一类绿松石仿制品的宝石学特征研究

绿松石的仿制品由来已久,早期主要以染色压制碳酸盐为主,后期陆续出现天然矿物的绿松石仿制品,如染色磷铝石、染色玉髓以及染色菱镁矿等,这些仿制品普遍不具有天然绿松石的颜色和结构特征,物理和光学性质与天然绿松石也有较大差异。选取市场上新出现的一类绿松石仿制品为研究对象,采用常规宝石学测试方法、红外吸收光谱及X射线粉晶衍射重点对其矿物组成、宝石学性质以及结构特征进行了研究。研究结果表明：该类绿松石仿制品表面可见角砾状构造,铁线浮于表面,分布形态单一,蓝色样品上可见明显的深蓝色颗粒,白色样品上见少量黑色点状物质,为典型的压制处理特征,蓝色绿松石仿制品则经染色压制处理。此类绿松石仿制品折射率在1.54～1.58,较天然绿松石低并具明显的蓝白色紫外荧光,可作为鉴别其与天然绿松石差异的重要证据。X射线粉晶衍射说明该类绿松石仿制品主要由顽火辉石与石英组成。红外吸收光谱显示该类绿松石仿制品的吸收谱峰主要表现为顽火辉石的典型吸收光谱,在1 088和799 cm-1附近的吸收峰则与石英中的Si—O和Si—O—Si伸缩振动有关;2 947和2 882 cm-1附近的吸收峰与外来的有机树脂中CH₂的伸缩振动有关,1 736和1 510 cm-1附近的吸收峰,则由CO伸缩振动和CH₂的弯曲振动所致。     

一种商业名为“象骨”材料的谱学分析

现如今一种商家称为"象骨"的工艺品在珠宝市场上十分普遍,仅用常规技术无法准确鉴定,为弄清此类工艺品的材料属性,本文通过宝石学常规测试、红外光谱(FTIR)、拉曼光谱(Raman)、X射线荧光光谱(EDXRF)等技术手段,分析其谱学特征,并与象牙进行了比较。研究结果表明:此类工艺品材料折射率RI:1.55±,呈较强蓝白色紫外荧光,具有断续平直的微裂纹。FTIR、Raman、EDXRF分析揭示由生物成因磷酸钙和胶原蛋白类有机物构成,含主要微量元素Al、Zn、Sr,物质组成与象牙相似。以无勒兹纹,缺少微量元素Mg、Si,主量元素Ca和P含量高于象牙,红外吸收光谱1500～1700 cm~(-1)之间指示胶原蛋白酰胺键C-O、C-H伸缩振动,及N-H面内弯曲振动的吸收峰明显弱于象牙等特征,可与象牙相区分。据其表面微裂纹、折射率以及物质组成等特征推断为骨制品。由于尚无象骨标准物质及特征数据做比对,笔者认为下一步通过市场调研掌握其产地、供货渠道、生产过程等真实来源信息是更准确鉴定此类工艺品材料的关键。     

周口店花岗闪长岩中斜长石晶体化学及谱学特征研究

前人研究多集中于碱性长石等其他长石系列,对斜长石的研究较少。在野外地质工作的基础上,采用电子探针仪、X光粉晶衍射仪、红外光谱仪和拉曼光谱仪对周口店花岗闪长岩中自然产出的斜长石进行了谱学特征和化学成分分析。电子探针分析获得该地斜长石的化学成分,端元组分在Ab_(85.21)Or_(0.18)An_(9.11)到Ab_(90.06)Or_(3.00)An_(13.27)之间;斜长石的X光粉晶衍射特征说明样品组成为较为纯净的钠长石,根据粉晶衍射峰及其衍射强度计算得出了样品晶胞参数;采用红外光谱和拉曼光谱分析了斜长石的谱学特征并对特征吸收谱带和特征峰进行了归属。在OH-红外吸收区(3 000～3 800 cm-1)出现了由OH的伸缩振动导致的特征吸收谱带: 3 200, 3 310,3 420和3 615 cm-1,表明研究区的钠长石普遍含有结构水,以OH-的形式存在。在以上分析的基础上对此种长石的晶体化学和结构特征进行了归纳总结。     

西藏“象牙玉”的矿物学及谱学特征

产自西藏丁青县的"象牙玉"结构致密,适于雕刻,绝大多数玉石呈白色,有的部位分布有红色细脉。采用常规宝石学仪器、扫描电子显微镜(SEM)、 X射线粉晶衍射(XRD)、傅里叶变换红外光谱(FTIR)和拉曼光谱(Raman)等测试方法对象牙玉进行了矿物学及谱学特征测试与研究。常规宝石学测试结果表明,象牙玉的相对密度为2.72～2.94,折射率为1.68(点测),在长波紫外光下呈强白色荧光。偏光显微镜下可见菱镁矿因为粒度极小而不具消光特征,石英呈脉状穿插菱镁矿,赤铁矿在菱镁矿裂隙中充填。背散射电子像表明绝大多数基质为菱镁矿与石英的微晶混合物,有的部位为较大石英颗粒(约25μm)散布在菱镁矿中,石英与赤铁矿呈微晶充填在菱镁矿的裂隙中。X射线粉晶衍射中具有3.34和4.25?石英的特征衍射峰, 2.74, 2.10和1.70?菱镁矿的特征衍射峰。在红外光谱中, 886, 1453和748 cm~(-1)为碳酸盐矿物的特征吸收峰,其中ν_4(面内弯曲振动)的频率与阳离子半径的变化成正比,因此748 cm~(-1)指示其为菱镁矿; 1 089, 1 165, 798, 779, 694, 515和465 cm~(-1)为石英的特征吸收峰。根据拉曼光谱可知,白色基质为菱镁矿与石英的混合,透明脉状矿物为石英,其中石英的拉曼图谱中还存在斜硅石的特征拉曼峰(500 cm~(-1)),在以α-石英为主的石英质玉石中,斜硅石的含量越高,其结晶程度越低,I_(500)/I_(465)的比值与结晶程度成反比,因此在菱镁矿中混杂的石英结晶程度比石英脉中的低,两处均为隐晶质石英;红色矿物具有1317, 655, 608, 492, 460, 406, 292, 242和222 cm~(-1)的赤铁矿典型拉曼峰。由于其原石并不存在生物迹象,所以其成因与生物无关,由于象牙玉为含隐晶质石英的泥晶质菱镁矿,所以推测其成因与超基性岩的风化淋滤作用有关。     

瘦长红珊瑚的振动光谱研究

瘦长红珊瑚是台湾贵珊瑚中最主要的品种,其颜色分布独具特色。以瘦长红珊瑚为研究对象,采用电子探针、X射线粉晶衍射、红外光谱和拉曼光谱对其进行测试分析。结果显示样品的矿物成分为高镁方解石,次要成分的含量稳定,样品中的生物成因方解石存在晶格畸变。实验探测到的代表有机质成分的1 517/1 128cm-1和1 296/1 016cm-1成套谱峰表明样品的红色与该有机成分有关。     

俄罗斯“绿龙晶”的成分和结构特征研究

随着近几年文玩市场的兴起,"绿龙晶"成为人们喜爱的一类新兴的宝玉石品种。目前对于"绿龙晶"的主要矿物组成的认识仍存分歧。采用常规宝石学仪器测试、电子探针、红外吸收光谱和X射线粉晶衍射测试方法对产自俄罗斯的"绿龙晶"玉的基本性质、化学成分、红外吸收光谱及矿物组成特征等进行了较为详细的研究分析。结果显示:俄罗斯"绿龙晶"玉主要为深绿至灰绿色,表面具有特殊的放射状花纹及典型的丝绢光泽,折射率约为1.57,密度为2.61g·cm-3。"绿龙晶"中SiO2的含量为36.177%~36.651%,MgO含量为36.439%~36.730%,Al2O3含量为11.961%~12.318%,FeO含量为2.304%~2.853%,具富镁贫铁特点。样品中Al/(Al+Mg+Fe)为0.185 3~0.215 9,推测其为镁铁质岩蚀变成因。样品中的Si=3.10~3.40,Fe~(2+)/R~(2+)=0~0.024 8,属叶绿泥石类型。"绿龙晶"的红外吸收光谱为特征的绿泥石振动谱峰,高频区3 673cm~(-1)附近的吸收峰为OH伸缩振动所致,1 400cm~(-1)附近吸收峰属OH弯曲频率,1 000cm~(-1)附近的三个吸收峰由Si—O伸缩振动致,400~600cm~(-1)之间的吸收谱带属于Si—O弯曲振动。其中中频区1 000cm~(-1)附近分裂的三个吸收峰1 051,1 006和968cm~(-1)可作为鉴定其为叶绿泥石的关键证据。X射线粉晶衍射分析结果与化学成分及红外吸收光谱分析结果一致,显示"绿龙晶"中的主要组成矿物为叶绿泥石,非斜绿泥石。     

中国山东方山与缅甸抹谷Le-shuza-kone矿区暗蓝色刚玉的谱学特征

为对比研究中国山东昌乐方山矿区与缅甸抹谷Le-shuza-kone矿区所产暗蓝色刚玉的光谱学特征,并确定方山矿区和Le-shuza-kone矿区刚玉中铁元素的价态及致色机理,采用X射线粉晶衍射（XRD）、显微拉曼光谱（RAMAN）、显微傅里叶红外光谱（FTIR）测试、电子探针（EPMA）及穆斯堡尔谱（CEMS）等方法,对产于方山矿区和Le-shuza-kone矿区暗蓝色刚玉的物相、光谱学特征及成分开展深入研究。X射线衍射结果表明,两个矿区所产的刚玉在2θ=25°～45°之间以3.408 8 Å（012）,2.551 8 Å（104）, 2.380 7 Å（110）和2.085 0 Å（113）四个衍射峰为特征。缅甸抹谷Le-shuza-kone矿区刚玉在2θ=22°～23°之间有3.981 5 Å（110）的弱衍射峰,在2θ=38°～40°之间有2.314 9 Å（111）的弱衍射峰,分别为硬水铝石和勃姆矿（一水软铝石）的特征。拉曼光谱散射峰主要分布于350～450和550～850 cm-1两个区间。416和378 cm-1为刚玉的特征峰,测试结果中415和377 cm-1的强峰属于内部结构变形导致的拉曼位移,749 cm-1处的拉曼散射峰归属于Al-O伸缩振动。方山矿区刚玉的793和811 cm-1拉曼峰和Le-shuza-kone矿区刚玉707, 793, 1 239和1 247 cm-1拉曼峰可作为区分产地的依据。红外光谱表现为两个矿区样品共有指纹区451,603,640, 779和1 088 cm-1的吸收峰,缅甸抹谷Le-shuza-kone矿区刚玉在官能团区有结构水（-OH）1 981, 2 110和3 311 cm-1的吸收峰,可作为特征峰与中国山东昌乐方山矿区刚玉相区别。缅甸抹谷Le-shuza-kone矿区暗蓝色刚玉含结构水,其形成过程中有水的参与,而山东昌乐方山矿区的刚玉中没有结构水。经电子探针测试和电价差法计算,中国山东昌乐方山矿区刚玉中铁元素的存在形式为Fe2+,Fe3+的含量为0,Le-shuza-kone矿区刚玉中Fe2+占Fe总量的91.9%,Fe3+占Fe总量的8.1%。创新性的在刚玉中铁元素的研究中引入了穆斯堡尔谱仪测试测得中国山东昌乐方山矿区刚玉内铁的赋存形式为Fe2+,而非Fe2++Fe3+,其深蓝色的体色是由Fe2+致色的,而非前人推测的Fe2++Fe3+或Fe2++Ti4+价间电荷转移致色。     

缅甸翡翠中黑色条带的表征研究

在缅甸矿区发现一种具有黑色条带的翡翠,外观呈现灰黑色至黑色。X射线粉晶衍射物相分析表明,该种翡翠的主要矿物成分为硬玉与少量的绿辉石。扫描电子显微镜观察到该翡翠的硬玉晶粒间隙与张性裂隙中密布着大量细小的黑色矿物包体,拉曼光谱观测到1 582 cm-1的特征峰,部分包体同时出现1 346 cm-1的峰,表明该矿物包体为石墨,根据其拉曼特征进一步标识为石墨单晶与无定形石墨。这些黑色石墨包体以各种形式结合成尺寸不一的组合,在3 000 nm至可见光波长范围区间造成极大的光散射损耗,导致包体密集区域透明度大大降低,形成黑色条带的外观。通过显微观察在样品中还发现两组锆石包体,经拉曼光谱测试证实其结晶度高,未出现明显的蜕晶化,属于高型锆石。     

燃烧法合成La_2Zr_2O_7粉及其光谱性能

以La_2O_3,Zr(NO_3)_4和甘氨酸为原料,采用燃烧法合成La_2Zr_2O_7粉。分别用发射光谱法(ICPAES)、能谱法(EDAX)、X衍射法(XRD)、红外光谱法(IR)和热重-差热法(TG-DTA)等对La_2Zr_2O_7粉进行表征。分别研究了热处理温度对La_2Zr_2O_7粉的X衍射谱和红外光谱的影响。La_2Zr_2O_7粉的ICP-AES和EDAX分析结果表明,用燃烧法可合成出La_2Zr_2O_7粉。不同温度热处理后La_2Zr_2O_7粉的XRD分析结果表明,当热处理温度为600℃时,出现一个衍射峰,且衍射峰较宽,该结构为半晶型结构;提高热处理温度,衍射峰逐渐尖锐,峰形变窄,衍射峰逐渐增多;热处理温度在750~800℃范围,可得到烧绿石结构的La_2Zr_2O_7粉。在650~750℃热处理后La_2Zr_2O_7粉的红外光谱分析结果与XRD分析结果相同,热处理温度为750℃时,可得到烧绿石结构的La_2Zr_2O_7粉。La_2Zr_2O_7粉的TG-DTG分析结果表明,在120~1 600℃范围,La_2Zr_2O_7粉的结构稳定。     

纳米磷化镓粉体中混杂石墨和金刚石微晶的拉曼光谱分析

利用Raman光谱并结合能量色散X射线显微分析(EDX)和X射线衍射图谱(XRD)对混杂于纳米磷化镓粉体内的石墨和金刚石纳米微晶进行了分析。结果表明,在纳米GaP粉体Raman光谱中,位于1324 cm-1和1572 cm-1的两个宽强散射谱带分别归属于金刚石的F2g模和石墨的E2g模振动。EDX结果证实纳米GaP粉体材料中含有碳元素。XRD图谱中出现了石墨和金刚石的低晶面指数衍射峰。     

The Goodmanham plane: Raman spectroscopic analysis of a Roman ivory artefact

Raman spectroscopy has been applied to the study of the exceptional ivory stock of an archaeological discovery of great importance for the history of woodworking tools: a virtually complete Roman plane that was found in a late fourth century A.D. context in North Yorkshire, UK, in A.D. 2000. An assessment has been made of the viability of Raman spectroscopy for the identification of ivories from archaeological excavations and comparisons made with similar studies of modern specimens. All of the attributed ivory specimens studied have suffered from deterioration in their burial environment, and severe degradation of their proteinaceous component was observed. In addition, spectral quality was affected through the absorption of fluorescent materials from their environment, and from the presence of emergency conservation procedures undertaken to preserve the integrity of very fragile specimens. The spectra of ivories dating from about 2000 years ago varied considerably because some specimens had experienced an almost complete leaching‐out of collagen, whereas in others, the degraded protein was still substantially identifiable. Generally, however, the protocols used successfully for the identification of modern ivories and for an assignment of their mammalian species were not transferable into archaeological ivory identification and classification because of the collagen degradation and decreased spectral quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Testing of Raman spectroscopy as a non‐invasive tool for the investigation of glass‐protected miniature portraits

Six French miniature portraits on ivory and paper dating back to the 18th to 19th centuries have been studied by Raman spectroscopy. The miniatures have been investigated through their protective glass cover using different operating conditions: various laser wavelengths (1064, 785 and 532 nm), spectrometers (fixed and mobile) and objectives (10× to 200×). The results obtained for black (carbon), grey (carbon + chalk), red (lead oxide, vermillion), blue (Prussian or phthalocyanine blue), green (emerald or Paris green) and white (lead white) pigments are presented. The consistency of the period of use of the pigments with the proposed dating for each artwork is evaluated. Attention is paid to the analysis of the ivory substrates (assigned to Asian elephant ivory) and to the protective glass. Copyright © 2011 John Wiley & Sons, Ltd.     

条形半导体激光器光束质量因子M2的理论计算

通过一个二维半矢量模型求得纯折射率导引脊形波导和掩埋波导这两种常见平面条形半导体激光器波导结构的模式光场分布，现通过描述光束传播的非傍轴矢量二阶矩，通过平面波谱的方法获得激光器出射光束在横向和侧向上的束腰、远场发散角和M^2因子。讨论了波导结构参量变化对M^2因子的影响，并对两种波导结构光束的性质与波导参量的关系进行了比较。     

Seismic properties of Asian elephant (Elephas maximus) vocalizations and locomotion

Seismic and acoustic data were recorded simultaneously from Asian elephants (Elephas maximus) during periods of vocalizations and locomotion. Acoustic and seismic signals from rumbles were highly correlated at near and far distances and were in phase near the elephant and were out of phase at an increased distance from the elephant. Data analyses indicated that elephant generated signals associated with rumbles and "foot stomps" propagated at different velocities in the two media, the acoustic signals traveling at 309 m/s and the seismic signals at 248-264 m/s. Both types of signals had predominant frequencies in the range of 20 Hz. Seismic signal amplitudes considerably above background noise were recorded at 40 m from the generating elephants for both the rumble and the stomp. Seismic propagation models suggest that seismic waveforms from vocalizations are potentially detectable by instruments at distances of up to 16 km, and up to 32 km for locomotion generated signals. Thus, if detectable by elephants, these seismic signals could be useful for long distance communication.     

Particular features of the application of IR reflection spectroscopy methods in studies in archeology and paleontology

We have considered an optical model of a porous rough surface with optical properties of objects (bone, flint) that are typical of archeology and paleontology. We have formulated an approach that makes it possible to perform mathematical processing of the IR reflection spectra of objects of this kind using standard algorithms and determine criteria that ensure obtaining reliable information on objects with a rough surface in the course of interpretation of frequencies in their IR reflection spectra. The potential of the approach has been demonstrated using as an example an investigation by the IR Fourier-transform reflection spectroscopy of mineralization processes of mammoth tusks from two paleolithic sites (14000 and 16000 BCE) located by the town of Yudinovo, Bryansk oblast, Russia.     

Wild African elephants (Loxodonta africana) discriminate between familiar and unfamiliar conspecific seismic alarm calls

The ability to discriminate between call types and callers as well as more subtle information about the importance of a call has been documented in a range of species. This type of discrimination is also important in the vibrotactile environment for species that communicate via vibrations. It has recently been shown that African elephants (Loxodonta africana) can detect seismic cues, but it is not known whether they discriminate seismic information from noise. In a series of experiments, familiar and unfamiliar alarm calls were transmitted seismically to wild African elephant family groups. Elephants respond significantly to the alarm calls of familiar herds (p=0.004) but not to the unfamiliar calls and two different controls, thus demonstrating the ability of elephants to discriminate subtle differences between seismic calls given in the same context. If elephants use the seismic environment to detect and discriminate between conspecific calls, based on the familiarity of the caller or some other physical property, they may be using the ground as a very sophisticated sounding board.     

碱性品红分子在正、负电性纳米银上的吸附取向

制备了两种不同电性的纳米银粒子的胶体,发现当碱性品红分子分别吸附的在这两种纳米银上时,其表面增强拉曼谱在谱线的强度及谱线数目上均有有明显的不同。在正电性纳米银上,主要是面内模式得到增强,且碱性品红特征峰的强度是I1589>I1524>I1371。而在负电性纳米银上,面内伸缩模式及面外弯曲模式均得到增强,且碱性品红特征峰的强度是I1588<I1520=I1371,通过分析增强谱的差异表明,分子在这两种不同电性胶态纳米银表面上可能分别以垂直及倾斜方式吸附。     

下地幔硅酸盐矿物的结构和电子相变对其高压下光学性质的影响

基于第一性原理平面波超软赝势法并结合局域密度近似,计算了(Mg_(0.875),Fe_(0.125))SiO_3钙钛矿和(Mg_(0.9),Fe_(0.1))SiO_3后钙钛矿晶体在高压下的光学性质.计算数据表明:(1)钙钛矿的结构相变将导致其吸收性增强,证实了基于实验数据的推断.(2)后钙钛矿二价铁吸收带的波数位置与实验观测结果相近.(3)在后钙钛矿相区,压力将导致吸收带的强度缓慢增加,但二价铁自旋态的转变对其吸收谱的影响却非常微弱.(4)钙钛矿的结构相变将导致其折射率升高;在后钙钛矿相区,压力及自旋态转变对折射率的影响不明显.(5)波数大约在12500 cm~(-1)以下,后钙钛矿折射率随波数的增加而降低,钙钛矿的折射率则变化不大;波数大约在12500 cm~(-1)以上,钙钛矿折射率随波数的增加而增大,后钙钛矿的折射率则显著上升.     

新疆软玉、辽宁岫岩软玉的XRD及红外光谱研究

选取新疆和辽宁岫岩两地不同颜色的软玉,青玉、黄玉、白玉、碧玉及岫岩的特殊品种——河磨玉作为研究对象,通过宝石学测试、红外吸收光谱和X粉晶衍射分析对两个产地不同种类及颜色软玉的宝石矿物学特征进行了系统研究和对比,以探索两产地相近颜色软玉的异同,为软玉的产地鉴别提供理论依据。研究结果表明,辽宁岫岩与新疆软玉的宝石学性质相似,折射率为1.60～1.62,密度为2.660~3.020 g·cm-3,密度随颜色的不同有一定差异,荧光特征均不明显,两产地软玉的主要组成矿物均为透闪石,其中新疆碧玉中含有少量绿泥石、伊利石等粘土矿物。两产地不同种类软玉的X粉晶衍射分析显示,不同种类软玉的衍射峰峰形特征及衍射强度在一定程度上可以反映软玉的质地及结晶颗粒大小。红外吸收光谱显示两产地软玉的红外吸收光谱特征类似,对鉴别软玉产地及种属意义不大。     

阶变折射率轴棱锥产生局域空心光束

提出利用折射率成阶跃性变化的轴棱锥产生局域空心光束(bottlebeam).讨论了折射率沿径向成阶跃式减小或增加两种模型,从几何光学角度分析了它们产生bottle beam的原理,利用衍射积分理论数值模拟两种轴棱锥光传输的光场分布和不同距离处的二维光斑图,研究结果表明折射率沿径向阶跃减小的轴棱锥产生单个bottle beam,而折射率沿径向阶跃增加的轴棱锥产生具有周期再现的bottle beams.bottle beam在原子引导和囚禁、光学俘获及光镊等方面有广泛的应用,因此本文的研究对bottlebeam的产生和实际应用具有指导意义.