过渡金属表面γ-氨丙基三甲氧基硅烷膜的研究

本文对在过渡金属铁、镍电极表面制备得到的γ-氨丙基三甲氧基硅烷(γ-APS)膜进行了研究。实验中对硅烷膜用X-射线光电子能谱(XPS)、现场表面增强拉曼散射光谱(SERS)和原子力显微镜(AFM)进行了表征。X-射线光电子能谱(XPS)的结果发现存在两个N1s峰,表明γ-APS膜中的氨基有两种存在方式:自由氨基和质子化氨基。实验中还发现现场表面增强拉曼散射光谱(SERS)是研究金属/γ-APS体系中界面层结构非常有效的手段,SERS结果表明硅醇羟基和氨基发生了竞争吸附,且γ-APS分子在外加电位等条件的影响下吸附状态会发生一定变化。原子力显微镜(AFM)的表征结果在微观上显示电极表面的γ-APS膜上形成了一种较规则的微孔结构,这种结构可能与基底的性质有关。     

石墨炉内石墨探针表面上的原子化机理研究 Ⅳ钒的原子化机理

本文通过X-射线衍射分析(XRD),扫描电子显微镜分析(SEM),化学分析光电子能谱分析(ESCA),并结合原子吸收测量,研究了钒在普通石墨管中石磨探针表面上发生的固相化学反应。结果表明,钒化合物在灰化阶段即可转化为热稳定性较高的碳化物,原子化的最后步骤为碳化物的热分解。     

激光清洗陶瓷文物表面污染层的实验研究

近年来激光清洗技术逐渐应用在文物保护领域。针对陶瓷文物样品表面的黄色污染层(铁锈)和黑色污染层(CaSO_4或PbCO_3与灰尘的混合物),进行纳秒激光清洗文物的实验研究。实验上采用肉眼观察和激光共聚焦高倍显微镜测量等手段,通过改变激光功率、扫描速度和清洗次数等参数,控制陶瓷表面污染物的烧蚀作用和清洗效果,探索两种污染物的优化清洗参数。实验中得到了陶瓷文物样品表面两种污染物的最佳清洗参数,为陶瓷文物的修复和保护提供数据支撑。     

XPS研究Nd表面氧化物的生长过程

用X射线光电子能谱(XPS)研究新鲜Nd表面在不同氧气和空气进气量的情况下,表面氧化物的生长过程.发现氧化层由氧化物、氢氧化物及表面化学吸附水三种成分,这三种成分的增加与进气量都存在正比对数关系,氧化物和吸附水在一定进气量后趋于饱和,而氢氧化物持续不断增加,最终氢氧化物占据主要地位. 关键词： X射线光电子能谱(XPS) Nd 氧化     

红外光谱法研究古代彩绘蛋白胶料光老化的二级结构变化

动物胶和蛋清是古代重要彩绘文物蛋白胶结材料,对其光老化蛋白质结构变化的研究与探索彩绘文物病变机理和选择科学保护材料、修复方法密切相关。以维也纳艺术历史博物馆的动物胶(骨胶、兔皮胶、鲟鱼胶)和蛋清为研究对象,利用红外光谱技术,结合酰胺Ⅰ带去卷积和高斯拟合法研究光老化过程中蛋白质二级结构的改变。结果表明,四种胶光老化后仍然具备蛋白质红外光谱的典型吸收特征。但红外吸收峰出现了不同程度的位移,其中蛋清糖苷键明显蓝移。酰胺Ⅰ带去卷积和高斯拟合结果显示,蛋白胶的二级结构占比发生了改变。其中,骨胶α-螺旋结构占比降低22.24%,逐渐解螺旋,无规则卷曲结构占比明显增高(9.76%);兔皮胶和鲟鱼胶α-螺旋结构占比分别降低5.31%,4.15%,前者无规则卷曲增幅最低(6.96%),后者反而减少,推测两者的光老化稳定性高。蛋清α-螺旋占比降低程度最高(44.45%),无规则卷曲占比增幅极大(27.49%),光老化稳定性最差。证实利用红外光谱技术,结合酰胺Ⅰ带去卷积和高斯拟合法研究文物蛋白胶料二级结构变化的方法是可行的,但其转化机理还需后期进一步探讨。     

Fe/ZnO (0001)体系界面相互作用中薄膜厚度效应的光电子能谱研究

利用同步辐射光电子能谱(SRPES)和X射线光电子能谱(XPS)技术,系统研究了室温下Fe/ZnO界面形成过程中Fe薄膜与氧结尾的ZnO(000 1 )衬底之间的相互作用,结果显示初始沉积的Fe明显被表面氧氧化为Fe²⁺离子,在Fe覆盖度为0—3 nm的范围内,分别观察到与界面电荷传输、化学反应以及薄膜磁性相关的三个有意义的临界厚度,这一结果将有助于基于Fe/ZnO界面的相关器件的设计和研发. 关键词： Fe/ZnO 界面作用 同步辐射光电子能谱 X射线光电子能谱     

高能氮离子轰击对四面体非晶碳膜的表面改性和摩擦系数影响的研究

利用过滤阴极真空电弧技术制备了sp³键含量不小于80%的四面体非晶碳(ta-C)膜.利用冷阴极潘宁离子源产生不同能量的氮离子对制备的ta-C薄膜进行轰击,通过X射线光电子能谱和原子力显微镜对薄膜表面结构与形貌进行分析研究.研究表明,随着氮离子的轰击能量的增大,薄膜中的CN键结构略有增大,形成了轻N掺杂;同时,在薄膜表层发生了sp³键结构向sp²键结构的转化;薄膜的表面粗糙度在经过氮离子轰击后从0.2 nm减小至0.18 nm,然后随着轰击能 关键词： 四面体非晶碳 X射线光电子能谱 摩擦系数     

分子束外延GaN薄膜的X射线光电子能谱和俄歇电子能谱研究

用XPS和AES电子能谱的方法对等离子体辅助分子束外延(MBE)生长的GaN薄膜进行了表面分析和深度剖析.发现红外分子束外延(RFMBE)生长的富镓GaN薄膜实际表面存在O和C吸附层,C主要为物理吸附,而O在GaN表面形成局域化学键产生氧络合物覆盖层,并形成一定的深度分布.杂质O在GaN带隙中导带底形成杂质带同时引入深受主能级,使得带隙变窄室温光吸收谱向低能方向移动,光致发光谱出现宽带发光峰.从而影响GaN薄膜的电学和光学性质 关键词： GaN薄膜 X射线光电子能谱 俄歇电子能谱 表面分析     

NiTi合金薄膜厚度对相变温度影响的X射线光电子能谱分析

采用X射线衍射和X射线光电子能谱实验手段对不同厚度的NiTi薄膜相变温度的变化进行了分析.结果表明在相同衬底温度和退火条件下,3?μm厚度的薄膜晶化温度高于18?μm厚度的薄膜.衬底温度越高,薄膜越易晶化,退火后薄膜奥氏体相转变温度As越低.薄膜的表面有TiO₂氧化层形成,氧化层阻止了Ni原子渗出;膜与基片的界面存在Ti₂O₃和NiO.由于表面和界面氧化层的存在,不同厚度的薄膜内层的厚度也不同,因而薄膜越薄,Ni原子的含量就越高.Ni原子的含量的不同会影响薄膜的相变温度. 关键词： NiTi合金薄膜 X射线衍射 相变 X射线光电子能谱     

FT-IR、XPS和DFT研究乙酰氧肟酸钠在针铁矿或赤铁矿表面的吸附机理

采用FT-IR、X射线光电子能谱以及基于周期平面波的DFT方法分别研究了乙酰氧肟酸钠(aHA)在针铁矿或赤铁矿表面上的吸附结构,并将计算得到的光电子能谱移动和电荷转移实验得到的XPS结果进行对比.红外结果显示aHA可能以五元环螯合物形式吸附于针铁矿或赤铁矿表面,DFT计算结果表明aHA中氧肟酸基团的两个氧原子与针铁矿(101)或(100)表面上的一个铁原子形成五元环结构,同时氧肟酸基团中的两个氧还相应的与针铁矿表面邻近两个铁原子成键,但氧肟酸基团中的两个氧原子却只与赤铁矿(001)表面上的一个铁原子形成五元环结构.对于针铁矿(101)、(100)和赤铁矿(001)表面上吸附位点对应的铁原子,计算得到的光电子能谱移动与实验得到的光电子能谱移动基本相等,说明了计算结果的可靠性和所得吸附结构的合理性.     

Characterization of laser cleaning of limestone

The precise and controlled cleaning of polluted limestone sculpture by a Q-switched Nd:YAG laser is described. Acoustic monitoring of the cleaning process is used to demonstrate the selective removal of black crusts from stone surfaces. Results are also presented which show that by applying a thin layer of water to the surface of the crust prior to irradiation, cleaning can be achieved at a lower energy than with normal laser cleaning. The probability of damage to the underlying stone is, therefore, reduced.     

Geochemical study of black crusts as a diagnostic tool in cultural heritage

This contribution focuses on spectrometric analyses carried out on crust samples covering the stone surface of the boundary walls of the Tower of London. The main goal of this research is to investigate the degradation processes related to the environmental impact on cultural heritage. Specifically, the chemical contamination of stone substrate in the Tower of London due to the crust formation was examined through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). This technique allowed us to achieve a complete characterization of the damage layers in terms of trace elements. In addition, optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDS) and infrared spectroscopic techniques (FT-IR) were also used for an exhaustive characterization of the examined samples. Results obtained demonstrated that such a geochemical approach represents a powerful diagnostic tool in the study of black crusts, since it represents a reliable indicator of the environmental pollution. The higher concentrations of most heavy metals in black crusts with respect to the underlying stone suggest that crusts were greatly influenced by atmospheric inputs in their formation, mainly represented by mobile combustion sources. In addition, the possibility of analyzing in some samples the portion of altered substrate allowed us to hypothesize that some specific heavy metals tend to migrate from the crust to the unaltered substrate over time, becoming catalysts for the formation of new crust. Therefore, this research focuses on the role of diagnostics in order to plan suitable cleaning and consolidation intervention aimed at a better protection of the monument.     

Nanoparticles for conservation of bio-calcarenite stone

In the present study, the consolidation effectiveness of some inorganic nanoparticles dispersions (silica, calcium hydroxide, and strontium hydroxide) has been evaluated when applied on a very porous stone substrate, i.e., Lecce stone. The strengthening effect of the nanoparticle-based treatments was compared to that exhibited by the well-known consolidant tetraethoxysilane. Ca(OH)₂ and Sr(OH)₂ nanoparticles were prepared in laboratory and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), dynamic light scattering (DLS), and Fourier transform infrared spectroscopy (FTIR). The kinetic stability of nanoparticles dispersions was determined by UV-vis spectrophotometric studies. Moreover, the study of the nanolime carbonatation process was carried out using FTIR spectroscopy. Distribution of the applied product into the stone substrate was examined by SEM-EDS. The chemical weathering effect of salt crystallization of the treated specimens was evaluated by performing the dry weight loss (DWL) test. All the results suggested that Ca(OH)₂ and Sr(OH)₂ nanoparticles, applied as 2-propanol dispersions, display some good properties as consolidating agents for a very porous bio-calcarenite such as Lecce stone.     

福建寿山黑田与坑头黑的谱学与矿物学研究

寿山石是我国国石候选石之一,也是四大图章石之首。寿山石中黑田为黑色田黄石,是田黄中的特殊品种,产于寿山溪两旁的田地中。母源区坑头占的位置产有黑色坑头石。本文将黑田与母源区的黑色坑头石(坑头黑)进行对比研究,采用X射线粉晶衍射(XRD)、红外吸收光谱(IR)、激光剥蚀等离子质谱仪(LA-ICP-MS)和扫描电镜(SEM)对它们的矿物成分、红外吸收峰特征、颜色成因以及矿物的微区形貌特征进行对比研究。测试结果显示,黑田与坑头黑的矿物成分不同,红外光谱和X射线粉晶衍射分析表明坑头黑以地开石为主;另外,X射线粉晶衍射分析表明坑头黑中可含有杂质矿物如叶蜡石、伊利石、黄铁矿和石英。而红外光谱和X射线粉晶衍射分析表明黑田的主要成分为地开石或者珍珠陶石;另外,X射线粉晶衍射分析表明黑田中含有少量的硫磷铝锶矿和镁硫铁矿。黑田与坑头黑的矿物微形貌也存在差异,黑田矿物晶粒大小不一致、片状晶体颗粒边缘圆化,说明黑田中矿物晶体曾遭受过水岩反应的溶蚀改造作用。而坑头黑中地开石结晶程度良好,晶粒呈片状,边棱尖锐,晶体颗粒大小较为一致,说明坑头黑为原生矿。根据LA-ICP-MS微量化学成分分析测试,初步认为黑田与坑头黑的黑色皆与Fe元素致色有关,该结论有待进一步测试研究。     

壳聚糖/SrHAP复合涂层的制备及其FTIR特征分析

在含有Sr2+,Ca2+,PO3-₄和壳聚糖(CHI)的电沉积液中,用恒电流沉积法,在医用纯钛(Ti)表面上得到壳聚糖/掺锶羟基磷灰石(SrHAP)复合涂层。采用扫描电镜(SEM)、能量弥散X射线谱(EDS)、X射线衍射(XRD)对涂层进行检测,用傅里叶变换红外光谱(FTIR)考察了壳聚糖和锶离子的掺杂对HAP涂层构象和生物活性的影响。结果表明：锶部分取代磷灰石中的钙,表面形貌由疏松的针状变为较致密的片状。FTIR分析表明,涂层中出现了典型的amideⅠ和amideⅡ的壳聚糖振动峰,则CHI与SrHAP杂化良好;模拟生理液浸泡后表面覆盖有球状类骨磷灰石,则涂层具备较好的生物活性。塔菲尔测试表明,复合涂层使得Ti表面的抗生理腐蚀性显著提高。     

Study of sulphation of Candoglia marble by means of micro X-ray diffraction experiments

This research is aimed at assessing the particular kind of damage caused by the interaction between atmospheric pollution and the marble surface of a magnificent late gothic church, Milan Cathedral, restored in the early 1970s. On the basis of visual inspections and diagnostic investigations the facade appears to be seriously damaged by surface erosion and thick black crusts; biological crusts, micro-fractures and detachments are widely present.This paper reports on SR-μXRD data collected at the Synchrotron Radiation Source (SRS), Daresbury Laboratory, and at the European Synchrotron Radiation Source (ESRF) from selected samples, covered with black crusts, originating from the Milan Cathedral facade. Mineralogical maps of the deterioration layers have been recorded by two spatial resolutions (5–100 μm), from the bulk of the stone material to the outer layer of the black surface. These maps help in elucidating the mechanism of formation of the black crusts. PACS 33.20.Rm; 61.10.Eq; 61.10.Nz; 78.70.Ck     

Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications

Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.     

锰和氟共修饰羟基磷灰石陶瓷涂层的制备与表征

由于钛及钛合金具有优越的理化性能,其已被广泛应用于各种植入体,例如骨科、牙科及心血管支架等。然而,钛基材表面具有生物惰性,其与周边骨组织形成骨整合的能力较弱,延缓了组织愈合的时间。因此,改善钛植入体表面生物性能具有重要的临床意义。钛基材表面羟基磷灰石(HAP)复合涂层的制备已成为一种重要的表面生物活性改良手段。在含有F-,Mn2+,Ca2+和PO3-₄的电解液中,用单电流阶跃沉积法,在钛金属(Ti)表面上涂覆锰和氟共修饰羟基磷灰石(FMnHAP)复合薄膜。采用扫描电子显微镜(SEM)、能量弥散X射线谱(EDS)、X-射线衍射(XRD)对涂层进行初步表征,用傅里叶变换红外光谱(FTIR)技术验证了氟离子和锰离子的共修饰对HAP分子构象和生物活性的影响。结果表明：锰部分取代磷灰石中的钙,氟部分取代磷灰石中的羟基,FMnHAP晶格常数变小,薄膜表面形貌由微米级的针状变为纳米级的绒毛状。FTIR技术验证显示,由于磷灰石晶体结构中F取代部分OH,致使改变了结构中OH的弯曲振动模式的对称性;模拟体液体外矿化表明,涂层表面有含碳酸根的类骨磷灰石形成,则涂层的体外生物活性较好。极化曲线测试表明,涂层提高了Ti在生理环境中的耐腐蚀性。     

镁合金阳极氧化膜腐蚀特性的红外显微成像分析

采用显微红外成像技术对镁合金阳极氧化膜表面的腐蚀特性进行了研究。镁合金在7.3 Wt% Na₂SO₄溶液中浸泡后,表面氧化层中的部分MgO逐渐转化为Mg(OH)₂,进而发生溶解和脱落,使得镁合金失去保护作用。当浸泡时间达到2 h时,显微红外成像结果表明阳极氧化膜中Mg(OH)₂的红外吸收信号最强,Mg(OH)₂的含量最多。而4 h后Mg(OH)₂的红外吸收信号开始减弱,Mg(OH)₂开始减少,镁合金不断被腐蚀。氧化膜中另一成分Al₂O₃随浸泡时间的显微红外成像信息与Mg(OH)₂的变化规律相同。采用电化学阻抗谱技术对阳极氧化膜的阻抗进行测试,其阻抗随时间的变化特点基本符合氧化膜腐蚀规律。本研究对于镁合金阳极氧化膜的表征具有很好的指导作用和推广应用价值。     

Investigation on porosity changes of Lecce stone due to conservation treatments by means of x‐ray nano‐ and improved micro‐computed tomography: preliminary results

Cultural heritage materials are subject to continuous chemical and physical changes depending on the establishment of a dynamic equilibrium with the environment in which they are placed. In particular, different phenomena can take place, such as formation of black crusts, corrosion of the material, internal cracks. Lecce stone, a biocalcarenite mainly used for historical buildings in South Italy, has a high total porosity. In order to prevent its deterioration, different kinds of hydrophobic organic products are applied on the surface of the restored artefacts. Since the efficacy of the treatments depends mostly on the penetration depth and the distribution of the products in the pores, porosity and internal structure of the stone material were mainly investigated in this research. Micro x‐ray computed tomography (µ‐CT) has been used to study and characterize the internal structure of different samples, untreated and treated with protective products. The porosity and other parameters of the rock were then calculated and compared, before and after the conservation treatment, in order to highlight the changes due to the application of the product. On the other hand, small pieces of the untreated and treated samples were analysed by sub‐micron resolution x‐ray tomography where it was possible to see the distribution of the products inside the pores. Copyright © 2007 John Wiley & Sons, Ltd.