Electron microscopy investigation of AlMg6 aluminum alloy surface defects caused by microorganisms extracted in space stations

The surfaces of AMg6 (aluminum-magnesium) alloy samples that have passed accelerated biocorrosion tests have been investigated in a Quanta-3D scanning electron microscope. The alloy samples have been treated with the Ulocladium botrytis Preuss fungus, which is an active destructive fungus and was previously extracted on surfaces of the International Space Station. Biocorrosion pits 2–10 μm in diameter, cavities the depths of which can reach 70–250 μm depth, and spots of modified color are found to be the most typical defects. The surfaces of large cavities consist of faceted cubic particles that are formed when the acid products of fungus metabolism interact with the alloy surface. The particles have an average size of 30 μm, which is close to the size of alloy grains. The microstructure of a biocorrosion layer has been investigated in a Quanta-3D microscope with the use of a focused Ga⁺ ion beam. The samples of 12-μm-wide transverse slices are obtained near large cavities and investigated in a Tecnai G₂₃0ST transmission electron microscope. The X-ray microanalysis of the defective layer has revealed the high concentration of oxygen in this layer. Obtained images indicate that the corrosion cavity surface has a complex porous structure.     

多层隔热材料飞行试验研究综述

考虑在低地球轨道中热控材料的性能变化直接影响航天器的温度,本文从3个方面研究了多层隔热组件的在轨性能变化。首先,介绍了地面模拟空间环境对热控材料的破坏试验;然后,重点对比分析了哈勃望远镜、长期暴露装置和国际空间站上多层隔热组件样本的试验数据,得到了相关的材料性能结果;最后,详细描述了哈勃望远镜维修用多层隔热组件面膜的地面筛选试验。通过对比在轨飞行数据和地面试验数据发现,影响近地轨道卫星多层隔热组件面膜寿命的首要因素是原子氧和温度循环的共同作用,紫外照射和带电粒子的影响相对较弱。该结论为地面加速试验的规划与修正和长寿命航天器的热设计提供了参考依据。     

A method for the study of surface corrosion beneath protective layers

This work is concerned with the development of a technique to observe the onset of corrosion as it occurs beneath a temporary protective layer. Such temporary protectives include paints, varnishes, greases and oils that are applied to metal surfaces to give short-term protection from corrosion. The objective of this project was to develop a technique that could be used to evaluate the effectiveness of various temporary protectives in different environments, without the need to remove the protective layer, thus eliminating the possibility of any chemical changes or loss of corrosion products occurring as a result of removal. The temporary protective layers are typically 25Μm for paints and 15Μm per layer for varnishes. The 6.3 keV fluorescence X-ray is able to penetrate such layers, but the large escape depth (∼10Μm) of the X-rays means that for a thin protective layer a large proportion of the X-rays detected will originate from deep within the substrate and the resultant spectrum will be representative of the bulk rather than the surface. To enhance the surface sensitivity of the CXMS technique, the near surface region must be enriched in the isotope Fe-57. To achieve this, Fe-57 was vacuum evaporated onto the surface of mild steel substrates and subsequently diffused into the near surface region. An approximate 20 nm Fe-57 layer was deposited onto mild steel samples. The surface enriched samples were then annealed to allow the Fe-57 to diffuse into the near surface region of the mild steel substrate, and also to allow back diffusion of the substrate. A diffusion model was developed to predict the surface distribution of Fe-57 as a function of annealing parameters. The computer diffusion model allowed the ideal annealing conditions to be estimated to obtain a required near surface environment. It was essential that the annealing conditions did not result in any surface oxidation, and did result in a surface that was characteristic of mild steel. CEMS and CXMS spectra were recorded of samples before and after annealing, and also dynamic Secondary Ion Mass Spectrometry (SIMS) was used to monitor the enrichment and diffusion process. Energy Dispersive X-ray Analysis (EDXA) was also used to characterize the surface. A number of enriched samples were prepared and treated with a variety of surface temporary protectives. The CXMS spectra were recorded before and after exposure of the coated samples to various aggressive environments.     

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.     

Physical-morphological and chemical changes leading to an increase in adhesion between plasma treated polyester fibres and a rubber matrix

The effects of plasma treatment, used to increase adhesion strength between poly(ethylene terephtalate) (PET) fibres and a rubber matrix, were investigated and compared. Morphological changes as a result of atmospheric plasma treatment were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Wettability analysis using a surface energy evaluation system (SEE system) suggested that the plasma treated fibre was more wetting towards a polar liquid. When treated, these fibres showed a new lamellar crystallization, as shown by a new melting peak using differential scanning calorimetry (DSC). X-ray photoelectron spectroscopy (XPS) has been used to study the chemical effect of inert (argon), active and reactive (nitrogen and oxygen) microwave-plasma treatments of a PET surface. Reactive oxygen plasma treatment by a de-convolution method shows new chemical species that drastically alter the chemical reactivity of the PET surface. These studies have also shown that the surface population of chemical species formed after microwave-plasma treatment is dependent on the plasma gas. All these changes cause better adhesion strength of the PET fibres to the rubber matrix.     

Flame treatment of low-density polyethylene: Surface chemistry across the length scales

The relationship between surface chemistry and morphology of flame treated low-density polyethylene (LDPE) was studied by various characterization techniques across different length scales. The chemical composition of the surface was determined on the micrometer scale by X-ray photoelectron spectroscopy (XPS) as well as with time of flight secondary ion mass spectrometry (ToF-SIMS), while surface wettability was obtained through contact angle (CA) measurements on the millimeter scale. The surface concentration of hydroxyl, carbonyl and carboxyl groups, as a function of the “number” of the flame treatment passes (which is proportional to the treatment time) was obtained. Moreover, a correlation was found with chemical composition and polarity, emphasizing the role of oxygen-containing functional groups introduced during the treatment. Carboxyl functional groups were specifically identified by fluorescent labeling and the results were compared with the ToF-SIMS data. In addition, atomic force microscopy (AFM) was used to evaluate changes in surface topography and roughness on the nanometer to micrometer length scales. After flame treatment, water-soluble low molecular weight oxidized materials (LMWOM), which were generated as products of oxidation and chain scission of the LDPE surface, agglomerated into small topographical mounds that were visible in the AFM micrographs. After rinsing the flame treated samples with water and ethanol, bead-like nodular surface structures were observed. The ionization state of flame treated LDPE surfaces was monitored by chemical force microscopy (CFM). The effective surface pK_a values of carboxylic acid (-COOH) obtained by AFM were revealed by chemical force titration curves and the effective surface pK_a values were found to be around 6.     

Conditions of formation of stable deposits of incomplete combustion products of liquid rocket fuels on the external elements of orbital stations

The results of the Dvicon and Kromka-1 space experiments aimed at studying the state of contaminant deposits on control samples exposed for a long time in the zone of emission incomplete combustion products from the orientation engines of the Mir Orbital Station and International Space Station. An analysis of the data on the intensity of the action of incomplete combustion products on the control samples during the space experiments made it possible to formulate a critical condition of formation of stable dry deposits of toxic contaminants.     

Nano-second pulse laser treatment of Incoloy 800 HT alloy-corrosion properties

Incoloy alloy 800 HT is widely used material of construction for equipment that must resist corrosion. Moreover, the corrosion properties of the alloy reduce considerably when the alloy is heat treated. However, the short pulse laser treatment of the alloy may offer alternative technique to improve the corrosion properties of the alloy. In the present study, nano-second pulse heating of Incoloy 800 HT alloy is carried out using a Nd-YAG laser. The heating rate and the temperature rise during the laser treatment are predicted theoretically. Electrochemical techniques are applied to determine the corrosion rates of the laser treated and untreated Incoloy 800 HT samples. SEM and EDS are introduced for metallographic examination of the treated alloy surface. It is found that the fine dentritic structures occur at the surface after the laser treatment. The local pitting is observed for the laser melted and re-solidified regions while the scattering of the pits are resulted for the laser heated and unmelted regions. In addition, the corrosion rate reduces for the laser-treated samples.     

Micro‐Raman investigations of early stage silver corrosion products occurring in sulfur containing atmospheres

Silver is a soft, lustrous metal with the highest electrical and thermal conductivity. Due to these properties, it has many applications as a precious material both in pure and alloy form (ornaments, jewellery, utensils, coins), but also in several technological fields, considering silver compounds (e.g. photography, electric and electronic industry). As a consequence of this, silver and its by‐products are regularly exposed to different atmospheres where a wide spectrum of agents (e.g. moisture, temperature, air pollutants, UV light) may cause metal corrosion and alteration of their surface characteristics and properties. The aim of this research is to deepen the potential and applicability of micro‐Raman spectroscopy as a surface‐sensitive technique to investigate the initial steps of atmospheric corrosion throughout the identification of surface chemical reactions and corrosion products formed on silver substrates. In a previous study, micro‐Raman analysis was carried out on pure silver powder compounds, selected among the most expected corrosion products occurring on silver substrates, in order to optimize experimental conditions and to obtain reference spectra ^[1]. Subsequently highly pure silver samples were exposed for 24 h to different controlled laboratory atmospheres (synthetic air, relative humidity, SO₂, H₂S), particularly focusing on sulfur containing gases, and the resulting surface reactions. The experiments highlight micro‐Raman spectroscopy as a highly surface‐sensitive technique enabling to detect both adsorbed chemical species and crystalline corrosion products of only several monolayers of thickness. Furthermore, these investigations could show the trends of primary and secondary corrosion mechanisms and their mutual interaction occurring on silver substrates. Copyright © 2013 John Wiley & Sons, Ltd.     

Production of reference alloys for the conservation of archaeological silver-based artifacts

In the framework of the EC PROMET project, the chemical composition and metallurgical features of a large number of archaeological artifacts were investigated by different analytical surface and bulk techniques, such as Optical Microscopy (OM), Scanning Electron Microscopy coupled with energy dispersive X-ray micro-analysis (SEM-EDS), X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The study of the corrosion products grown on the archaeological Ag-based artifacts revealed a quite ubiquitous and nearly constant presence of chlorine from the soil as the main corroding agent, mainly producing chlorargyrite (AgCl). Results of this extensive chemical, physical and metallurgical characterization were used to produce modern reference Ag-based alloys with a chemical composition and micro-chemical structure similar to that of ancient alloys. Furthermore, these reference Ag-based alloys were submitted to an accelerated degradation method in order to produce corroded samples to be used as sacrificial materials for testing corrosion inhibiting products. The production of artificial “patinas” and corrosion layers was made by a chemical and soil-induced degradation procedure. The comparison of the micro-chemical structures of natural and artificial corrosion layers shows that the selected degradation method produces “patinas” resembling those grown on archaeological artifacts from a chemical, structural and micro-morphological point of view.     

聚四氟乙烯材料表面激光改性与刻蚀

利用波长为248 nm的准分子激光束在不同激光能量密度下照射聚四氟乙烯(PTFE)材料的表面,并用扫描电镜(SEM)、X射线光电子能谱(XPS)、拉曼(Raman)光谱等手段对激光处理前后样品的表面形貌、化学成分和结构进行测量和分析,进而对激光与聚四氟乙烯相互作用的机理进行了研究。实验结果表明,激光辐照使聚四氟乙烯表面产生去氟效应,导致表面碳化、分子链的交联以及含氧基团的产生,随着激光能量密度的增加,C=C双键逐渐形成。这些结构的变化可以导致表面硬度和粘结性增强。激光能量密度的大小对照射后样品表面的物理性质和化学结构有着重要的影响,它是聚合物表面激光改性和烧蚀的关键因素。     

Effect of laboratory and ionospheric plasma on the polymeric materials of spacecraft

A study of the erosion of a number of polymeric and carbon materials used to construct elements of the outer surface of spacecraft upon exposure to oxygen plasma streams with ion energies of 20–30 eV is conducted. It is shown that the relative erosion coefficients (normalized with respect to polyimide) of the studied materials are practically equal to those determined in real experiments aboard the International Space Station. The obtained results give grounds for using the studied plasma-generation mode to conduct accelerated tests of material resistance for prolonged flights in the ionosphere.     

Stability of atmospheric-pressure plasma induced changes on polycarbonate surfaces

Polycarbonate films are subjected to plasma treatment in a number of applications such as improving adhesion between polycarbonate and silicon alloy in protective and optical coatings. The surfaces that undergo changes in surface properties due to plasma treatment have a tendency to revert back to their original states. Thus, the stability of the plasma induced changes on polymer surfaces over a desired time period is an important issue. The objective of this study was to examine the effect of ageing on atmospheric-pressure helium-plasma treated polycarbonate (PC) sample as a function of treatment time. The ageing effects were studied over a period of 10 days. The samples were plasma treated for 0.5, 2, 5 and 10 min. Contact angle made by water droplet on polymer surfaces were measured to study surface energy changes. Modification of surface chemical structure was examined using X-ray photoelectron spectroscopy (XPS). Contact angle decreased from 93° for untreated samples to 30° for samples treated with plasma for 10 min. After 10 days the contact angle for the 10 min plasma treated sample increased to 67°, but it never reverted back to that of the untreated surface. Similarly, the oxygen-carbon (O:C) ratio increased from 0.136 for untreated samples to 0.321 for 10 min plasma-treated samples, indicating an increase in surface energy.     

XPS analysis of the oxidation reaction of ruthenium-chalcogenide photoelectrodes

The oxidation of RuS₂, RuSe₂, and RuTe₂ single crystals and polycrystalline samples by air and electrochemical / photoelectrochemical means have been studied by XPS. The amount of oxidized species detected at the surface can be related to the tendency of the material to electrochemical corrosion. For RuS₂, which is able to oxidize H₂O to O₂ only an oxidation of the top surface layer can be derived from the changes of the O1s is signal. For RuSe₂ and RuTe₂ Ru-oxide/hydroxide and chalcogenide-oxide species are detected in correspondence to their corrosion tendency. The results of the XPS analysis are discussed with respect to the electrocatalytic properties of the materials.     

Effect of dry-ozone exposure on different polymer surfaces and their resulting biocidal action on sporulated bacteria

The current work describes a novel technique by which certain types of polymers subjected to dry gaseous ozone acquire the ability to inactivate microorganisms, including those as resistant as bacterial spores. The originality and advantages of this ozone treatment of polymer surfaces rest on its simplicity (achieved at ambient temperature and pressure, a one step process …) and its efficacy. The inactivation efficiency is found to be specific to the nature of the treated polymer: 24 h after deposition of 10⁶ B. atrophaeus spores from a 100 µL suspension, high inactivation rates are observed with polymethyldisiloxane (99.997%, almost 5 log) and polystyrene (99.7%, more than 2 log), a lower rate with polyurethane (99.1%, 2 log) whereas polytetrafluoroethylene shows no detectable biocidal activity. Changes in hydrophilicity of these surfaces are monitored by means of contact-angle measurements while topographic modifications are characterized through atomic force microscopy. Ozone exposure brings about important topographic changes and chemical modifications on some polymers, which can be correlated with oxidation processes, increased wettability and surface energy. Variations of the dispersive and non-dispersive (polar) components of the surface energy are partially correlated with the polymer biocidal response. Furthermore, the basic component of the treated polymer (in contrast to its acidic component) seems to be correlated with the biocidal activity of the treated surfaces. Chemical species bearing ester groups, probably partially-oxidized styrene oligomers, as revealed by chemical analysis, could be involved in the biocidal activity. On practical grounds, since some of these treated polymers can strongly reduce microorganism loads on their surfaces, they could be particularly useful in hospital environment.     

Influence of N~+ implantation on structure,morphology, and corrosion behavior of Al in NaCl solution

Structural and morphological changes as well as corrosion behavior of N~+ implanted Al in 0.6 M Na Cl solution as function of N~+ fluence are investigated. The x-ray diffraction results confirmed Al N formation. The atomic force microscope(AFM) images showed larger grains on the surface of Al with increasing N~+ fluence. This can be due to the increased number of impacts of N~+ with Al atoms and energy conversion to heat, which increases the diffusion rate of the incident ions in the target. Hence, the number of the grain boundaries is reduced, resulting in corrosion resistance enhancement. Electrochemical impedance spectroscopy(EIS) and polarization results showed the increase of corrosion resistance of Al with increasing N~+ fluence. EIS data was used to simulate equivalent electric circuits(EC) for the samples.Strong dependence of the surface morphology on the EC elements was observed. The scanning electron microscope(SEM)analysis of the samples after corrosion test also showed that the surfaces of the implanted Al samples remain more intact relative to the untreated Al sample, consistent with the EIS and polarization results.     

Corrosion behavior of boride layers evaluated by the EIS technique

The corrosion behavior of boride layers at the AISI 304 steel surface is evaluated in the present study. Electrochemical impedance spectroscopy (EIS) technique was used for the evaluation of the polarization resistance at the steel surface, with the aid of AUTOLAB potentiostat. Samples were treated with boron paste thickness of 4 and 5 mm, in the range of temperatures 1123 ≤ T ≤ 1273 K and exposed time of 4 and 6 h. The electrochemical technique employed 10 mV AC with a frequency scan range from 8 kHz to 3 mHz in deaerated 0.1 M NaCl solution. Nyquist diagrams show that the highest values of corrosion resistance are present in the samples borided at the temperature of 1273 K, with treatment time of 4 h and 4 mm of boron paste thickness. The values of corrosion resistance on borided steels are compared with the porosity exhibited in the layers.     

HZE dosimetry in space using plastic track detectors

Plastic nuclear track detectors were used to measure the contribution of High charge Z and energy E (HZE) particles to the radiation exposure of manned space missions. Results from numerous space missions in the orbit planned for the International Space Station are compared. The measurements cover the declining phase of the last solar cycle during the past 7 years and various shielding conditions inside the US Space Shuttle and the Russian MIR-station.     

Composition and corrosion resistance of cerium conversion films on the AZ31 magnesium alloy and its relation to the salt anion

Pre-treatments based on different cerium salts were applied to the AZ31 Mg alloy. The pre-treatments were performed by immersion in solutions of various Ce(III) salts: cerium chloride, cerium nitrate, cerium sulphate and cerium phosphate. The chemical composition of the treated surfaces was investigated by X-ray photoelectron spectroscopy and Auger electron spectroscopy, whereas the corrosion behaviour of the pre-treated AZ31 substrates was investigated in 0.005 M NaCl solutions using potentiodynamic polarisation and open circuit potential monitoring. The surface film contained a mixture of Ce(IV) and Ce(III) salts. The film thickness depends upon the cerium salt used. The electrochemical results show that all the conversion pre-treatments reduced the corrosion activity of the AZ31 Mg alloy substrates in the presence of chloride ions. The corrosion protection efficiency is related with the anion present in the cerium salt.     

Effect of surface nanocrystallization induced by fast multiple rotation rolling on hardness and corrosion behavior of 316L stainless steel

A nanostructured layer was fabricated by using fast multiple rotation rolling (FMRR) on the surface of 316L stainless steel. The microstructure in the surface was characterized by transmission electron microscopy and X-ray diffraction. The effects of FMRR on the microhardness, surface roughness and corrosion behavior of the stainless steel were investigated by microhardness measurements, surface roughness measurements, potentiodynamic polarization curves and pitting corrosion tests. The surface morphologies of pitting corrosion specimens were characterized by scanning electron microscopy. The results show that FMRR can cause surface nanocrystallization with the grain size ranges from 6 to 24 nm in the top surface layer of the sample. The microhardness of FMRR specimen in the top surface layer remarkably increases from 190 to 530 HV. However, the surface roughness slightly rises after FMRR treatment. The potentiodynamic polarization curves and pitting corrosion tests indicated that the FMRR treated 316L stainless steel with a surface nanocrystallized layer reduced the corrosion resistance in a 3.5% NaCl solution and enhanced the pitting corrosion rate in a FeCl₃ solution. Possible reasons leading to the decrease in corrosion resistance were discussed.