新疆巴里坤石人子沟遗址群出土玻璃珠的成分分析

巴里坤县位于新疆东部哈密地区,是连接内地与北疆的重要通道,巴里坤县境内的石人子沟遗址群是新疆东天山地区的古代游牧民族大型聚落遗址,其中西沟遗址M1墓和石人子沟遗址M011墓分别出土了一批战国晚期至西汉早期的古代玻璃珠,为了解这批玻璃珠的来源,采用激光剥蚀电感耦合等离子体发射光谱(LA-ICP-AES)和激光拉曼光谱(LRS)方法对这两批玻璃珠样品进行化学成分分析。结果表明,西沟遗址M1墓出土玻璃珠均为钠钙玻璃体系,以植物灰作为助熔剂,同时其中七件绿色玻璃珠样品均以锑酸铅作为乳浊剂;石人子沟遗址M011墓出土玻璃珠均为铅钡玻璃体系,以含铅矿物作为助熔剂。与同时期其他已经发表的玻璃数据进行比较,显示西沟遗址出土玻璃珠在成分上与美索不达米亚及古埃及钠钙玻璃不同,推测西沟遗址出土玻璃珠在中亚或新疆地区制作而成;石人子沟遗址出土玻璃珠的化学组成相对集中,应在同一地点制作而成,可能为中原地区传入。本研究证实了新疆巴里坤地区是古代东西方物质文化交流的重要节点,而游牧民族在玻璃制品传播和交流过程中扮演着重要的角色。     

甘肃马家塬战国墓地M4出土硅酸盐珠饰的科学分析研究

结合X射线荧光光谱、拉曼光谱和X射线衍射分析,对甘肃马家塬战国墓地M4出土的11件装饰性硅酸盐珠饰进行了无损分析研究。依据分析结果将这些样品划分为钠钙硅酸盐玻璃、铅钡硅酸盐玻璃和釉砂三种类型。化学成分分析结果表明：钠钙硅酸盐蜻蜓眼玻璃珠的蓝色眼珠部分采用Co2+着色。拉曼光谱分析在铅钡体系硅酸盐样品中检测到了人工合成的硅酸钡铜系中国蓝和中国紫颜料,在钠钙蜻蜓眼玻璃的白色区域检测到了锑酸钙(CaSb₂O₆)乳浊剂/着色剂。结合已有的研究结果,探讨了所分析样品的可能来源及其反映的早期文化和技术交流状况。含有中国蓝、中国紫的装饰性珠子的制作材料和工艺应当是受到当时秦人的影响。而钠钙蜻蜓眼珠的成分特点,又与新疆等西北地区出土的同类珠子有相似之处。可见西戎人在玻璃制作技术方面同时受到北方草原民族文化和秦文化的共同影响。这批样品中以泥芯和玻璃化材料共同组成的装饰珠子,可能是从釉砂珠向玻璃珠的过渡类型,这对于研究我国玻璃的起源问题提供了新的参考资料。     

一批金元时期古玻璃的EDXRF探针无损分析

利用EDXRF探针无损分析技术,分析了河南禹县阳翟遗址出土的一批金元时期的玻璃样品,以研究这批古玻璃的工艺技术特点.分析显示,所有蓝色玻璃样品的呈色剂均为CuO,而非CoO.从化学组成来看,这批古玻璃的种类较为复杂,主要包括钾钙玻璃、钠钙玻璃和铅钾钙玻璃等.     

陕西战国秦墓出土玻璃和汉紫六博棋子分析研究

利用超景深显微镜（OM）、激光拉曼光谱仪(Raman)、X射线荧光光谱仪(XRF)、扫描电子显微镜能谱(SEM-EDS)、色度仪等多种手段,对陕西战国秦墓出土的两种质地、颜色不同的六博棋子进行了综合分析检测。鉴定出蓝色样品为铅钡玻璃,紫色样品为中国紫制品,发现了中国紫在战国时期的新用途。并对比陕西出土的铅钡玻璃制品与两湖、四川地区出土的同时代的铅钡玻璃制品在成分组成上的差异,推测战国时期铅钡玻璃的制作工艺已成熟,可根据器物形制的需求进行不同的成分配比。同时,还发现当时的玻璃制作已有旧料重熔制作新器的现象。在确定中国紫成分的基础上,利用色度计进行色度测试,根据光谱数据,首次为人造硅酸铜钡颜料确定了特征光谱峰,使快速、无损的对人造硅酸铜钡颜料的鉴定识别成为可能。     

北魏墓彩绘陶俑颜料的显微拉曼光谱分析

利用拉曼光谱对洛阳地区两座北魏墓出土陶俑的彩绘颜料进行了分析, 与标准颜料样品的拉曼光谱相比较, 识别出了陶俑所使用的红色、黑色、白色和蓝色颜料的显色成分。研究结果表明, 显微拉曼光谱分析技术非常适合对古墓葬彩绘陶俑进行成分分析。     

含稀土元素的矿渣纳米晶玻璃陶瓷的光谱学研究

利用白云鄂博矿资源废弃物中有价元素以共伴生形成存在的特点制备了高性能的矿渣纳米晶玻璃陶瓷。本文采用电感耦合等离子发射光谱（ICP）、X射线衍射（XRD）、拉曼光谱（Raman）、扫描电子显微镜（SEM）等测试方法对样品的成分和结构进行了深入分析。ICP和XRD、SEM实验结果表明,我们制备的玻璃陶瓷是主晶相为透辉石,晶粒尺寸在45～100nm范围含稀土元素的纳米晶玻璃陶瓷,SEM面扫所显示的元素与ICP成分分析结果较为一致。Raman分析表明,其非晶相主要由具有不同非桥氧键的硅氧四面体结构单元构成的三维网络结构,进一步分析发现稀土微量元素对网络结构有十分明显的影响。我们把矿渣纳米晶玻璃陶瓷与相似成分的玻璃陶瓷的拉曼光谱对比,发现矿渣纳米晶玻璃陶瓷的拉曼谱带普遍比玻璃陶瓷对应的拉曼谱带波数低。相似成分的玻璃陶瓷与矿渣纳米晶玻璃陶瓷的成分差别主要是稀土元素等微量元素。本文的研究方法为研究玻璃陶瓷的成分与结构、性能之间的关系提供了一种研究思路。     

具有高机械强度的掺Er~(3 )∶TeO_2-Nb_2O_5玻璃的光谱性质研究

熔制了掺铒碲铌玻璃样品(100-X)TeO2-XNb2O5(X=5,10,15,20mol%),测试了其密度、折射率、转变温度、析晶温度、维氏机械强度、吸收光谱、荧光光谱、荧光寿命等参量。利用Judd-Ofelt和McCumber理论分别计算了铒离子强度参量Ωt(t=2,4,6)和受激发射截面σemi的大小,研究了掺铒碲铌玻璃样品光谱参量对Nb2O5成分的依赖性,并与典型的碲锌钠玻璃(75TeO2-20ZnO-5Na2O)在热学、机械强度、光谱性质和放大品行四个方面进行了比较.     

河南宝丰和新郑出土硅酸盐制品的无损分析研究

无损分析是文物样品研究的重要内容,研究中采用便携式能量色散型X射线荧光光谱仪(pXRF)和激光拉曼光谱仪(LRS),对河南宝丰和新郑出土的21件战国晚期到汉代的硅酸盐制品进行了化学成分分析和微区物相分析。依据化学成分分析结果,将样品划分为铅钡硅酸盐玻璃、钾硅酸盐玻璃、釉砂和铅钡釉砂四类分别进行讨论,并对样品的着色机理进行了初步探讨;利用激光拉曼光谱在部分蜻蜓眼和圆环珠蓝色颜料中检测到了中国蓝(BaCuSi₄O₁₀)、中国紫(BaCuSi₂O₆)和中国深蓝(BaCu₂Si₂O₇),同时成功确定了部分样品中存在石英、方解石、碳酸铅、煅棕土、绿土等多种物相;结合考古研究资料,对这些样品的来源进行了简要讨论,其中本实验铅钡硅酸盐玻璃、钾硅酸盐玻璃耳珰和铅钡釉砂为我国自制,而另外1件釉砂可能属于舶来品,反映了我国古代中原各地区间,以及中原与西域间有着广泛的文化技术交流。便携式能量色散型X射线荧光光谱仪和激光拉曼光谱仪的相互结合,能够提供硅酸盐制品的有效化学成分和结构信息,在文物科学分析中显示出特有的优势,为其考古研究提供有益的信息。     

Gd掺杂对La0.67Sr0.33CoO3、 La0.67Sr0.33MnO3体系磁行为的影响

通过实验研究了La0.67-xGdxSr0.33CoO3、La0.67-xGdxSr0.33MnO3(x=0.00、0.05、0.10、0.20、0.30、0.40、0.50、0.60、0.67)体系的磁化强度与温度的关系(M～T)曲线、磁化强度与磁场强度的关系(M～H)曲线.实验结果表明,随Gd掺杂浓度增高,La0.67-xGdxSr0.33CoO3体系的磁结构表现为团簇玻璃态,x>0.10样品的M～T曲线出现了低温区M值急剧上升的奇特现象;La0.67-xGdxSr0.33MnO3体系的磁结构从长程铁磁有序向团簇玻璃态、反铁磁状态转变,x≥0.50样品的M～T曲线在低温区急剧下降.两种体系呈现的不同现象,来源于Gd与Co、Mn不同的耦合作用和Co的自旋态的转变.     

利用多光程光谱法检测血液多种成分含量的研究

为研究利用血清多光程光谱信息检测血液成分含量的可行性,通过设计自动微位移测量装置实现了对200份血清样品0～4.0 mm(间隔0.2 mm)近红外多光程光谱的测量。利用多光程光谱的非线性特性,使用血清多光程光谱共同参与建模的方法,对血清样品的葡萄糖(GLU)、总胆固醇(TC)、总蛋白(TP)和白蛋白(ALB)四种成分含量进行定量分析。采用偏最小二乘法(PLS)对160个血清样本的多光程近红外吸收谱与全自动生化分析仪得到的生化分析结果建立校正模型,并对预测集40个样本进行预测。４种血液成分预测值与生化分析结果的相关系数(r)分别为0.932 0,0.971 2,0.946 2和0.948 3。研究结果证明多光程光谱法建模方法用于血液成分含量分析的可行性,为利用多光程光谱法实现方便、快捷的检测血液以及其他液体成分含量奠定了基础。     

广西合浦九只岭汉墓出土石榴子石珠饰的科学分析

为探明广西合浦九只岭汉墓出土的一批紫色珠饰的材质、制作工艺和可能的原料来源,应用X射线荧光光谱、激光拉曼光谱和以及超景深三维显微系统三种分析技术科学分析了其中8枚珠饰。根据X射线荧光光谱和激光拉曼光谱分析结果,从矿物学特征上讲,这些珠饰是由石榴子石族矿物中的铝系石榴石加工而成,除一件样品属于铁铝-镁铝榴石型外,其矿物成分体系具有较高一致性,其他样品均属于富铁铝榴石型石榴子石。结合超景深数码显微系统所获取的样品加工痕迹信息以及近年考古学和科技研究成果,探讨了这批石榴子石的加工工艺和可能的来源。判断这批珠饰采用了旋磨工艺和皮囊球磨工艺两种打磨工艺,采用双钻石钻具对钻的钻孔工艺。这批铁铝榴石宝石珠饰应是由南亚或南亚经东南亚通过海上丝绸之路输入到合浦的,是汉代海上丝绸之路贸易的重要物证,对研究海上丝绸之路的历史和文化交流等具有重要的意义。     

Effect of neutron irradiation on etching,optical and structural properties of microscopic glass slide used as a solid state nuclear track detector

Microscopic glass slides are soda-lime glasses which are readily available and are easy to manufacture with low production cost. The application of these glasses as nuclear track detector will help us to make use of these glasses as solid-state nuclear track detector. The present paper describes the variation in the etching, optical and structural properties of the soda-lime microscopic glass slides due to neutron irradiation of different fluences. The color transformation and an increase in the optical absorption with neutron irradiation are observed. Both the bulk and track etch rates are found to increase with neutron fluence, thus showing a similar dependence on neutron fluence, but the sensitivity remains almost constant.     

Silver nanoclusters formation in ion-exchanged waveguides by annealing in hydrogen atmosphere

Light waveguides containing silver, introduced by ion-exchange process in soda-lime glass, has been annealed in hydrogen atmosphere at temperatures in the 120–250°C range. Annealings cause a near-surface precipitation of metallic silver to form nanometer-size clusters with good uniformity in size and spatial distribution. Hydrogen permeation and ion-exchange between hydrogen and sodium (which remains in the glass matrix after silver-for-sodium exchange) are steps of the annealing process. A further step is the diffusion of silver ions towards the surface, and its eventual precipitation, with an activation energy close to that measured for silver-sodium interdiffusion in glasses of comparable composition.     

In situ analysis of stratified glass eye beads from the tomb of Marquis Yi of the Zeng State in Hubei Province,China using XRF and micro‐Raman spectrometry

A total of 46 stratified glass eye beads in Hubei Provincial Museum, Wuhan, China were analyzed in situ by means of portable X‐ray fluorescence and Raman spectrometers. These beads were excavated from the famous tomb of Marquis Yi of the Zeng State, which was dated back to the early Warring States Period (433 bc or little late), in Hubei Province. It is determined that most of these elegant glass beads belong to the typical soda‐lime‐silicate glasses with low contents of MgO and K₂O. The colorants used within these beads are attributed to two types: antimony‐based compound opacifiers/colorants and the transition metals in their oxidized state such as Co, Cu, and Fe ions. According to their characteristics of typology, chemical composition, and micro‐crystals within samples, we classified them into three subtypes and evaluated the possible relations among them. In addition, through comparing with the similar contemporary samples unearthed from Xu Jialing Tomb (5th–4th century bc ) in Henan Province, we discussed the provenance of these stratified glass eye beads and relative issues briefly. Copyright © 2014 John Wiley & Sons, Ltd.     

Sputter-deposited network glasses

Thin films of lithium borate, sodium borate, rubidium borate, and lithium silicate glasses are prepared by ion beam sputter deposition in a thickness range between 70 and 1,400 nm. The chemical, structural, and electrical properties of the films are determined by transmission electron microscopy and impedance spectroscopy. A comparison between the thin glass layers and the corresponding bulk glasses, prepared from the melt, shows that both have similar chemical compositions and atomic short range orders. In contrast, the ionic conductivities of the borate glass films are found to be significantly increased compared to the corresponding bulk materials, while the increase depends on the chemical composition of the glasses and is not observed in the case of the silicate system. We propose a modified network structure of the sputter-deposited glass layers, namely, an increased nonbridging oxygen concentration, to be responsible for the elevated ionic conductivity.     

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO₃ (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO₃. These amorphous thin films of about 4 μm in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO₃ microcrystals in the amorphous phase.     

Surface modification of polyvalent element-containing glasses

Seven soda-lime silicate glasses, each of which contains one of the following polyvalent metals: Fe, Mn, Cu, Ce, Ti, V, and Cr, are oxidized in air and reduced in H₂/N₂ (1/99) at their respective glass transition temperature for some period. A crystalline oxide surface layer is created on the glasses (except the vanadium-bearing glass) under the oxidizing condition, since the metallic ions are oxidized from lower to higher valence state, and thereby calcium ions diffuse outward and react with oxygen ions. In contrast, a silica-rich surface layer is created on the glasses under the reducing condition, since sodium and calcium ions diffuse inward. It is found that the extents of both outward and inward diffusions strongly depend on the type of the polyvalent ions for the same conditions of heat-treatment. Out of the seven polyvalent metals studied in this work, copper induces the highest extent of both the inward and outward diffusion, and hence, the thickest surface layer of both amorphous silica and crystalline alkaline earth oxides. The oxide layer lowers the onset temperature of the primary crystallization. The silica-rich surface layer enhances the chemical resistance of the glass in a hot basic solution.     

湖北随州曾侯乙墓出土玉器材质分析与产源初探

曾侯乙墓位于湖北省随州市郊,是二十世纪重大考古发现之一,其中出土玉石器数量达五百余件,且种类齐全、工艺精湛。利用现代测试仪器对这批玉石器进行全面而科学的鉴定,对于东周时期曾国用玉水平的研究具有重要的学术意义。为了探知曾侯乙墓出土玉器的玉料类型及透闪石玉料可能来源地,以其中的319件玉器为研究对象,采用宝石学与光谱学的研究思路和方法对这些样品进行无损测试。通过十倍放大镜及天平等常规宝石学检测仪器对样品的表面特征、受沁程度及种类做出初步判断,利用傅里叶变换红外光谱仪（FTIR）和X射线荧光光谱仪（XRF）快速、无损的分析出土玉器样品的矿物相及化学成分。研究结果表明,常规仪器测试结合红外光谱及X射线荧光光谱可以很好的区分出土玉器的材质,在曾侯乙墓出土的319件玉器中,有264件透闪石质玉器,43件大理岩石璧、8件云母质玉器、1件石英岩、1件萤石以及2件水晶环。XRF测试结果显示,透闪石炙玉占全部检测样品的82.8%,其主要化学成分为MgO约占20.03%～27.00%（平均值为24.46%）, SiO₂约56.31%～61.17%（平均值为58.99%）, CaO约14.25%～19.91%（平均值为15.42%）, Fe_TO约0.19%～2.06%（平均值为0.551%）,计算可知m（Mg）/m（Mg+Fe）的值在0.91~0.99之间,其测试结果范围与标准透闪石含量很接近,该批样品中未检测出阳起石质的软玉。其中,大部分优质透闪石质玉器均出土自主墓室,反映出当时人们的用玉水平及用玉习惯。根据已有研究结果,结合化学成分分析及部分具有特征风化皮层及戈壁料特征的样品,推测曾侯乙墓部分出土玉器的玉料来源于甘肃古玉矿。该结论为进一步研究曾国用玉制度和战国时期玉石之路提供了更多的研究资料。     

Analyses of ion-exchanged glass optical waveguides by means of secondary ion mass spectroscopy: Condensation of impurity halide ions at the surface

We analyzed the chemical composition of K⁺-exchanged glass optical waveguides (OWGs) by secondary ion mass spectroscopy. Extensive condensation of impurity halide ions took place at the surface of the OWGs in the ion-exchanging and annealing processes. The condensation of Cl ions is likely a cause of the abnormal behavior observed for soda-lime glass OWGs; that is, a guided mode having appeared during the annealing did not disappear even after long annealing. Moreover, it was suggested that a space charge layer was formed at the OWG surfaces owing to the condensation of the halide ions.