石墨化碳质物质拉曼光谱温度计原理与应用

doi:10.11867/j.issn.1001-8166.2020.029

总结了石墨化碳质物质拉曼光谱温度计的原理、样品制备、测试流程、影响因素和地质应用。该温度计基于沉积岩变质过程中发生的不可逆的碳质物质石墨化，利用拉曼光谱量化石墨化的程度，进而限制峰期变质的温度。近年来的研究量化了温度计算模型；同时发现除温度外，石墨化碳质物质拉曼光谱的影响因素还包括：石墨结构与成分的非均匀性、抛光制靶时引起的结构损伤、测试激光的波长和能量、赤铁矿含量等。因此，石墨化碳质物质拉曼光谱温度计的应用需要注意如下事项：野外需采集新鲜样品，排除风化产物赤铁矿的影响；使用标准的样品制备与测试流程，避免抛光和激光烧蚀的影响；并通过多点测试(通常为25个以上)的方式，统计测试结果的平均值与误差，以提高温度计算结果的准度。该方法适用的温度范围为100~700 ℃，在变质—变形分析、沉积岩埋藏历史、断层泥与有机质成熟度等研究领域均有较为广泛的应用。

关键词: 碳质物质, 石墨化, 拉曼光谱, 变质温度计, 中—低级变质作用

This contribution attempts to summarize the principles, sample preparation, analytical procedures, influencing factors, and geological applications of Raman Spectroscopy of Carbonaceous Material (RSCM) thermometry. Irreversible graphitization of carbonaceous material in sedimentary rocks occurs during the process of reaching peak metamorphic temperature and can be effectively quantified by Raman spectroscopy. However, in addition to temperature, other factors, such as structural and compositional heterogeneity of carbonaceous materials, structural damage caused by polishing, wavelength and energy of laser used for analyses, hematite content,etc., also have significant influence on the Raman signals of carbonaceous materials. Therefore, fresh samples should be collected for analyses to eliminate the influence of hematite. Further, standard experimental procedure should be practiced to avoid the effects of polishing and laser parameter setups. Additionally, multiple (usually more than 25) analyses per sample should be carried out for deriving statistical average and uncertainty values so as to minimize the influence of sample heterogeneity. RSCM thermometry is applicable to a temperature range between 100~700 ℃, and has been widely used in many fields of geological studies, including metamorphism and deformation of orogens, sediment burial history, fault gouge characteristics and evolution, and maturation grade of carbonaceous materials,etc.

Key words: Carbonaceous material, Graphitization, Raman spectroscopy, Geothermometer, Metamorphism and deformation

中图分类号:

P588.3

图1 碳质物质拉曼光谱特征、光谱拟合及经历了不同变质温度样品光谱信号
(a)光谱拟合示意图(据参考文献[ 19 ]修改)，其中实线为原始光谱图像，虚线为分峰拟合结果：G(graphite)峰表示石墨峰，D(defect)峰表示缺陷峰；(b)不同峰期变质温度样品的拉曼光谱图像与对应温度计算结果；用于分析的石墨化碳质物质分别来自龙门山映秀断裂断层泥、松潘—甘孜地体东部的复理石、龙门山腹地志留纪云母片岩和胶北矽线石榴片麻岩样品；随着样品峰期变质温度增高，G峰信号增强、D峰信号减弱

Fig.1 Images of typical raman spectra, spectral fitting results and the spectra of samples that have experienced different peak metamorphic temperatures
(a) Images of typical raman spectra and spectral fitting results (modified after reference [ 19 ]), where the solid line is the original spectral signal, and the dash lines are the peak fitting results: The G-band represents the graphite peak and the D-bands represent defect peaks； (b) Raman spectra of samples with different peak metamorphic temperatures and corresponding temperature calculation results； The samples are fault gouge of the Yingxiu fault in the Longmenshan, Triassic flysch in the eastern Songpan-Ganzi terrane， Silurian mica schist in the hinterland of the Longmenshan, and metamorphic rocks in the Khondalite belt of North China； As shown, the G-band signal increases and the D-band signal decreases with the increase of sample peak temperatures

图2 龙门山云母片岩样品
(a)透射光显微照片； (b)反射光显微照片

Fig.2 Micrographs of a mica schist sample from the Longmenshan
(a) Transmitted； (b) Reflected lights

图3 不同峰期变质温度样品的荧光背景
(a)中高温变质碳质物质拉曼光谱(实线)具有近线性荧光背景(虚线)；(b)低温变质样品具有非线性荧光背景(虚线)

Fig.3 Fluorescent background of samples with different peak metamorphic temperatures
(a) Samples with a moderate peak metamorphic temperature often show linear fluorescent background (dashed line)； (b) Samples with a peak metamorphic temperature often yield non-linear fluorescent background (dashed line)

图4 温度计算模型对比图
(a)高温样品的经验公式计算结果对比图，结果显示，除个别异常点，公式(4)与(6)的计算温度明显高于公式(2)；(b)适用于相对低温样品的经验公式(6)(横坐标)与公式(7)(纵坐标)低温(<400 ℃)计算结果对比，二者计算相对误差均较大，整体上公式(7)计算结果小于公式(6)；拉曼数据源自参考文献[ 21 ]和图1b中的样品

Fig.4 Comparison of different Raman spectroscopy of carbonaceous material thermometry models
(a) Comparison of the temperatures calculated by equations (2) (x-axis) and (4), (6) (y-axis) that are suitable for a relatively higher temperature range； The calculation results show that except for several outliners, the calculated temperatures by formula (4) and (6) are higher than that by formula (2)； (b) Comparison of equation 6 (x-axis) and 7 (y-axis) at low temperature (<400 ℃). Both errors are large, and the calculated results of equation 7 are relatively smaller than those of equation 6. Raman data are derived from reference[ 21 ] and Fig.1b

图5 石墨拉曼光谱各向异性分析图(据参考文献[ 57 ]修改)
由上至下为在石墨不同晶轴方向上的测试结果；由左至右为使用不同波长激光的分析结果，右下角双向箭头为激光偏振方向

Fig.5 Raman spectra of graphite anisotropy (modified after reference [ 57 ])
From top to bottom are the Raman spectra of graphite in different crystal axis directions; From left to right are the analysis results using lasers with different wavelengths. The double-headed arrows in the lower right corner of the panels mark the laser polarization direction

图6 碳质物质高分辨率透射电镜显微形貌照片(据参考文献[ 58 ]修改)
(a)002晶面：可见到洋葱式结构，外圈比内圈有序度要高;(b)002晶面：有序度小于(a)，发育显微气孔结构，不同区域有序度不同;(a)和(b)来自同一个样品的不同位置

Fig.6 HRTEM pictures from carbonaceous material (modified after reference [ 58 ])
(a) 002 lattice fringes image showing onion ring microtextures, the core is poorly organized in comparison with the outer part; (b) 002 lattice fringes image of microporous poorly organized carbonaceous material. The two pictures are taken from different locations of the same sample

图7 激光波长对碳质拉曼光谱的影响(据参考文献[ 67 ]修改)
随波长增加，石墨峰(G峰)频移基本不变，缺陷峰(D1峰)频移增大，同时石墨峰信号相对于缺陷峰减弱

Fig.7 Effect of laser wavelength on Raman spectroscopy of carbonaceous material (modified after reference [ 67 ])
With an increasing laser wavelength, the Raman shift of the G-band is relatively stable; The Raman shift of the D1-band increases; The
G-band signal is weakened compare to the D1-band

图8 测试前(a)与经过不同能量激光测试后(b~e)的碳质物质显微照片，及对应的拉曼光谱结果(f)(据参考文献[ 69 ]修改)

Fig.8 Images of carbonaceous material before(a)and after Raman spectroscopy analysis using different laser energy(b~e)，and the corresponding Raman spectra(f)(modified after reference［ 69 ］)

图9 抛光对拉曼测试结果的影响(据参考文献[ 9 , 72 ]修改)
(a)显微镜下石墨照片，部分石墨直被抛光暴露(黑色点标注的透射光下的不透明、反射光下灰白色强反射的区域)，部分处于透明矿物之下(白点所标注的反射光下的较虚的灰白色区域)；(b)抛光暴露的与透明矿物下的石墨拉曼光谱测试结果

Fig.9 Raman spectra of polished graphite and that of grains beneath quartz (modified after references [9,72])
(a) Microscopic photos of graphite exposed by polishing (opaque under transmitted light and gray-white under reflected light, marked by black spots) and those beneath transparent miners (marked by white spots); (b) Raman spectra of those two types of graphite

图10 赤铁矿对拉曼光谱影响(据参考文献[ 73 ]修改)
(a)为石墨光谱形态与同频移段内赤铁矿光谱形态，其中赤铁矿谱峰位置为1 320 cm ^-1，与石墨D1缺陷峰位置(1 350 cm ^-1)接近，插图为氧化(灰色)与未氧化(黑色)样品的测试谱图，显示氧化样品受赤铁矿谱峰影响而产生虚假的强D1缺陷峰;(b)为是否经HF酸处理的碳质物质 R1与 R2值的变化：未经过HF处理的氧化样品(灰色) R1与 R2值明显大于未氧化样品(黑色)；处理后两类样品基本相同

Fig.10 Effect of hematite on Raman Spectra of graphite (modified after reference [ 73 ])
(a) Raman spectra of hematite (grey) and graphite (black). The Raman shift of hematite is located at 1 320 cm ^-1, close to D1 band (1 350 cm ^-1) of graphite. The insetted panel shows a comparison of Raman spectra of oxidized (grey) and non-oxidised (black) samples, and the former shows a fake and strong D1 band due to influence of hematite. (b) R1 and R2 plots for untreated and HF-treated samples. Blue points indicate non-oxidised samples. Red points indicate oxidised samples. After treatment, the two types of samples yield similar R1 and R2 values

图11 尼泊尔西部地质图、拉曼测温结果及NE-SW向A-A'构造—变质温度剖面（据参考文献［ 74 ］修改）
图中给出构造地层的接触关系及一些样品的拉曼测温结果，（a）图为地质图所属地理位置；（b）NE-SW向剖面AA';LH: 低喜马拉雅；MCT：主中央逆冲断层；MBT：主边界逆冲断层；MFT：主前缘逆冲断层

Fig.11 Geological map of western Nepal, on which Raman Spectroscopy of Carbonaceous Material (RSCM) thermometer results are compiled, and there also have a NE-SW cross-section A-A' with temperature and main thrusts (modified after reference［ 74 ］)
There are major tectonostratigraphic zones and tectonic contacts and some RSCM thermometer results in the map. (a) Location of the studied area at the scale of Nepal. (b) A simplified NE-SW crosssection AAV with temperature and main thrusts. Abbreviation: LH：Lesser Himalaya，MCT：Main Central Thrust，MBT：Main Boundary Thrust，MFT：Main Frontal Thrust

图12 剪切摩擦实验后样品拉曼光谱特征，及其与初始材料的对比(据参考文献[ 88 ]修改)
(a) 初始样品与剪切摩擦实验后样品拉曼光谱D1/G峰宽值与D1/G强度值的变化;(b) 经初始样品标准化后的剪切样品D1/G半高宽值与D1与G峰拉曼频移位置

Fig.12 Raman spectra analyses of gouges sheared in rock friction experiments, and comparison with the initial material (modified after reference [ 88 ])
(a) Defect band to graphite band (D1/G) width versus intensity ratios of samples before and after friction experiments； (b) Plots of D1 and G peak widths of sheared gouges verseus the D1/G width ratio normalized by average starting material

图13 汶川地震科学钻井-1岩芯照片及不同位置拉曼分析结果(据参考文献[ 88 ]修改)
(a)龙门山断裂主要岩芯照片；(b)断层泥与角砾岩D1/G峰宽度比值与强度比值对比图；(c) 断层泥与角砾岩G、D1峰宽比及G峰与D1峰拉曼频移位置。插图显示断层泥G峰频移相对角砾岩增大；PSZ: 主滑动区域

Fig.13 Wenchuan Earthquake Fault Scientific Drilling WFSD-1 borehole core with sample depth locations and results of Raman analyses (modified after reference [ 88 ])
(a) Core images of the WFSD-1 borehole； (b) Defect to graphite band (D1/G) peak width ratio versus D1/G intensity ratio； (c) Ratio of G and D1 peak width of gouge to average breccia peak width versus G band peak position. Inset shows systematic shift toward higher frequencies of G band observed in black gouge with respect to fault breccia； PSZ denotes the Principal Slip Zone

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Fundamentals and Applications of Raman Spectroscopy of Carbonaceous Material( RSCM) Thermometry