汽车车身油漆红外光谱特征

采集了287份汽车车身油漆样本,使用傅里叶变换显微红外光谱仪获取了940份油漆层光谱,对不同车型、颜色的汽车油漆的清漆层、面漆层、中涂层的光谱特征进行分析,并对其光谱相似度进行比较。结果表明,同车型不同颜色的清漆层光谱相似度达到99.5%,部分相近车型的清漆层光谱高度相似;面漆层光谱因车型、颜色不同而差异较大,相似度在70%以下;中涂层的普通腻子光谱间的相似度在83.33%～96.91%,水基腻子光谱间的相似度在70.12%～96.44%;油漆中的金属成分会影响面漆层光谱的吸收特征;汽车油漆光谱随使用时间变化而发生变化。     

红外光谱结合多元统计学检验汽车前保险杠

在交通肇事逃逸和刑事案件中,常涉及对汽车前保险杠物证的检验鉴定,本实验采集了31款车型的汽车前保险杠碎片的红外光谱图,借助分类算法,结合多元统计学中的主成分分析法和判别分析法,建立数学模型,对光谱数据逐步展开了挖掘与分析,成功将31种汽车前保险杠样本分为了17类,分类正确率达92.5%,分类结果理想。本研究将现代仪器分析技术和多元统计法相结合实现了对汽车前保险杠碎片的分类和识别,为现场物证的检验提供了一定的理论依据。     

太赫兹脉冲光谱法测量微米级多层油漆涂层厚度技术

在汽车工业、飞机、船舶等领域中,油漆的涂层厚度管理对产品防水、防锈功能和颜色效果有着重要影响,但是目前采用的商业化涂层测厚仪都是接触式,并且很难直接获得多层涂层中的各层厚度。利用反射式太赫兹时域光谱(THz-TDS)系统探测样品的太赫兹脉冲光谱,基于脉冲回波的飞行时间建立简易的单点漆膜厚度提取模型。并通过最小二乘法拟合油漆样品的光学厚度与几何厚度之间的线性关系计算出12种涂覆在铝板上的油漆样品的测量折射率,发现金属油漆与非金属油漆在太赫兹波段的折射率存在较大的差异,闪光银色油漆样品的测量折射率为5.15,而白色油漆样品的测量折射率仅为2.64。在单层白色油漆样品厚度分布均匀的区域内测量50个点的膜厚,以磁/涡流感应涂层测厚仪的测量数据为参考标准,得到的厚度平均值为71.7 μm,测量误差为3.5 μm。对双层油漆样品进行二维扫描,测得白色油漆和底漆的厚度分布分别是(233±13)和(130±11) μm。同样,通过黑色三层油漆样品和银色三层油漆样品的二维分布图,分析了各层的漆膜厚度及其分布的均匀性。结果表明,太赫兹脉冲光谱法实现了1～3层漆膜的厚度测量及其分布均匀性评估,该方法对金属油漆的厚度分辨力较高,并且可通过非接触探测样品的太赫兹脉冲光谱,获得多层油漆的各层厚度及厚度的二维分布信息,易于实现喷涂质量的评估。     

基于小波多尺度分解的红外光谱谱图比对检索方法研究

谱图比对检索是指计算提问谱和数据库中标准谱图的相似度,以查出与提问谱相同或近似的谱图,其中,提问谱的质量是影响谱图比对检索结果的一个重要因素.从削弱谱图的无关信息对谱图比对检索的影响、提高检索准确性出发,以提问谱噪声为例,分析了谱图噪声对相似度计算结果的影响;针对红外光谱谱图经过小波多尺度分解后,其有用信息主要集中在低频部分,高频部分主要是噪声的特点,提出了基于小波多尺度分解的红外光谱谱图比对检索方法;分析了小波分解层数对相似度计算结果的影响;选择去噪整波形比对检索作为参照方法,利用MATLAB 7.0分别设计了这两种比对检索程序,实验结果证实了基于小波多尺度分解的红外光谱谱图比对检索方法的可行性.     

阵列相关系数比对法在中药鉴别中的应用研究

中药材红外光谱具有“指纹”性,通过对红外特征吸收谱图的比对可达到区分和鉴别药材的目的。该研究用Visual Basic 6.0设计了中药材红外光谱阵列相关系数比对软件,建立了300多种中药药材的红外光谱数据库,将未知药材的红外光谱与数据库中药材的红外光谱进行比对,它能依11个波段两光谱相关系数的大小自动找到与库中最相似的光谱的药材,从而达到鉴别未知药材的目的。研究结果表明：在光谱数据库所包含的药材范围内,指定阵列相关系数的阈值,抓住特征波段光谱的比对,可避开CO₂和H₂O等外界因素对谱图的干扰,使比对结果准确可靠。该法有望成为中药材快速鉴别的一种常规手段。     

法庭科学领域中微量物证的显微红外技术鉴定

在法庭科学领域中,由于案件现场提取到的物证通常是极微量的,另外样品形态各异、成分复杂,常规红外光谱分析技术常常无法达到检测要求。显微红外技术是基于傅里叶变换红外光谱技术与显微镜技术的结合发展起来的。与常规红外光谱技术相比,显微红外技术具有检测灵敏度高、微区分析和无损检测等优点,测试时几乎不引入外部干扰,卓有成效地解决了法庭科学领域中微量物证鉴定的难题,可以满足微量物证必须保留以用于法庭作证的特殊需要。通过本实验中心测试的真实案例分析,详细阐述了显微红外技术在法庭科学领域中微量物证鉴定方面的优势。采用显微红外技术,本文分别对油漆物证、塑料物证、橡胶物证、纤维物证、药物和毒物物证进行了红外光谱振动特征的比对分析,为各类刑事案件和交通肇事案件的定性提供有力的谱学依据。实验结果表明,显微红外技术具有常规红外测试技术无法比拟的优势,是法庭科学领域中微量物证鉴定的有效手段。     

红外光谱技术在物证鉴定中的应用

物证鉴定过程中,利用仪器分析技术快速准确的检测物证的化学组成会有助于获取更多案件相关的信息,常用的技术手段有色谱、质谱和光谱技术。法庭科学实验室涉及鉴定的物证种类繁多、情形复杂,需要根据物证的种类和仪器特性决定使用何种分析方法。比如气相色谱-质谱联用技术具有高分辨率、高灵敏度、强鉴别能力的优点,常被用于火灾现场易燃液体等物证的检测分析。法庭科学实验室更常见的应用情形是对与案件有关的各种有机物证(墨迹、油漆、塑料等)及无机物(矿物、无机填料等)进行快速有效分析。红外光谱法是鉴定化合物和测定分子结构的最有效的常规分析方法之一,尤其在法庭科学领域物证鉴定中被广泛应用,红外光谱技术可用来确定物证的种类,同时红外光谱又是一种有效的比对检验手段,检验结果可以为法庭断案提供证据。该文综述了红外光谱技术在法庭科学文件检验、油脂检验、塑料检验、油漆检验、纤维检验以及常见毒品等物证检验领域的应用现状及最新的研究进展,并对红外光谱技术在物证鉴定领域的应用前景进行了展望,以期从实际应用的角度为法庭科学研究人员提供红外光谱技术在该领域的研究概貌。     

傅里叶变换红外光谱用于肿瘤细胞株检测的研究

采取在体外培养胃癌细胞株(SGC7901), 将培养细胞涂于BaF₂窗片的方法,应用美国Nicolet(尼高力)公司Magna750-Ⅱ型红外光谱仪对细胞株进行透射红外光谱检测, 得到了时间轴上体外培养细胞株的光谱图, 将特征性光谱与胃癌组织光谱进行了比对。发现胃癌细胞株红外光谱特征与相应癌组织光谱特征存在异同,说明细胞胃癌组织所表现的红外光谱特征可以反映胃癌细胞本身的红外光谱特征, 同时也具有自身的复杂特点。实验为红外光谱法诊断胃癌奠定了细胞学基础。     

一种2～14μm红外光谱辐射计的辐射定标方法

提出了一种分区多点标定的辐射定标方法。定标原理如下:将测量目标的温度区间分为n个子区间,测量并记录目标温度区间内n+1个不同温度黑体对应的红外光谱辐射计输出数据,并分别计算各个子区间的定标系数;进行红外光谱辐射测量时,比对红外光谱辐射计输出数据和记录数据,确定待测目标所属温度子区间;使用对应子区间的定标系数进行辐射定标,以提高测量精度。使用该方法对研制的渐变滤光片型红外光谱辐射计进行辐射定标,并根据定标结果反演测量黑体的等效亮温温差。实验结果表明,该方法的辐射定标精度优于1.5 K,可应用于红外光谱辐射计的辐射定标。     

用激光诱导击穿光谱快速分析油漆中的重金属含量

 将电光调Q Nd：YAG激光脉冲聚焦于油漆样品表面以产生激光诱导等离子体。等离子体的光辐射经过一组透镜收集进入单色仪并由光电倍增管探测。通过对等离子体辐射光谱的研究,能够实现对油漆样品中重金属元素含量的快速定性分析。实验分析了多种市售油漆中重金属元素Pb, Cu, Cr, Mn的含量。实验表明：对于同一种类的油漆样品,在相同检测条件下,重金属元素的特征光谱线强度与元素质量分数成正比,因此利用激光诱导击穿光谱来快速分析油漆中重金属元素含量是完全可行的。     

基于LIBS光谱与成分分析的飞机蒙皮激光除漆可控性研究

激光除漆作为激光清洗技术的分支,有望替代传统打磨及化学除漆工艺,实现飞机蒙皮表面漆层的可控清除,但除漆过程及质量的可控性依赖于有效的原位、在线监测技术。针对飞机铝合金蒙皮表面多漆层结构,采用LIBS技术对不同漆层、不同厚度时漆层特征元素进行光谱与成分分析,在信号解译基础上建立漆层去除层数、去除厚度与LIBS光谱变化的内在关联,实现除漆过程质量的实时监测与反馈控制。结果表明,分层除漆过程中面漆、底漆完全清除后,漆层特征元素（Fe,Ti）的光谱峰消失。LIBS监测到面漆的特征元素Fe在501.494 1和521.517 9 nm处Fe Ⅰ 的光谱特征峰消失时,判定面漆完全清除。监测到底漆特征元素Ti在498.173 0,499.107 0和521.039 0 nm处Ti Ⅰ 的光谱特征峰消失时,判定底漆完全清除。厚度除漆时,随漆层厚度降低或激光脉冲作用次数增加,漆层特征元素（Ca）的光谱峰强相应降低,至漆层厚度为0时（完全去除）,漆层特征元素光谱峰消失,同时基体特征元素（Al）光谱峰出现。LIBS监测616.217 0,643.907 0和422.673 0 nm处Ca Ⅰ 的光谱信号强度变化能够监测激光除漆时剩余漆层厚度,实现对激光除漆厚度的可控清除监测。另外,结合EDS与SEM测试分析,验证了LIBS用于飞机蒙皮激光除漆过程与效果监测、分层与厚度控制的可行性,表明在不损伤基体氧化层的前提下,通过监测对应波长位置的面漆、底漆特征元素光谱与成分变化规律能够实现激光分层可控、厚度可控除漆。     

Raman spectroscopy of automotive paints: Forensic analysis of variability and spectral quality

Raman spectroscopy was evaluated as a forensic technique for the analysis of automotive paints with the purpose to verify the measurement variability as well as to study the spectral quality by means of parameters and conditions. The objective lens, accumulation number, and laser (power, mode, and wavelength) were observed to significantly affect the spectral quality and thus should be taken into consideration during the development of a forensic database. On the other hand, exposure time, Raman shift range, and baseline correction had less influence on the features of the obtained spectra. Interestingly, samples collected from the bumper coating composed of a plastic substrate in comparison with fragments obtained from other parts of the same vehicle containing metallic substrate showed different absorption band patterns. In addition, less variability of data acquired directly onto the paint chip’s surface has demonstrated that direct analysis should be preferred during spectra library development as opposed to cross-section measurements. Sample homogeneity and distinction power of the technique combined with Principal Components Analysis were also investigated. The preliminary results showed that although Raman spectroscopy is extremely accurate in the identification of vehicles, it is necessary to pay particular attention to the spectral variability in order to avoid false database matching and misleading of forensic investigations. Therefore, we suggest that separated spectra library shall be developed for each laser wavelength as well as for each sample substrate. Further studies with a higher number of paint chips will enable the establishment of prediction models aimed to identify unknown samples involved in hit-and-run cases.     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Nanoindentation and the micromechanics of Van Gogh oil paints

Understanding the mechanical properties of ancient paintings is a major issue for conservation and restoration. One strategy is to measure the mechanical properties of reconstructed paints: however, the aging process is poorly known, so it is also desirable to measure mechanical properties directly on ancient paint samples. Using nanoindentation, we have characterized submillimetric samples recovered from restoration of two Van Gogh paintings and compared the results with reconstructed paint samples. We demonstrate that the reduced modulus and hardness of historical paints can be measured at a very local scale, even differentiating between each paint layer. Our reconstructed paint samples exhibit elastic moduli comparable to values of the literature, but the values measured on the two 19th century paint samples are found to be significantly larger. Similarly, the compositional dependence of the elastic modulus is consistent with literature results for our reconstructed samples while our preliminary results for ancient samples do not readily fall into the same pattern. These results all point out to a significant impact of long term aging, in a manner which is difficult to predict in our present state of understanding. They demonstrate that nanoindentation is a very adequate tool to improve our knowledge of art paint mechanics and aging.     

X‐ray techniques applied to surface paintings of ceramic pottery pieces from Aguada Culture (Catamarca,Argentina)

X‐ray diffraction (XRD), energy dispersive spectrometry (EDS), x‐ray imaging (XRI) and scanning electron microscopy (SEM) techniques were applied to characterize and differentiate surface paintings of archeological pottery from the Aguada Ambato and Portezuelo styles (Catamarca, Argentina). Standard procedures are not always appropriate for such samples (paint layers are porous, nonplanar and discontinue). Image processing is necessary when chemical contrast is not discriminated. Soft x‐ray lines (e.g. Fe L) are more revealing because those detected come from shallower depths, clearly depicting the composition of the paint layer. These styles differ in mineralogy and chemistry suggesting that they are two distinctive entities not only on their designs but also on the materials chosen and the technology used. Aguada Portezuelo paints contain Ca (white), Fe? Mn (black), Fe? Mn? Ca (dark reddish) and Fe? Ca (reddish). The white ones correspond to gehlenite, a firing product (possible firing temperature ≥900–1000 °C); calcite and CaO occur in cases of firing temperatures <900 °C. Aguada Ambato presents difficulties for paint discrimination; only EDS spectra show slight differences. White paint from Tricolor Ambato contains mainly Pb‐phases (hatchite, anglesite, plumalsite), reddish paint resembles the paste (～Fe, hematite); reddish surfaces may have not been painted but polished. Black paint has scarce Mn–minerals. On Black Incised sherds no particular phase was identified suggesting possible organic pigments or resulting from the firing technique. The chemistry and mineralogy of the paste almost always overlap that of the paints; painted layer is irregular and partially worn by years of burial. Copyright © 2009 John Wiley & Sons, Ltd.     

Optimum spectral window for imaging of art with optical coherence tomography

Optical coherence tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS–NIR (400–2,400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use OCT for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 μm are highly desirable for OCT applications in art and potentially material science in general.     

Forensic analysis of automotive paints by Raman spectroscopy

In this work, the possible contribution of Raman spectroscopy in forensic science is evaluated, more specifically for the analysis of automotive paint samples. Spectra from paint flakes as well as from cross sections were examined, in order to identify not only the pigments but also binders and extenders in all paint layers. Moreover, the possibility of distinguishing paint samples from different cars was evaluated to assess the use of vibrational spectroscopic techniques in the investigation of a hit-and-run accident. The presence of rutile and extenders, such as calcite and barium sulphate, could be demonstrated by their characteristic Raman bands. However, the identification of the binder by Raman spectroscopy was hampered: only with additional information from IR analysis could most of the bands in the spectrum be assigned to molecular vibrations of the binders. In contrast, organic pigments, having very distinctive and well-resolved characteristic bands, could easily be identified by comparing the spectra from the basecoat of the sample with spectra from a reference database. Because of these characteristic bands, the basecoat seems to provide the best spectra to distinguish paint samples. Moreover, some paints can also be distinguished by the absence or presence of the bands from calcium carbonate and barium sulphate in the primer surfacer. When recording spectra from paint flakes, Raman bands from the spectra of the clearcoat as well as from the basecoat are obtained. Copyright © 2005 John Wiley & Sons, Ltd.     

Application of a likelihood ratio approach in solving a comparison problem of Raman spectra recorded for blue automotive paints

Evidential values of Raman spectra recorded for solid and metallic blue car paints were evaluated using visual comparison as well as a statistical approach, i.e. likelihood ratio (LR) test supported by Empirical Cross Entropy (ECE) results. Raman spectra were obtained using a Renishaw inVia spectrometer equipped with a confocal Leica microscope and a near infrared semiconductor laser (785 nm) as an excitation source. When a visual comparison was performed for solid paints, in 17.7% of comparisons (53 pairs out of 300) the samples were indistinguishable, whereas for metallic paints this value was 8.5% of such comparisons (37 pairs out of 435). Comparing the spectra using an LR approach was based on variables being the areas under the most significant Raman spectra bands of pigments present in the analysed samples. Proposed LR models delivered low false positive and false negative rates (for many models lower than 10%), and the ECE plots confirmed that their performance was much better than visual comparison. Copyright © 2015 John Wiley & Sons, Ltd.