化学成份在钧瓷胎釉反应层中分布模式的线扫描分析

利用能量色散X射线荧光(EDXRF)探针, 对一批金元时期的钧瓷样品进行了线扫描分析, 以研究钧瓷胎釉间薄层物质的性质及其它相关问题. 结果显示, 胎釉间薄层物质的化学组成介于胎釉之间, 因此其应为在烧制过程中形成的反应层. 分析还发现, 反应层中的K₂O含量高于瓷釉和瓷胎, 与其它氧化物均有不同. 推断反应层中K₂O含量高的现象, 是瓷釉和反应层中特定的SiO₂和Al₂O₃组成, 硅酸盐玻璃的特定网络结构, 以及SiO₂, Al₂O₃及K₂O在玻璃体中的作用和特性等因素的综合作用结果, 而非单纯的K^＋具有较强的渗透能力所致.     

能量色散X射线荧光光谱法探针线扫描分析"长沙窑"彩绘工艺

应用能量色散X射线荧光光谱（EDXRF）探针及线扫描技术对我国唐代和宋代的5块“长沙窑”彩瓷样品的彩绘工艺进行了研究。根据所测得的从釉到胎中着色元素铜或铁的含量变化可以看出,此5块样品的彩绘工艺均不完全属于典型的釉下彩工艺,而是属于高温釉上彩工艺。     

能量色散X射线探针技术对汝瓷成分的线扫描分析

用能量色散X射线探针技术对汝瓷残片的剖面从釉到胎进行了主要成分含量的线扫描分析, 结果表明: 在釉胎之间的确存在一个中间层, 在这中间层各元素从釉的含量变化到胎的含量, 而且这种变化是连续的, 每个元素含量变化的起点与终点略有不同, 变化曲线也不一样. 这是在汝瓷烧制过程中, 瓷釉在形成玻璃态的同时渗入了瓷胎表面而形成的, 这与在实体光学显微镜上能明显看出而在偏光显微镜和扫描电子显微镜下看不到此中间层的情况相符合.     

能量色散X射线荧光光谱法分析金元时代的钧窑瓷器

应用能量色散X射线荧光光谱法测定了16个金元时期钧窑瓷器胎、釉样品的化学组成。由结果可知:金元钧瓷胎具有低硅高铝的北方瓷器特点,釉则多为钙碱釉。金元时期样品与北宋时期钧窑瓷器胎釉化学组成比较,金元时期钧窑样品的化学组成变化较大,从因子分析散点图可见,北宋钧官窑样品化学组成变化不大;金元钧窑与北宋钧民窑样品制作工艺上存在继承和发展的关系,但金元时期对原料选择和配方的控制已不如北宋时期严格,反映出金元时期的钧窑已处于衰落阶段。     

基于适配体的石墨烯修饰玻碳电极检测卡那霉素

建立了一种基于适配体和石墨烯修饰玻碳电极检测卡那霉素的方法。卡那霉素适配体(Kanaaptamer)可以吸附在石墨烯(Gr)修饰的电极表面,从而阻碍电化学探针[Fe(CN)6]3-/4-与电极表面的电子传递,然而与含有卡那霉素的样品反应后,卡那霉素能与适配体结合并使其从电极上置换脱落,对界面电子传递的阻碍作用降低,探针的电化学信号得到恢复。通过循环伏安法和原子力显微镜法对该过程进行了表征。该原理被用于对卡那霉素进行电化学检测,结果表明:在优化条件下,用差分脉冲伏安法(DPV)检测卡那霉素时,其线性范围为1×10-6~1×10-5mol/L,检出限为5×10-7mol/L。该方法应用于牛奶样品中卡那霉素的检测,结果满意。     

基于磁性金属有机框架化合物-适配体探针的氯霉素仿生比色传感器研究

构建了一种基于磁性金属有机框架化合物( MOF)-适配体探针的仿生比色传感器,用于食品中氯霉素残留分析。首先将氯霉素( CAP)的适配体标记到Fe3 O4磁珠上获得捕获探针,进而采用该适配体的互补链标记到铁基MOF( Fe-MOF)上作为纳米示踪剂( MOF-cDNA),将捕获探针和示踪剂杂交结合后,可获得铁磁性仿生复合探针。当氯霉素和此类探针孵育后,其与捕获探针上的适配体结合,将纳米示踪剂释放到溶液中,并经过磁分离后进入上清液。由于Fe-MOF具有过氧化物酶的性质,可以催化TMB-H2 O2系统显色,由此构建了一种高选择性的氯霉素比色传感器。在最佳反应条件下,本法对氯霉素的检测范围在0.001~10 ng/mL之间,最低检出限为0.3 pg/mL(S/N=3),实际样品的加标回收率为86.9%~93.5%,且不受其它抗生素干扰。用此方法检测牛奶样品中氯霉素的结果与商业化ELISA方法一致。此类无酶标记仿生探针具有高催化活性且成本较酶标探针大大降低;该分析方法利用磁分离简化了前处理步骤,可用于奶制品中氯霉素的快速灵敏分析。     

介孔分子筛KIT-1表面磷酸改性及其催化性能

采用后合成法将磷酸固载在纯硅介孔分子筛KIT-1表面上,制备出了表面含磷酸的样品P-KIT-1.利用X射线粉末衍射(XRD),红外光谱(IR)、低温N2吸附-脱附等手段对样品结构进行了表征,用化学滴定法测定了样品的表面酸性,以对苯二酚与叔丁醇的烷基化反应为探针反应对催化剂的性能进行了评价.实验结果表明,样品P-KIT-1保持了基体分子筛KIT-1的介孔结构,由于磷酸占据了分子筛的内外表面,占据了孔道内部空间,使其比表面积、孔容和孔径都减小,但减少不大.随着磷酸负载量的增加,样品的酸量和催化活性也随之增加,当磷酸负载量为7%时催化活性为最好,且明显高于微孔 ZSM-5和β沸石,说明该催化剂样品在烷基化反应中的活性除了与样品的酸量有关外还与孔径的大小有关,是大分子反应有用的固体酸催化剂.     

关于影响镧、钐与铕测定灵敏度原因的探讨

实验证明，在石墨表面上原子化时，镧、钐或铕与炽热的石墨反应生成难解离的碳化物是导致镧、钐和铕测定灵敏度低与严重记忆效应的原因。用钽探针原子化测定钐样品时，钐物种与钽氧化物之间发生反应，生成复合物SmTaO4、镶嵌于钽探针表面的裂痕内，阻碍了钐原子化，导致测定钐的灵敏度下降。     

蛋白质与光谱探针的反应机理与分析应用研究—在碱性介质中Calcon－Cu（Ⅱ）络合物与蛋白质的反应

本文研究了在碱性介质中，金属络合物Ｃａｌｃｏｎ－Ｃｕ（Ⅱ）作为光谱探针与蛋白质的反应．结果表明，Ｃａｌｃｏｎ－Ｃｕ（Ⅱ）与蛋白质反应生成复合物可作为蛋白质测定的基础．研究了反应条件，干扰物质及进行了样品分析．提出了用双波长技术直接求出一个蛋白质分子结合探针个数的方法，并对反应机理进行了初步研究．     

钛矿石与钛精矿X射线荧光光谱分析与化学分析用标准样品的研制

研制了钛矿石与钛精矿X射线荧光光谱分析与化学分析用标准样品。从国内外有代表性的矿区取点,采用了多级破碎、三维机械混筛工艺,确保了标准样品化学成分的均匀性,多家权威实验室用准确可靠的分析方法确定了16种化学成分的标准值和不确定度,实验表明,标准样品的线性与稳定性良好。该项目标准样品填补了国内外同类X射线荧光光谱分析标准样品的空白,已被国家检验检疫总局和国家标准化管理委员会批准为国家级标准样品。     

Line scanning analysis of the component of Ru Porcelain by micro energy disperse X-ray fluorescence probe

The Ru kiln is one of the five famous kilns of the Song Dynasty in China, and it is said that the Ru Porcelain is the chief of the five. As the Ru Porcelain was produced for a short time in history, no other than approximately 20 a, and exclusively fired only for the royalty, the remains are rather rare, with the total number falling short of one hundred pieces all over the world excluding the ones excavated in Qingliang Temple, Baofeng County, Henan Province. Especially, the celadon of …     

激光电离飞行时间质谱技术用于古代瓷片中元素的检测及元素成像分析

采用自制激光电离飞行时间质谱(LI-TOF-MS)及多元素成像体系,尝试分析了古瓷片中的多种元素.对一块北宋龙泉青瓷瓷片及一块仿古青瓷瓷片样品进行了表面元素分析,所得多元素半定量分析结果表明,这两种瓷片的胎体和釉面中所含元素的种类及含量存在差异;同时对一块明代青花瓷片进行表面多元素成像分析,获得Co,Mn,Fe,Ni,Ba,Ca,Mg,Na,Al,Si,P,K,Cu,Zn和Rb的元素成像图.     

Provenance studies of pottery fragments from medieval Cairo, Egypt

In the analysis of archeological pottery fragments, instrumental neutron activation analysis has been utilized to establish the elemental concentrations of up to 37 chemical elements for each of 53 archeological pottery samples from medieval Cairo, Egypt, and one additional sample of Chinese porcelain. These elemental concentrations have been utilized in a statistical analysis procedure in order to determine similarities and correlations between the various samples. Multivariate analyses have been used to quantitatively determine these interrelationships. This methodology successfully separated the Egyptian samples into two broad categories: (1) polychrome decorated ceramic ware and (2) monochrome celadon ware. In addition the methodology successfully identified the one unique sample of Chinese porcelain. Several samples appeared to be either a mixture of categories or outliers in the data set and were not attributable to any distinct category.     

Integrated investigations for the characterisation of Roman lead-glazed pottery from Pompeii and Herculaneum (Italy)

A multi-analytical approach was used to investigate Roman lead-glazed ceramic artefacts from archaeological excavations at Pompeii and Herculaneum (Italy) aiming at defining the production technology of both glaze and ceramic body, by way of integrated investigations. The chemical, structural, and micro-morphological characterisations were performed using a combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), optical microscopy (OM), scanning electron microscopy (SEM), and micro-Raman spectroscopy. Fragments of artefacts (skyphoi, oil lamps, bowls, askoi, amphorae, krateres) of great historical and archaeological interest were sampled. LA-ICP-MS was used to determine the elemental composition by virtue of its effective lateral resolution, its ability to detect most elements and also to analyse comparably small samples. All the archaeological objects were coated with a lead-based glaze produced using a lead oxide-plus-quartz mixture, with sodium/potassium feldspars added as a flux and two different metals used: copper and iron. Two types of ceramic pastes have been identified, but chemometric techniques support the hypothesis of a Campanian provenance for the raw materials. Degradation phenomena such as the partial devitrification of the glaze, i.e. the slow structural reorganisation towards stable crystalline phases, and the leaching by mineral dissolution in the soil, were determined.     

X-ray emission fluorescence (XRF) analysis of origin of raw materials of light dark reddish brown porcelain and porcelain with black flower on a white background of Dangyangyu kiln

Dangyangyu kiln was an important civil porcelain production place in the North China during the Song Dynasty. In order to find out the source of raw materials of the porcelain body and glaze and their classification relationship so as to correctly distinguish them, we have used XRF to determine the major chemical elements of some porcelain samples with light brown and samples with black flower on a white background. Dynamic fuzzy cluster analysis was applied to the data. Results indicate that the origin of raw materials of light brown porcelain body samples is comparatively more concentrated, while that of the porcelain with black flower on a white background is scattered about. The origin of the body materials of those two kinds of porcelain samples is obviously different. The origin of raw materials of light brown porcelain samples is comparatively concentrated and stable, while that of the porcelain with black flower on a white background is scattered about, moreover, the origin of glaze raw materials and the formula of the two kinds are obviously different. The origin and formula of the light brown porcelain with white glaze in the interior are close to those of the white glaze of porcelain with black flower on a white background, but they are not entirely identical.     

我国北方古白瓷釉化学组成的能量色散X荧光光谱分析

利用能量色散X荧光光谱分析法（EDXRFS）测定了我国北方的四个窑口——邢窑、定窑、巩窑和宜阳窑所烧制白瓷釉的主量元素和微量元素，通过化学成分分析和多元统计的方法，揭示出不同窑口化学组成的分区特征，并且发现宜阳窑的白瓷与我国北方三个代表性白瓷窑口之一——巩窑之间存在着密切的联系。     

Effect of particle-size distribution on the surface appearance of glazed surface

Glazes have great influence on most of the final properties of sanitary wares, such as color, glossy, and surface roughness. Generally, these properties have been changed by chemical composition and firing parameters. In addition, the selection of particle-size distribution of raw glaze can affect on the surface appearance and cleanability of glazed surface. In this paper, raw glazes were milled in ball mill for different time. Prepared glaze slurry was applied to green bodies, later dried and fired. The same glaze was also uniaxially pressed to form cylindrical sample; the specimen was placed on substrate surface and fired in hot stage microscope. The glaze evolution upon heating was recorded by CCD camera, the contact angle between molten glaze and substrate was measured to determine the wettability. The results showed that particle-size distributions have great influence on the melting behavior of glaze and the surface appearance of glazed ceramics.     

Study of provenance character on ancient porcelain of Yue Kiln at Silongkou with NAA

Chemical composition is an important information of studying the provenance character of ancient pottery and porcelain. The ancient celadon samples produced in Later Tang (850–907 A.D.) to Former Southern Song (1127–1279 A.D.) have been analyzed with NAA. Its provenance characteristic was compared with that of Hongzhou Kiln of Jiangxi Province and Yaozhou Kiln of Shanxi Province in this paper. The experimental data were studied with statistic methods. The results indicated that the chemical compositions of ancient porcelain body samples made in three kilns were different. The difference is able to be identified. The porcelain body materials of both Silongkou Yue Kiln and Hongzhou Kiln were similar. The samples of Yaozhou kiln in north of China existed obvious difference.     

紫外光引发LDPE膜接枝含氟丙烯酸酯的研究

通过紫外光引发表面接枝聚合反应的方法 ,把含氟丙烯酸酯单体R 5 6 1 0引到LDPE薄膜上 .对经丁酮抽提后的接枝膜进行FTIR、ESCA、SEM和DSC等表征 ,证实含氟聚合物以化学键的方式接枝在LDPE基体膜上 .在一定范围内 ,增加紫外光强、引发剂和单体浓度以及反应温度等均有利于提高接枝率 .经计算R 5 6 1 0的紫外光引发接枝聚合反应总活化能为 5 4 2kJ mol.接枝膜的接触角随着接枝率的提高逐步增大 ,直至趋于恒定 .作者提出接枝膜存在一个在接触角测定时影响基体膜与探测水滴相互作用过程的边界层 .当接枝率较低、接枝层厚度小于边界层临界厚度时 ,基体LDPE影响接触角的大小 ,但随着接枝率提高 ,接枝层逐渐变厚 ,氟聚合物层对接触角的贡献逐渐占优势 ,导致接触角随之增大 .当接枝率超过一定值以后 ,接枝层厚度超过边界层临界厚度 ,接枝层对接枝膜的接触角起全部贡献 ,接触角测定值随之稳定