Intrinsically flame retardant epoxy resin - Fire performance and background - Part II

The flame retardant mechanism of a newly synthesized phosphorus-containing reactive amine, which can be used both as crosslinking agent in epoxy resins and as flame retardant, was investigated. The mode of action and degradation pathway were investigated by in situ analysis of the gases evolved during the degradation by thermogravimetric measurements coupled online with infrared (TG-EGA-FTIR) and mass spectroscopy (TG/DTA-EGA-MS) and by solid residue analysis by infrared (ATR) spectroscopic methods and X-ray photoelectron spectroscopy (XPS). It was observed that the main difference in the degradation of the reference and the flame retardant system is that the degradation of the latter begins at lower temperature mainly with the emission of degradation products of the phosphorus amine, which act as flame retardants in the gas phase slowing down the further degradation steps. At the high temperature degradation stage the solid phase effect of the phosphorus prevails: the formation of phosphorocarbonaceous intumescent char results in a mass residue of 23.4%. The ratio of phosphorus acting in gas phase and solid phase, respectively, was determined on the basis of thermogravimetric and XPS measurements.     

Raman spectra and XPS studies of phase changes in Ge2Sb2Te5 films

Ge_2Sb_2Te_5 film was deposited by RF magnetron sputtering on Si (100) substrate. The structure of amorphous and crystalline Ge_2Sb_2Te_5 thin films was investigated using XRD, Raman spectra and XPS. XRD measurements revealed the existence of two different crystalline phases, which has a FCC structure and a hexagonal structure, respectively. The broad peak in the Raman spectra of amorphous Ge_2Sb_2Te_5 film is due to the amorphous －Te－-Te－ stretching. As the annealing temperature increases, the broad peak separates into two peaks, which indicates that the heteropolar bond in GeTe_4 and the Sb－Sb bond are connected with four Te atoms, and other units such as (TeSb) Sb－Sb (Te_2) and (Sb_2) Sb－Sb (Te_2), where some of the four Te atoms in the above formula are replaced by Sb atoms, remain in crystalline Ge_2Sb_2Te_5 thin film. And from the results of Raman spectra and XPS, higher the annealing temperature, more Te atoms bond to Ge atoms and more Sb atoms substitute Te in (Te_2) Sb－Sb (Te_2).     

Antibacterial and physicochemical properties of co‐sputtered CuSn thin films

Copper‐tin thin films (CT TFs) were deposited on p‐type Si(100) by radio frequency (RF) magnetron co‐sputtering method. The atomic ratio of Cu and Sn showed complementary tendency with various RF powers on metal targets. Antibacterial test was conducted with Gram‐negative Escherichia coli. The ratio of Cu and Sn ions and the contact time with E. coli affected the antibacterial efficiency. Increasing the ratio of Cu ions and contact time showed higher antibacterial activity. Cu₂₀Sn₆ called as bronze structure, metallic Cu, and copper oxide phases were identified from X‐ray diffraction data after sterilization. The lattice strain that was changed due to the substitution of Cu and Sn was also calculated. The surface morphology of CT TFs was entirely grown to round shape when the dominant element was Sn. But, as the content of Cu increased, the surface morphology was changed from ball shape to sharp column shape. When fixed contact time, the intensities of Cu 2p increased but the intensities of Sn 3d decreased as increasing the atomic ratio of Cu. The oxidation of Cu was more sharply progressed as the RF power on Cu target increased. When fixed CT TFs, the intensities of Cu 2p were consistent but the intensities of Sn 3d_3/2 decreased as increasing contact time between CT TF and E. coli.     

A growth mechanism for carbon nanotubes using metal oxides as catalysts

Metal oxides have only recently begun to be used as catalysts for the growth of carbon nanotubes. Here, we propose a new model for the growth of carbon nanotubes, based on the intra‐granular charge transfer transition and the lattice strain of the catalyst nanoparticles. This is supported by results obtained from the doped metal oxides like samarium doped zinc oxide (SmZnO) and terbium doped zinc oxide (TbZnO). The intragranular charge transfer transition is believed to be responsible for the dissociation of the hydrocarbon molecules. The lattice strain of the catalyst nanoparticles appears to be responsible for the diffusion of carbon atoms through the catalyst particles.     

六氰合铁酸铜钴薄膜修饰铂电极的电化学、XRD及XPS研究

采用循环伏安法在铂电极上电聚合了六氰合铁酸铜钴薄膜,并用电化学、XRD 和XPS对该薄膜进行了表征。研究表明此薄膜属于取代型的多核六氰合铁酸盐,由 Cu~(2+),Co~(2+)和Fe~(2+)共同占据晶格格点。通过改变Cu~(2+),Co~(2+)和 Fe~(3+)在沉积液中的比例可以改变聚合膜的性质。随沉积液中Cu~(2+)含量的增加 ,聚合膜中铜的含量相应增加而晶格常数则逐渐减小,但保持着面心立方的晶格对 称性。当沉积液中Cu~(2+):Co~(2+):Fe~(3+) = 1:1:2时,得到的聚合膜具有比较 典型的性质,该薄膜修饰的铂电极在pH 4～10之间均能保持着稳定的电化学响应。 其对一价阳离子的选择性顺序为K~+ > Li~+ > Na~+ > NH_4~+,与单组分的六氰铁 酸酮和六氰合铁酸钴都存在着较大的差别。XPS实验表明氧化态薄膜中铁元素以Fe (III)存在,并且在X射线的照射下很快转化为Fe(II)。     

Quantitative analysis of complex amino acids and RGD peptides by X‐ray photoelectron spectroscopy (XPS)

The C 1 s, N 1 s, and O 1 s core level binding energies (BEs) of the functional groups in amino acids (glycine, aspartic acid, glutamic acid, arginine, and histidine) with varied side‐chains and cell‐binding RGD‐based peptides have been determined and characterized by X‐ray photoelectron spectroscopy with a monochromatic Al K_α source. The zwitterionic nature of the amino acids in the solid state is unequivocally evident from the N 1 s signals of the protonated amine groups and the C 1 s signature of carboxylate groups. Significant adventitious carbon contamination is evident for all samples but can be quantitatively accounted for. No intrinsic differences in the XP spectra are evident between two polymorphs (α and γ) of glycine, indicating that the crystallographic differences have a minor influence on the core level BEs for this system. The two nitrogen centers in the imidazole group of histidine exhibit an N 1 s BE shift that is in line with previously reported data for theophylline and aqueous imidazole solutions, while the nitrogen and carbon chemical shifts reflect the unusual guanidinium chemical environment in arginine. It is shown that the complex envelopes of C 1 s and O 1 s photoemission spectra for short‐chain peptides can be analyzed quantitatively by reference to the less complex XP spectra of the constituent amino acids, provided the peptides are of high enough purity. The distinctive N 1 s photoemission from the amide linkages provides an indicator of peptide formation even in the presence of common impurities, and variations in the relative intensities of N 1 s were found to be diagnostic for each of the three peptides investigated (RGD, RGDS, and RGDSC). Copyright © 2013 John Wiley & Sons, Ltd.     

棒状CuFe4Ox的可控合成及其异戊醇脱氢反应的催化性能

利用液相沉淀法可控合成了均匀的棒状CuFe₄O_x催化剂。通过原位X射线粉末衍射（XRD）、高分辨透射电子显微镜（TEM）及程序升温还原（TPR）等手段表征其晶相结构、形貌和还原性能。通过还原棒状CuFe₄O_x获得Cu⁰/Fe₃O₄ 纳米棒,原位X射线光电子能谱（XPS）用于确定Cu⁰/Fe₃O₄ 表面的相组成。通过液相沉淀法制备棒状CuFe₄O_x,在120℃保持3 h后加入Na₂CO₃溶液至pH等于9时所得棒状形貌最为规整。以异戊醇脱氢反应作为探针反应,比较了Cu⁰/Fe₃O₄ 纳米棒和Cu⁰/Fe₃O₄ 纳米颗粒的催化反应性能,发现Cu⁰/Fe₃O₄ 纳米棒比Cu⁰/Fe₃O₄ 纳米粒子具有更好的活性和稳定性,表明棒状Fe₃O₄ 担载的Cu纳米粒子具有更好的结构稳定性。     

High power impulse magnetron sputtering (HIPIMS) and traditional pulsed sputtering (DCMSP) Ag-surfaces leading to E. coli inactivation

This study addresses the high power impulse magnetron sputtering (HIPIMS) deposition of Ag-nanoparticle films on polyester and the comparison with films deposited by direct current pulsed magnetron sputtering (DCMSP). The first evidence is presented for the Escherichia coli bacterial inactivation by HIPIMS sputtered polyester compared to Ag-polyester sputtered by DCMSP. HIPIMS layers were significantly thinner than the DCMSP sputtered layers needing a much lower Ag-loading to inactivate E. coli within the same time scale. The Ag-nanoparticle films sputtered by DCMSP at 300 mA for 160 s was observed to inactivate completely E. coli within 2 h having a content of 0.205% Ag wt%/polyester wt%. HIPIMS-sputtered at 5 A for 75 s led to complete E. coli bacterial inactivation also within 2 h having a content Ag 0.031% Ag wt%/polyester wt%. The atomic rate of deposition with DCMSP is 6.2 × 10¹⁵ atoms Ag/cm² s while with HPIMS this rate was 2.7 × 10¹⁵ atoms Ag/cm² s. The degree of ionization of Ag⁺/Ag²⁺ and Ar⁺/Ar²⁺ was proportional to the target current applied during HIPIMS-sputtering as determined by mass spectroscopy. These experiments reveal significant differences at the higher end of the currents applied during HIPIMS sputtering as illustrated by the ion-flux composition. X-ray photoelectron spectroscopy (XPS) was used to determine the surface atomic concentration of O, Ag, and C on the Ag-polyester. These surface atomic concentrations were followed during the E. coli inactivation time providing the evidence for the E. coli oxidation on the Ag-polyester. X-ray diffraction shows Ag-metallic character for DCMSP sputtered samples for longer times compared to the Ag-clusters sputtered by HIPIMS leading to Ag-clusters aggregates. Ag-nanoparticle films on polyester sputtered by HIPIMS contain less Ag and are thinner compared to Ag-nanoparticle films sputtered by DCMSP.     

Fluorine plasma treatment of bare and nitrilotris(methylene)triphosphonic acid (NP) protected aluminum: an XPS and ToF‐SIMS study

Nitrilotris(methylene)triphosphonic acid (NP) is a technologically important molecule that has been used for years as a corrosion inhibitor and/or adhesion promoter on aluminum and other metal surfaces. However, to the best of our knowledge, the detailed surface characterization of NP adsorbed on aluminum, or on any other surface, has not been reported. Herein, we report an X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) analysis of a series of untreated and NP‐coated aluminum substrates that were exposed to the downstream products of a fluoroalkane + oxygen plasma for different amounts of time (from 0 to 20 s). As indicated by P 2p, N 1s, Al 2p, O 1s, and F 1s narrow scans, even a 4‐s plasma treatment significantly damages the NP protective layer and converts the native aluminum oxide into aluminum oxyfluoride. Heat treatment of the fluorine plasma‐treated samples in the air substantially converts the aluminum oxyfluoride back to aluminum oxide, while similar heating under vacuum results in little change to the materials. A slow loss of fluorine from the samples occurs over the course of weeks when they are stored in the air. A ToF‐SIMS analysis reveals sets of signals that are consistent with no surface treatment, NP treatment, or fluorine plasma treatment. A principal component analysis of the negative ion ToF‐SIMS spectra from the samples shows the expected differentiation of the samples. Copyright © 2014 John Wiley & Sons, Ltd.