Decomposition of thin titanium deuteride films: thermal desorption kinetics studies combined with microstructure analysis

The thermal evolution of deuterium from thin titanium films, prepared under UHV conditions and deuterated in situ at room temperature, has been studied by means of thermal desorption mass spectrometry (TDMS) and a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The observed Ti film thickness dependent morphology was found to play a crucial role in the titanium deuteride (TiDy) film formation and its decomposition at elevated temperatures. TDMS heating induced decomposition of fine-grained thin Ti films, of 10–20 nm thickness, proceeds at low temperature (maximum peak temperature Tm about 500 K) and its kinetics is dominated by a low energy desorption (ED = 0.61 eV) of deuterium from surface and subsurface areas of the Ti film. The origin of this process is discussed as an intermediate decomposition state towards recombinative desorption of molecular deuterium. The TiDy bulk phase decomposition becomes dominant in the kinetics of deuterium evolution from thicker TiDy films. The dominant TDMS peak at approx. Tm = 670 K, attributed to this process, is characterized by ED = 1.49 eV

Structural and chemical characterisation of titanium deuteride films covered by nanoscale evaporated palladium layers

Thin titanium deuteride (TiDy) films, covered by an ultra-thin palladium layer, have been compared with the corresponding titanium and palladium films using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The TiDy layers were prepared under ultra-high vacuum (UHV) conditions by precisely controlled deuterium sorption at 298 K on a Ti film evaporated onto a Si(100) substrate. Both Ti and TiDy films were then covered in situ by a nanoscale Pd layer. It was found that a 10- to 12-nm-thick Pd layer protects the TiDy films efficiently against extensive air interaction. The morphology of both the surface and bulk Pd/TiDy (Ti) films have been observed using SEM and cross-sectional TEM analysis, respectively. A polycrystalline bulk morphology in both Ti and TiDy films accompanied by a fine-grained Pd surface was observed. High-magnification cross-sectional TEM images reveal the TiDy film to be plastically deformed leading to an increase in the roughness of the top Pd layer. Complex structures, including Moiré patterns, have been identified within the Pd/TiDy interface. The chemical nature of this interface has been analysed after partial sputtering of the Pd top layer using XPS. Besides TiDy and Pd, TiO and PdO were found to be the main chemical species in the interface region of the Pd/TiHy film. The XPS valence-band spectra of the Pd/TiDy interface reveal electronic features characteristic of a Pd–Ti bimetallic structure

Microstructural and chemical transformation of thin Ti/Pd and TiDy/Pd bi-later films induced by vacuum annealing

Using a combination of scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction and X-ray photoelectron spectroscopy (XPS), we made a comparative study of the high-temperature annealing impact on thin titanium deuteride (TiD y ) films covered by an ultrathin Pd layer, and on Ti/Pd bilayer films. The bilayer films were prepared under ultrahigh vacuum conditions and were in situ annealed using the same annealing procedure. It was found that the surface and the bulk morphology of both films undergo different annealing-induced transformations, leading to an extensive intermixing between the Ti and Pd layers and the formation of a new PdTi2 bimetallic phase. Energy-filtered TEM imaging and energy-dispersive X-ray spectrometry analysis, as well as XPS depth profiling all provided evidence of a different distribution of Pd and Ti in the annealed TiD y /Pd film compared with the annealed Ti/Pd film. Our results show that thermal decomposition of TiD y , as a consequence of annealing the TiD y /Pd film, modifies the intermixing process, thereby promoting Ti diffusion into the Pd-rich top layer of the TiD y film and thus providing a more likely path for the formation of the PdTi2 phase than in an annealed Ti/Pd fil

To see or not to see: Imaging surfactant coated nano--particles using HIM and SEM

Nano--particles are of great interest in fundamental and applied research. However, their accurate visualization is often difficult and the interpretation of the obtained images can be complicated. We present a comparative scanning electron microscopy and helium ion microscopy study of cetyltrimethylammonium--bromide (CTAB) coated gold nano--rods. Using both methods we show how the gold core as well as the surrounding thin CTAB shell can selectively be visualized. This allows for a quantitative determination of the dimensions of the gold core or the CTAB shell. The obtained CTAB shell thickness of 1.0 nm--1.5 nm is in excellent agreement with earlier results using more demanding and reciprocal space techniques.Comment: revised versio

Baseline neutrophil-lymphocyte ratio holds no prognostic value for esophageal and junctional adenocarcinoma in patients treated with neoadjuvant chemotherapy

BACKGROUND: Several studies have reported that neutrophil-lymphocyte ratio (NLR) can predict survival in esophageal and gastroesophageal junction adenocarcinoma, as it reflects systemic inflammation. Hence, we aimed to determine whether baseline NLR holds prognostic value for esophageal adenocarcinoma patients treated with neoadjuvant chemotherapy (nCT) followed by surgery. METHODS: We studied the data of 139 patients that received nCT before undergoing esophagectomy with curative intent, all identified from a prospectively maintained database (1998-2016). Pretreatment hematology reports were used to calculate the baseline NLR. A receiver operating characteristic curve (ROC-curve) was plotted to determine an optimal cutoff value. NLR quartiles were used to display possible differences between groups in relation to overall survival (OS) and disease-free survival (DFS) using the method of Kaplan-Meier. Cox regression analysis was performed to assess the prognostic value of NLR. RESULTS: The median OS and DFS times were 46 months (interquartile range [IQR]: 19-166) and 30 months (IQR: 13-166], respectively, for the entire cohort. The ROC-curve showed that NLR has no discriminating power for survival status (area under the curve = 0.462) and therefore no optimal cutoff value could be determined. There were no statistically significant differences in median OS times for NLR quartiles: 65 (Q1), 32 (Q2), 45 (Q3), and 46 months (Q4) (P = 0.926). Similarly, DFS showed no difference between quartile groups, with median survival times of 27 (Q1), 19 (Q2), 36 (Q3), and 20 months (Q4) (P = 0.973). Age, pN, pM, and resection margin were independent prognostic factors for both OS and DFS. On the contrary, NLR was not associated with OS or DFS in univariable and multivariable analyses. CONCLUSION: Baseline NLR holds no prognostic value for esophageal and gastroesophageal junction adenocarcinoma patients treated with nCT in this study, in contrast to other recently published papers. This result questions the validity of NLR as a reliable prognostic indicator and its clinical usefulness in these patients

Similarity of aberrant DNA methylation in Barrett's esophagus and esophageal adenocarcinoma

Background Barrett's esophagus (BE) is the metaplastic replacement of squamous with columnar epithelium in the esophagus, as a result of reflux. It is the major risk factor for the development of esophageal adenocarcinoma (EAC). Methylation of CpG dinucleotides of normally unmethylated genes is associated with silencing of their expression, and is common in EAC. This study was designed to determine at what stage, in the progression from BE to EAC, methylation of key genes occurs. Results We examined nine genes (APC, CDKN2A, ID4, MGMT, RBP1, RUNX3, SFRP1, TIMP3, and TMEFF2), frequently methylated in multiple cancer types, in a panel of squamous (19 biopsies from patients without BE or EAC, 16 from patients with BE, 21 from patients with EAC), BE (40 metaplastic, seven high grade dysplastic) and 37 EAC tissues. The methylation frequency, the percentage of samples that had any extent of methylation, for each of the nine genes in the EAC (95%, 59%, 76%, 57%, 70%, 73%, 95%, 74% and 83% respectively) was significantly higher than in any of the squamous groups. The methylation frequency for each of the nine genes in the metaplastic BE (95%, 28%, 78%, 48%, 58%, 48%, 93%, 88% and 75% respectively) was significantly higher than in the squamous samples except for CDKN2A and RBP1. The methylation frequency did not differ between BE and EAC samples, except for CDKN2A and RUNX3 which were significantly higher in EAC. The methylation extent was an estimate of both the number of methylated alleles and the density of methylation on these alleles. This was significantly greater in EAC than in metaplastic BE for all genes except APC, MGMT and TIMP3. There was no significant difference in methylation extent for any gene between high grade dysplastic BE and EAC. Conclusion We found significant methylation in metaplastic BE, which for seven of the nine genes studied did not differ in frequency from that found in EAC. This is also the first report of gene silencing by methylation of ID4 in BE or EAC. This study suggests that metaplastic BE is a highly abnormal tissue, more similar to cancer tissue than to normal epithelium.Eric Smith, Neville J De Young, Sandra J Pavey, Nicholas K Hayward, Derek J Nancarrow, David C Whiteman, B Mark Smithers, Andrew R Ruszkiewicz, Andrew D Clouston, David C Gotley, Peter G Devitt, Glyn G Jamieson and Paul A Dre

Global Discourses and national reconstruction: the impact of globalization on curriculum policy

Globalization has been widely discussed and much contested. It has been claimed that the process of globalization has impacted greatly on the capacity of the nation-state to formulate policy (e.g. Reich, 1992). Moreover, globalization has been accompanied by, or at least runs parallel to, a seemingly endless process of change within education. This process has assumed a worldwide character, as policies have migrated around the world; thus there have existed many similarities in terms of, for instance, curriculum provision, or school governance, between New Zealand, Australia, the United Kingdom and the USA. This article examines the nature and extent of education change in general terms, and the concept of globalization, before analysing the links between globalization and the process of change in one area of education, that is, the development of national frameworks for curriculum and assessment within anglophone nations