Si，Ag，F离子共修饰HA纳米生物薄膜的制备与表征

采用单电流阶跃电化学沉积技术,在商业纯钛(CP-Ti)表面构建硅、银、氟离子共修饰羟基磷灰石(Si-Ag-F-HA)纳米复合薄膜。Ag+的持续释放可以提供有效的抗菌性,Si4+作为生物活性元素可以有效地抵消Ag+的潜在细胞毒性。采用电感耦合等离子体质谱法(ICP-MS)测定涂层中硅和银元素的释放规律。采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、能量弥散X射线谱(EDS)、X-射线衍射(XRD)等技术对得到的材料进行了表征。结果表明：Si,Ag和F三种元素均匀地掺杂到了HA的晶体结构中。Si-Ag-F-HA为纳米级的针状晶体结构,薄膜整体致密且均匀。Si-Ag-F-HA纳米生物薄膜可以在一周内很好地诱导类骨磷灰石的形成,具有优异的生物活性。塔菲尔曲线测试结果证实涂层的耐SBF腐蚀性较好。ICP-MS测试结果表明Si-Ag-F-HA纳米生物薄膜可以提供持续的Si和Ag离子释放。FTIR 和ICP-MS等光谱技术为开发新型抗菌硬组织修复材料提供了高效快速的检测手段。     

Tentative differentiation between Iznik tiles and copies with Raman spectroscopy using both laboratory and portable instruments

Iznik tiles dated from the 16th century, copies of tiles and pottery of Théodore Deck from the 19th century and also tiles without any information on their origin were analyzed with both laboratory and portable Raman instruments. As the original tiles are generally fixed on the walls of historical buildings, the portable Raman spectrometer is more convenient for the analysis but the information obtained from the spectra is not very useful because of the medium resolution and complex baseline of the instrument in spite of its speed and ease of use. The Raman signature of the glazes is the most pertinent and easily accessible fingerprint of the artifacts. The differentiation between Iznik ceramics and other samples could be made with Raman spectrometers, according to the specific signature of Si O stretching and bending bands of Iznik glazes. Copyright © 2009 John Wiley & Sons, Ltd.     

太平天国侍王府壁画表面修复材料的原位无损FTIR分析

太平天国侍王府壁画是中国南方壁画的典型代表,具有重要的历史、文化和艺术价值。历史上曾对多幅壁画进行过化学保护,部分壁画表面形成了一定厚度的有机物涂层,分析研究壁画保护修复材料成分对于文物保护具有重要的理论和现实意义。由于文物的珍贵性与不可再生性,原位无损分析技术的研究和应用是未来文物分析的发展趋势,基于便携红外光谱仪的反射红外光谱技术是对文物表面材质较为理想的无损分析手段。利用反射傅里叶变换红外(FTIR)光谱对侍王府壁画的地仗层和表面修复材料涂层进行了现场原位无损分析,这在我国古代壁画及其保护修复材料分析中属首次。首先测试了无涂层壁画白色背景位置反射FTIR光谱,并与标准无机矿物光谱比对确定了壁画地仗层成分主要为方解石和生石膏。在此基础上,分析了无涂层和有涂层壁画表面的红外反射特性及地仗层化学成分对表面涂层反射FTIR光谱测试的影响,探讨了应用Kramers-Kronig(K-K)变换处理数据的可行性,确定了K-K变换的应用范围,分析了壁画涂层K-K变换后反射光谱与衰减全反射(ATR)光谱的差异,并通过显微ATR FTIR光谱和热裂解气相色谱质谱联用(Py-GC/MS)技术分析验证了原位反射FTIR光谱测试结果的可靠性,扫描电子显微镜(SEM)测量了涂层厚度,证明不同厚度涂层均能得到可解析的高质量反射FTIR光谱。最终确定侍王府壁画曾使用过聚醋酸乙烯酯、聚二甲基硅氧烷和三甲树脂三种高分子材料进行过表面加固,并得出壁画保存现状和修复材料及涂层厚度有较大关系。证明了基于反射模式的FTIR光谱技术能准确有效地获取文物表面有机物和部分无机物成分信息。该方法对表面有机涂层尤为敏感,是壁画类文物较为理想的无损分析方法,在壁画保护研究领域具有十分广阔的应用前景。同时,该研究弥补了我国壁画类文物表面有机物原位无损分析的不足,为该领域研究提供了一条新思路。     

基底温度对α-C:H膜微观结构的影响

使用RF-PECVD法分别在基底温度为60℃、120℃和200℃的N型单晶锗表面制备了α-C:H膜,采用拉曼光谱、傅里叶变换红外吸收光谱和原子力显微镜等技术手段研究分析了α-C:H膜的价键组成及表面形貌,讨论了基底温度对α-C:H膜微结构及部分性能的影响。结果表明,在α-C:H膜沉积过程中,基底温度对膜层微观结构有较大影响,基底温度60℃时,膜层表面光滑、致密无石墨化现象。随着基底温度的升高,α-C:H膜中含H量和微晶石墨量逐渐增多,α-C:H膜层性能也逐步退化。     

空间材料抗原子氧有机涂层防护作用的光谱分析

用Fourier变换红外光谱(FTIR)、光电子能谱(XPS)和扫描电镜(SEM)对在模拟原子氧(AO)环境中,空间材料及在其表面涂覆的有机防护涂层的表面所发生的侵蚀与防护作用进行了研究。结果表明：采用环氧树脂、聚胺脂、醇酸树脂作为防护涂层,经AO辐照后,它们的表面形貌均发生了较大变化,腐蚀严重;而用有机硅涂层的表面形貌变化却甚小,具有较明显的防护效果。光谱分析表明,这种防护作用缘于有机硅涂层表面经AO辐照后生成了致密的氧化硅膜层,对抑制AO的进一步侵蚀起到了抑制作用。     

Comparison of anti-corrosion properties of polyurethane based composite coatings with low infrared emissivity

Four polyurethane resins, pure polyurethane (PU), epoxy modified polyurethane (EPU), fluorinated polyurethane (FPU) and epoxy modified fluorinated polyurethane (EFPU), with similar polyurethane backbone structure but different grafting group were used as organic adhesive for preparing low infrared emissivity coatings with an extremely low emissivity near 0.10 at 8-14 μm, respectively. By using these four resins, the effect of different resin matrics on the corrosion protection of the low infrared emissivity coatings was investigated in detail by using neutral salt spray test, SEM and FTIR. It was found that the emissivity of the coatings with different resin matrics changes significantly in corrosion media. And the results indicated that the coating using EFPU as organic adhesive exhibited excellent corrosion resistance property which was mainly attributed to the presence of epoxy group and atomic fluorine in binder simultaneously.     

Goldstone mode of a magnon Bose−Einstein condensate in MnCO<Subscript>3</Subscript>

The dependence of the enhancement of the Raman scattering on the size of a dielectric column is measured in structures with the spatial modulation of the height and lateral sizes of the dielectric coated with a thick metal layer (10–80 nm). It is established that, in the case of a thick metal coating (silver, gold, and copper coatings are used) at dimensions of the dielectric column close to the laser pump wavelength, considerable enhancement of the Raman signal oscillating upon the variation of the geometrical dimensions of the structure is observed. It is shown that the observed resonance enhancement of the Raman signal is associated with the transformation of the electromagnetic radiation into localized plasmon–polariton modes, and the efficiency of such transformation is determined by the commensurability of the wavelength of the plasmon–polariton mode and the planar size of the metal film. For different metal coatings, the dependence of the enhancement of the Raman scattering on the laser wavelength is measured.     

KPCA-聚类分析法和用便携式拉曼仪快速鉴别降糖药

对不同种类的降糖药片进行拉曼光谱的核主成分分析(KPCA)-聚类分析,实现快速、简便的鉴别。KPCA可以有效地避免主成分分析(PCA)只能处理线性问题和降维效果不明显的弊端。它通过一个非线性变换,首先将原变量空间映射到高维特征空间,然后在这个高维特征空间中进行线性主成分分析。采集得到的药片拉曼光谱的KPCA-聚类分析结果表明,采用KPCA提取特征变量的聚类结果比采用PCA提取特征变量后进行聚类分析的效果好,并且未经刮除表面包膜的降糖药片识别准确率为96.5%,经过刮除表面包膜处理的降糖药片的识别准确率为100%。便携式拉曼光谱仪结合该方法以其检测速度快、准确率高、使用简便、无样品前处理等显著优势,为药品的快速检验技术提供一种新的有效的鉴别手段。     

Low-temperature biomimetic formation of apatite/TiO2 composite coatings on Ti and NiTi shape memory alloy and their characterization

Through a low temperature process, a bilayer composite coating was formed on Ti and NiTi shape memory alloy (SMA). The composite coating consisted of a layer of titania, which was formed using a H₂O₂-oxidation and hot water aging technique, and a layer of apatite, which was formed through an accelerated biomimetic process by immersing as-oxidized metals in a high-strength simulated body fluid (5SBF). Various techniques including X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the surfaces of samples at different stages of coating formation and the coatings formed. Bioactive apatite/TiO₂ coatings could be formed on NiTi SMA and firmly bonded to the metal substrate. But there were differences for the formation of the composite coating on Ti and NiTi SMA substrates. The composite coatings formed will render both metals bioactive and hence bone-bonding.     

Influence of NH beam bombarding energy on structural characterization and cell attachment of CNx coating

The carbon nitride (CN_x) coating with its novel properties will be excellent candidate for biomedical applications. CN_x coatings were prepared on the surface of Ti–6Al–4V by ion-beam-assisted deposition (IBAD) with different NHⁿ⁺ beam bombarding energies at low substrate temperature. The coatings were characterized by Scanning electron microscopy (SEM), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier-transform infrared (FTIR) spectroscopy. The result showed that the wear-resistance of CN_x coatings was better at higher beam bombarding energy. The cell attachment tests also gave interesting results that CN_x coatings exhibited low macrophage attachment and provide desirable surface for the normal cellular growth and morphology of the fibroblasts. Structural analysis showed that NHⁿ⁺ beam bombardment at the energies of 300–400 eV could result in more nitrogen concentration and fraction of sp³CN bonds in the structure of CN_x coatings, which may be responsible for the improvement in the wear-resistance and the cell attachment.     

Nanostructured bioactive glass-ceramic coatings deposited by the liquid precursor plasma spraying process

Bioactive glass-ceramic coatings have great potential in dental and orthopedic medical implant applications, due to its excellent bioactivity, biocompatibility and osteoinductivity. However, most of the coating preparation techniques either produce only thin thickness coatings or require tedious preparation steps. In this study, a new attempt was made to deposit bioactive glass-ceramic coatings on titanium substrates by the liquid precursor plasma spraying (LPPS) process. Tetraethyl orthosilicate, triethyl phosphate, calcium nitrate and sodium nitrate solutions were mixed together to form a suspension after hydrolysis, and the liquid suspension was used as the feedstock for plasma spraying of P₂O₅-Na₂O-CaO-SiO₂ bioactive glass-ceramic coatings. The in vitro bioactivities of the as-deposited coatings were evaluated by soaking the samples in simulated body fluid (SBF) for 4 h, 1, 2, 4, 7, 14, and 21 days, respectively. The as-deposited coating and its microstructure evolution behavior under SBF soaking were systematically analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma (ICP), and Fourier transform infrared (FTIR) spectroscopy. The results showed that P₂O₅-Na₂O-CaO-SiO₂ bioactive glass-ceramic coatings with nanostructure had been successfully synthesized by the LPPS technique and the synthesized coatings showed quick formation of a nanostructured HCA layer after being soaked in SBF. Overall, our results indicate that the LPPS process is an effective and simple method to synthesize nanostructured bioactive glass-ceramic coatings with good in vitro bioactivity.     

焦炉上升管内壁结焦炭层的光谱学分析及结焦机理研究

以焦炉上升管内壁结焦炭层块为研究对象，采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和激光共聚焦拉曼光谱仪（Raman）对结焦炭层的元素组成，以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性，揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe，S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭，在焦炉上升管内壁形成炭颗粒沉积，为焦油凝结挂壁提供载体，在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构，随着结焦炭层从外表面向内表面过渡，各结焦炭层的面层间距(d₀₀₂)逐渐降低、层片直径(L_a)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行，主要包括其片层外缘的羧基和部分C-O结构的降解剥离，从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题，提高换热器换热效率，有效回收焦炉荒煤气显热，降低焦化企业能耗提供实验基础和理论依据。     

Characterization of oxide coatings formed on tantalum by plasma electrolytic oxidation in 12-tungstosilicic acid

Oxide coatings were formed on tantalum by plasma electrolytic oxidation (PEO) process in 12-tungstosilicic acid. The PEO process can be divided into three stages with respect to change of the voltage-time response. The contribution of electron current density in total current density during anodization results in the transformation of the slope of voltage-time curve. The surface morphology, chemical and phase composition of oxide coatings were investigated by AFM, SEM-EDX, XRD and Raman spectroscopy. Oxide coating morphology is strongly dependent of PEO time. The elemental components of PEO coatings are Ta, O, Si and W. The oxide coatings are partly crystallized and mainly composed of WO₃, Ta₂O₅ and SiO₂. Raman spectroscopy showed that the outer layer of oxide coatings formed during the PEO process is silicate tungsten bronze.     

Raman spectroscopy of automotive paints: Forensic analysis of variability and spectral quality

Raman spectroscopy was evaluated as a forensic technique for the analysis of automotive paints with the purpose to verify the measurement variability as well as to study the spectral quality by means of parameters and conditions. The objective lens, accumulation number, and laser (power, mode, and wavelength) were observed to significantly affect the spectral quality and thus should be taken into consideration during the development of a forensic database. On the other hand, exposure time, Raman shift range, and baseline correction had less influence on the features of the obtained spectra. Interestingly, samples collected from the bumper coating composed of a plastic substrate in comparison with fragments obtained from other parts of the same vehicle containing metallic substrate showed different absorption band patterns. In addition, less variability of data acquired directly onto the paint chip’s surface has demonstrated that direct analysis should be preferred during spectra library development as opposed to cross-section measurements. Sample homogeneity and distinction power of the technique combined with Principal Components Analysis were also investigated. The preliminary results showed that although Raman spectroscopy is extremely accurate in the identification of vehicles, it is necessary to pay particular attention to the spectral variability in order to avoid false database matching and misleading of forensic investigations. Therefore, we suggest that separated spectra library shall be developed for each laser wavelength as well as for each sample substrate. Further studies with a higher number of paint chips will enable the establishment of prediction models aimed to identify unknown samples involved in hit-and-run cases.     

Nanoscale morphology for high hydrophobicity of a hard sol-gel thin film

It is challenging to obtain a hydrophobic smooth coating with high optical and mechanical properties at the same time because the hydrophobic additives are soft in nature resulting in reduced hardness and durability. This paper reports a durable hydrophobic transparent coating on glass fabricated by sol-gel technology and a low volume medium pressure (LVMP) spray process. The sol-gel formula consists of a pre-linked hydrophobic nano-cluster from hydroxyl-terminated polydimethylsiloxane, titanium tetraisopropoxide and a silica-based sol-gel matrix with silica hard fillers. Polydimethylsiloxane (PDMS) is uniformly distributed throughout the coating layer providing durable hydrophobic property. Mechanical properties are achieved by the hard matrix and hard fillers with the nano-structures. Due to the surface nano-morphology, a high degree of hydrophobicity was maintained with only 10 vol.% PDMS, while the hardness and abrasion resistance of the coatings were not significantly compromised. Chemical analyses by FTIR confirmed the uniform distribution of the PDMS and surface morphology analyses by atomic force microscopy (AFM) displayed the nano-surface structures that enhanced the hydrophobicity. The special surface nanostructures can be quantified using surface Kurtosis and ratio between asperity peak height to distance between peaks. The LVMP process influences the spray droplet size resulting in different surface structures.     

The Uniform Si-O Coating on Cotton Fibers by an Atmospheric Pressure Plasma Treatment

A uniform Si-O coating on cotton fabric was produced at atmospheric pressure by a plasma treatment. Before the plasma discharge, a pretreatment with hexamethyldisiloxane (HMDSO)-ethanol mixture solvents on the fabric was employed. The surface morphology and chemical structure of the plasma-treated fibers were analyzed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analyses. The SEM results showed that a uniform, continuous film was formed on the cotton fiber surface. It was much rougher than the uncoated fiber. The FTIR results showed that the coatings contained most of the Si-O functional groups. These Si-O bonds, broken from the Si-O-Si functional groups by the plasma electron impact, had connected with the cellulose by chemical bonds of Si-O-Cellulose. XRD patterns revealed the existence of a crystalline structure within the thin coating film. The UV-vis transmission of the cotton textile was greatly reduced by such coatings.     

Plasmon‐enhanced polarized Raman spectroscopy for sensitive surface characterization

Local‐mode and localized surface plasmons generated on the silver thin film can selectively enhance the Raman signal from the surface. Further improvement of surface signal can be obtained by using the polarized Raman technique that results in a dramatic enhancement of the surface sensitivity by up to 25.4 times as compared to that without a silver coating. This technique will be very useful for Raman study on samples that suffer overlapping background signal. In this article, we show that it can be used to significantly improve the signal of thin strained‐Si layer on top of SiGe buffer layer. Copyright © 2008 John Wiley & Sons, Ltd.     

缓冲层对LBO晶体上1 064 nm，532 nm增透膜附着力的影响

 采用电子束蒸发方法在LBO晶体上制备了无缓冲层和具有不同缓冲层的1 064 nm,532 nm二倍频增透膜。利用分光光度计、纳米力学综合测试系统以及调Q脉冲激光装置对样品的光学性能、附着力以及抗激光损伤性能进行了测试分析。结果表明：所有样品在1 064 nm和532 nm波长的剩余反射率都分别小于0.1％和0.2％;与无缓冲层样品相比,预镀Al₂O₃缓冲层样品的附着力提高了43.1％,具有SiO₂缓冲层样品的附着力显著提高,而MgF₂缓冲层的插入却导致薄膜附着力降低。应用全塑性压痕理论和剪切理论对薄膜的附着力增强机制进行了分析。薄膜的抗激光损伤性能分析表明,SiO₂缓冲层也有助于改进薄膜的激光损伤阈值。     

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。     

CCD紫外敏感Lumogen薄膜制备与光谱表征

传统的CCD和CMOS成像传感器对紫外区域响应比较弱,这是因为多晶硅栅对紫外光有强的吸收能力,从而阻碍了紫外光进入CCD沟道。为了提高探测器对紫外辐射的敏感性,可行的一种办法是在器件上镀一层可以将紫外光转化为可见光的变频膜。采用真空蒸发法制备了有机Lumogen薄膜,并用发光官能团分析、椭圆偏振技术研究了Lumogen薄膜的发光原理与光学常数。分析与实验结果表明：Lumogen可连续光致发光原因是其分子具有四类双键结构;椭圆偏振法测得该Lumogen薄膜折射率在1.3左右,说明该膜具有增透效果。同时,通过测量Lumogen薄膜的透射光谱、吸收光谱、光致发光发射谱和激发谱,表征了Lumogen薄膜的光谱性质,发现Lumogen薄膜在可见波段(>470 nm)有较好的透过性,用紫外光激发会产生较强的黄绿光(中心波长位于523 nm),且激发光谱宽(240～490 nm)。结论表明Lumogen薄膜的发射光谱能够与CCD等传统硅基成像器件的响应光谱匹配,是一种符合实际要求的紫外敏感薄膜。