lamp aging, high temperatures, and coffee/tea contamination, this study systematically investigated the effects of these factors on ink stability. The results demonstrate that: (1) Short-term UV exposure has limited impact on the mass spectrometric signal responses of PEG series characteristic peaks; (2) At temperatures between 120°C and 150°C, temperature effects on PEG are minimal; however, when temperatures exceed 170°C, PEG components at various molecular weights undergo significant volatilization or decomposition, leading to a marked reduction in characteristic peak intensity; (3) Coffee and tea stains significantly interfere with ink analysis, manifested as substantial loss of relevant peak information and a sharp decline in PEG characteristic peak intensity, a phenomenon likely attributable to the dilution effect of contaminants on the ink. These findings provide crucial reference data for interpreting ink analysis results and assessing environmental interference in practical applications. In summary, this study proposes and validates a novel strategy for gel ink analysis based on LDI-TOF-MS. The conclusions are as follows: First, the method requires no matrix assistance, is operationally simple, enables high-sensitivity determination of molecular weight distribution characteristics of polyols such as PEG, rapidly identifies types of black gel ink, and achieves effective classification of 31 common ink varieties; Second, it investigates the intensity decay patterns of characteristic peaks corresponding to different molecular weights of polyethylene glycol during natural aging over time, demonstrating the feasibility of using this technique to estimate short-term ink formation durations and exploring its potential for detecting ink traces formed after more than two years of writing, thereby providing new approaches to addressing challenges in determining ink formation timelines; Third, it elucidates how ultraviolet radiation, high temperatures, and common liquid contaminants affect analytical results, offering scientific foundations for practical applications and result interpretation. This study introduces a promising new methodology for document authentication, enhances the efficiency and accuracy of ink type identification, and provides innovative technical pathways along with experimental data for resolving challenges in determining ink formation timelines, holding significant theoretical and practical value.
  • dc.date.issued
  • 2026-06-03
  • dc.date.oralDefense
  • 2026-05-23
  • dc.relation.citedreferences
  • 一、中文参考文献（一）著作类1.于湛.原位电离质谱技术与应用[M].北京: 科学出版社, 2017: 76-77.2.（德）于尔根H.格罗斯著；王昊阳、李博等译：基础质谱学，北京：化学工业出版社，2024年版。3.王跃：文件检验[M].北京:知识产权出版社有限责任公司,2022:09. 4.王彦吉,王景翰.字迹色痕分析与书写时间鉴定[M].北京:中国人民公安大学出版.社,2010:131-135.（二）论文类5.王晓青, 陈栓虎. 基质辅助激光解吸电离飞行时间质谱在聚合物表征中的应用[J]. 质谱学报, 2008(1): 51-596.王方丽, 洪敏, 许丽丹, 等. 基于纳米材料的表面辅助激光解吸离子化质谱研究[J]. 化学进展, 2015, 27(5): 571-584.7.王闯, 覃露媛, 李冬梅, 等. 纳米材料在激光解吸电离质谱技术中的应用进展[J]. 分析化学, 2023, 51(2): 172-187.8.叶卓龙,王长亮,崔岚.利用显微分光光度计鉴别黑色中性笔墨水[J].中国司法鉴定,2019(3):40-44.9.王晓宾, 马枭, 杨蕾, 等. 基于PLS-DA拉曼光谱特征提取的中性笔油墨MLP模式识别[J]. 激光与光电子学进展, 2021, 58(1): 329-335.10.许英健,史晓凡,王彦吉,等.高效液相色谱法鉴别黑色签字笔墨水字迹形成时间的研究[J].分析测试学报, 2006,(04): 52-54+58.11.连园园, 梁鲁宁.国产与进口黑色签字笔墨迹的拉曼光谱比较分析[J].光散射学报,2016,28(03):245-251.12.赵鹏程, 柳林, 贾铠, 等. 中性笔字迹色度差值递变规律初探[J]. 中国刑警学院学报, 2018(6): 108-111.13.葛千红.中性笔的开发及其发展[J].中国制笔,2001,(1):38-39.14.姜东.中性墨水用炭黑色浆的制备与研究[D].上海:东华大学,2015.15.张祉悦, 赵鹏程, 叶祯, 等. 基于油墨色料成分判鉴文件色痕来源与形成时间的研究进展[J].应用化学, 2025, 42(9).16.宁倩.中性笔及其书写字迹档案研究现状调研[J].中国档案,2021,(09):70-71.17.史金.黑色中性笔书写字迹耐久性实验分析[J].档案学通讯,2020,(02):104-108.18.周勇强, 饶建顺, 郑成,等. 分散剂对中性墨水性能的影响[J]. 日用化学工业, 2012, 42(5).19.徐捷,张红鸣.中性墨水的消泡和消泡剂[J].中国制笔,2017(1)：18-3220.张瑞东. 黑色颜料型中性墨水配方设计[D]. 太原: 太原理工大学, 2011.21.牛凡. 基于光谱法和色谱法对蓝色圆珠笔墨迹添改文件的模式识别新方法研究[D]. 北京: 中国人民公安大学, 2018.22.何海洋, 赵鹏程, 何宁, 等. 基于气相色谱技术研究黑色中性笔字迹中3种溶剂随书写时间的变化规律[J]. 理化检验(化学分册), 2021, 57(9): 769-775.23.赵鹏程, 王彦吉, 赵彦军, 等. 裂解气相色谱法分析蓝色中性笔字迹的书写墨水种类及墨迹随书写时间的变化规律[J]. 色谱, 2007(5): 762-765.24.陈明星, 潘伟, 苏佳利, 等. 圆珠笔油墨中三苯甲烷类染料老化规律的研究[J]. 实验室研究与探索, 2015, 34(4): 30-33.25.陈明星, 苏佳利, 潘伟, 等. 圆珠笔墨水中染料成分在不同条件下的老化研究[J]. 实验技术与管理, 2014, 31(4): 57-60.26.吴国萍, 赵瑜, 秦晋. 显微分光光度法与显微红外光谱综合方法在黑色中性笔字迹鉴定中的应用[J]. 分析测试学报, 2009, 28(9): 999-1003.27.韩伟, 李江春, 谭瑞国. 拉曼光谱与电阻测量技术联用鉴别签字笔墨水种类的研究[J]. 光散射学报, 2018, 30(4): 344-350.28.李路希,周文,成小林,等.基于DART-MS的纸质文物墨迹着色剂快速识别方法初探[J/OL].复旦学报(自然科学版), 1-12[2026-06-02].29.杨旭,施少培,徐彻,等.VSC文检仪在文件鉴定中的应用研究[J].中国司法鉴定,2007(6): 16-21.30.何海洋,赵鹏程,何宁,等.基于气相色谱技术研究黑色中性笔字迹中3种溶剂随书写时间的变化规律[J].理化检验(化学分册),2021,57(9):769-775.31.孙其然,沈敏,徐彻,等.书写时间鉴定方法研究进展[J].中国司法鉴定,2015(1):45-54.32.黄建同.鉴定书写时间的方法研究[J].中国人民公安大学学报(自然科学版),2004(3):16-19.33.孙其然,张清华,王雅晨,等.环境因素对黑色中性笔墨迹中PEG低聚物降解的影响研究[J].中国司法鉴定,2018(2):37-41.34.王伟超.碳黑中性墨水润滑性和流变学研究及红色中性墨水开发[D].华东理工大学,2014.35.李小娜,廖菊平,刘波,等.抑制聚乙二醇老化研究[C]//中国材料研究学会.中国材料大会2025论文汇编.（三）标准类36.GB/T37853-2019中性墨水圆珠笔和笔芯，2019.37.SF/ZJD0203004-2018，书写墨迹中9种挥发性溶剂的检测气相色谱-质谱法.38.SF/Z JD0203005—2018；书写墨迹中9种染料的检测 液相色谱-高分辨质谱法.二、外文参考文献（一）著作类39.Young-Jin Lee,Mass Spectrometry Imaging of Small Molecules,Humana Press,2007.（二）论文类40.Reed G, Savage K, Edwards D, et al. Hyperspectral imaging of gel pen inks: An emerging tool in document analysis[J]. Science & Justice, 2014, 54(1): 71-80.41. Biao Li, Peng Xie, Ying‐min Guo, et al. GC Analysis of Black Gel Pen Ink Stored under Different Conditions[J]. Journal of Forensic Sciences, 2014, 59(2): 543-549.42.Weyermann C, Bucher L, Majcherczyk P, et al. Statistical discrimination of black gel pen inks43.analyzed by laser desorption/ionization mass spectrometry[J]. Forensic Science International, 2012, 217(1-3): 127-133.44.Andrasko J. HPLC analysis of ballpoint pen inks stored at different light conditions[J]. Journal of Forensic Sciences, 2001, 46(1): 21-30.45.Ferrari A C, Robertson J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon[J]. Physical Review B, 2001, 64(7): 075414.46.Wu Y, Zhou C X, Yu J, et al. Differentiation and dating of gel pen ink entries on paper by laser desorption ionization- and quadruple-time of flight mass spectrometry[J]. Dyes and Pigments, 2012, 94(3): 525-532.47.Sisco E, Forbes T P. Forensic applications of DART-MS: A review of recent literature[J]. Forensic Chemistry, 2021, 22: 100294.48.Jones R W, McClelland J F. Analysis of writing inks on paper using direct analysis in real time mass spectrometry[J]. Forensic Science International, 2013.49.Sun Q, Luo Y, Xiang P, et al. Analysis of PEG oligomers in black gel inks: Discrimination and ink dating[J]. Forensic Science International, 2017, 277: 1-9.50.Siegel J, Allison J, Mohr D, Dunn J. The use of laser desorption/ionization mass spectrometry in the analysis of inks in questioned documents. Talanta. 2005 Aug 15;67(2):425-9.51.Young-Jin Lee,Mass Spectrometry Imaging of Small Molecules,Humana Press,2007.52.Wang XF, Zhang Y, Wu Y, Yu J, Xie MX. Identification and differentiation of the red ink entries of seals on document by laser desorption ionization mass spectrometry. Forensic Sci Int. 2014 Mar;236:99-108.53.Matthews B ,Walker S G ,Kobus H , et al.The analysis of dyes in ball point pen inks on single paper fibres using laser desorption ionisation time of flight mass spectrometry (LDI-TOFMS)[J].Forensic Science International,2011,209(1):e26-e30.54.Sun Q, Luo Y, Wang Y, et al. Comparative analysis of aged documents by desorption electrospray ionization-Mass spectrometry ( DESI-MS ) imaging[J]. Journal of Forensic Sciences, 2022, 67(5): 2062-2072.55.Smalldon KW, Moffat AC. The calculation of discriminating power for a series of correlated attributes. Journal - Forensic Science Society. 1973 Oct;13(4):291-295. 56.Ferrari A C, Robertson J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon[J]. Physical Review B, 2001, 64(7): 075414.57.Weyermann C, Bucher L, Majcherczyk P. A statistical methodology for the comparison of blue gel pen inks analyzed by laser desorption/ionization mass spectrometry[J]. Science & Justice, 2011, 51(3): 122-130.
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