Diagnostics of high-temperature steel pipes in industrial environment by laser-induced breakdown spectroscopy technique: the LIBSGRAIN project

In this paper are presented the results of the feasibility study for the application of non-destructive spectroscopic methods to the diagnostics of steel pipes in industrial environment. The activities here described are part of the LIBSGRAIN project, funded by the European Commission; the main aim of the project is correlating the probability of failure of industrial plants components with the results of space-resolved elemental analysis carried out with laser-induced breakdown spectroscopy (LIBS) technique. Several simulations have been made in order to check the detectability of dangerous deterioration of steel pipes and to optimize some experimental parameters as the laser focal spot size and the traverse scanning step of the laser head. A design of a laser head which can operate in a real plant and can overcome the problems related to high temperature and vibration is proposed. The feasibility of remote controlled measurements at high temperature has been demonstrated in laboratory tests. The accuracy of LIBS measurements on steel target has been tested on NIST certified steel samples.     

Using developed creep constitutive model for optimum design of HDPE pipes

Unlike metal pipes, high density polyethylene (HDPE) pipes are not susceptible to erosion and corrosion. However, the most important mechanical feature of the HDPE pipes is that this material creeps even at room temperature. Therefore, it is essential to study the creep behavior of this material in order to develop a model. In this paper, creep behavior of HDPE at different temperature and stress levels has been experimentally studied to obtain the creep constitutive parameters of the material. These parameters are used to predict the creep behavior of different structures such as HDPE pipes. For this purpose, a number of specimens have been machined from industrial manufactured pipe walls. Uniaxial creep tests have been carried out and creep strain curves with time for each test were recorded. Then, a constitutive model is proposed for HDPE based on the experimental data and optimization methods. The results of this model have been compared with the test data and good agreement is observed. The developed constitutive model and reference stress method (RSM) were used to produce graphs which provide optimum creep lifetime and design conditions for HDPE pipes that are subjected to combined internal pressure and rotation. These graphs can facilitate the design process of HDPE pipes.     

Assessing the long-term performance of polyethylene stabilised with phenolic antioxidants exposed to water containing chlorine dioxide

The addition of chlorine dioxide disinfectant to tap water prevents the spread of infection but has a serious drawback in that it degrades materials used in piping, including pipes made of polyethylene. Efficient methods are required to assess the long-term performance of different combinations of antioxidants and polyethylene grades. We have previously presented a screening method which exposes solutions of phenolic antioxidants in squalane (a liquid, low molar mass analogue of polyethylene) to 70 °C water containing either chlorine dioxide or chlorine. This method assesses the stability of the antioxidants towards these aqueous chlorinated media by determining the oxidation induction time through differential scanning calorimetry. The same experimental set-up with two modifications was used in developing a new method. A 0.3 mm thick polyethylene tape replaced the squalane phase and the supply of fresh water containing chlorine dioxide (10 ppm at pH = 6.8) was continuous; this required minimum attention from the operator over the longer exposure time periods used. Tapes of medium-density polyethylene containing 0.1 wt.% of six different phenolic antioxidants were studied. A linear relationship was established between the times to reach antioxidant depletion in the polyethylene tape samples and the times in the squalane samples (with the same antioxidants at the same concentration). A linear relationship was also found between the initial antioxidant consumption rates in polyethylene and squalane. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion.     

Eigen-line in welded structures of thermoplastic polymers

Welding is widely used as a joining method for thermoplastics, and it is imperative to ensure the joining quality, particularly for critical applications. In a previous work by the authors, an Eigen-line was found in the electrofusion joint of polyethylene (PE) pipes based on ultrasonic tests and it could be used to detect and assess cold welding defects. However, the nature of the Eigen-line and reasons for the Eigen-line's existence in ultrasonic images have not yet been fully understood, which limited its applications. In this paper, Eigen-lines were observed in other thermoplastics including polypropylene (PP), polyamide 6 (PA 6), polyoxymethylene (POM) and polyethylene terephthalate (PET), suggesting that Eigen-lines have common existence. Microindentation tests were conducted on specimens cut from electrofusion joints and butt joints of PE pipes. It was found that a significant change of elastic modulus exists around the Eigen-line, which can partly explain the appearance of an Eigen-line in ultrasonic images. Scanning electron microscopy (SEM) and reflective optical microscopy were also employed to explore the nature of the Eigen-line. The results showed that an Eigen-line is a thin layer with polymer chain orientation between base material and welded zone.     

Two new criteria for the service life prediction of plastics pipes

In this contribution, two new criteria and related methodologies for the prediction of the long-term (creep rupture) behavior of single layer and multilayer plastics pipes under hydrostatic pressure are presented. One of these is the ultimate strain extrapolation method (USEM) and the other is called the distortion energy extrapolation method (DEEM). The strain concept is based on the use of the failure strain criteria instead of the normally employed stress concept. A related long-term extrapolation methodology is presented that employs the ultimate strain instead of the rupture stress. The strain energy concept is based on the use of the distortion energy corresponding to the failure stress. For both of these two criteria, related extrapolation methodologies are introduced. An example is presented that compares the classical standard extrapolation method (SEM) with the ultimate strain and the energy methods. For correlation of various models, an example of a PVC-U pipe under internal hydrostatic pressure at T=20 °C was studied. The three models employed were the stress-based, the strain-based, and the energy-based regression analyses. Direct regression analysis was performed for all three failure criteria. However, for comparison, the modified version of the SEM was also used. In all cases, a complete match between the independent model and the modified SEM analysis was obtained. A backward calculation of failure stress from the long-term failure distortion energy gave a 50-year failure stress equal to 18.59 MPa. This value was lower than the stress-based extrapolation (25.37 MPa) and higher than the strain-based extrapolation. The proposed USEM is suitable for materials which fail due to the ultimate strain state and not necessarily due to the maximum stresses. Thus, the proposed strain extrapolation criteria may prove to be especially suitable for brittle and fiber reinforced materials. The strain-based extrapolation can be used in connection with rupture data in internal hydrostatic tests or creep rupture of pipe samples under other loading conditions. The DEEM, on the other hand, is believed to be applicable to a broad range of material types. The proposed methodologies can be used as a new guideline for prediction of the service life of single layer brittle thermoplastics pipes, glass fiber reinforced laminate pipes, and multilayer plastics pipes with fiber reinforced layers.     

Rapid method for evaluating reversed-phase high-performance liquid chromatography column stability

A procedure is presented for the rapid evaluation of HPLC stationary phase stability at pH 8.4 or 10.1 using a temperature of 60 degrees C. Mobile phase (MeOH-0.1 mol l(-1) aqueous NaHCO3, 50:50, v/v) is continuously passed through the column with periodic injections of a test solution until the several chromatographic parameters of the resulting chromatograms are degraded. The tests were applied to several commercial and laboratory-made stationary phases. After degradation two of these phases, one commercial and one laboratory-made, were examined by elemental analysis and scanning electron microscopy to elucidate the degradation process.     

Investigations of local electrical surface characteristics by dynamical scanning force microscopy

A technique is presented that allows to obtain information about sample surface topography and local electrical surface properties simultaneously. A scanning electrical force microscope is used for that purpose which is based on an atomic force microscope (AFM) working in the dynamical mode. Different information channels contained in the cantilever excitation spectrum are separated by a lock-in technique. The physical content of the technique is discussed in detail and the influence of surface topography on the non-topographic imaging is demonstrated. Finally, the real advantages of cross-sectional sample preparation (as known from electron microscopy) for this kind of scanning probe microscopy with respect to various applications is presented.     

Differential resin-dentin bonds created after caries removal with polymer burs

The objective of this article was to investigate the effect of carbide and polymer burs caries removal methods on the bond strength of different adhesives to dentin. Resin restorations were performed in sound and caries-affected dentin, after using polymer or carbide burs and bonding with four different adhesive (Single bond, SB; Clearfil SE bond, SEB; FL-Bond II, FLB; and Fuji II-LC, FUJI). Microtensile bond strength (MTBS) was measured. Data were analyzed with ANOVA and Student-Newman-Keuls tests. Debonded surfaces were observed by scanning electron microscopy. Bonded interfaces were examined using light microscopy (Masson's trichrome staining). In sound dentin, MTBS was similar for SEB and SB, and higher than that of FLB and FUJI. Bond strength to carbide bur prepared dentin was similar for SB, SEB, and FLB; FUJI presented the lowest. SB applied on polymer bur excavated dentin presented similar values to those of the carbide bur group; MTBS attained by SEB, FLB, and FUJI decreased when bonding to dentin treated with polymer burs; FUJI yielded pretesting failures in all specimens. Polymer burs created a thick smear layer that was not infiltrated by tested self-etching agents. The bonding effectiveness of self-etching and glass-ionomer-like adhesives to dentin decreased when polymer burs were used.     

The effect of silica morphology on properties of PVA/silica nano-composites

Two kinds of poly(vinyl alcohol)(PVA)-silica composites were prepared with different methods. One composite was prepared by directly mixing PVA with 80 nm silica nano-particles which were made from tetraethoxysilane(TEOS). The another was obtained by the mixing PVA and hydrolyzed TEOS in the presence of acid-catalyst. The properties of the two PVA/silica hybrids were characterized by means of scanning electron microscopy(SEM), UV-Visible spectroscopy,solubility tests, limiting oxygen index(LOI) test, tensile test and dynamical mechanical analysis(DMA), respectively. The results indicate that PVA-TEOS composites(PT for short) display more transparency than PVA-silica nano-particles hybrids(PS for short). At the same time, The PT composites presented more excellent performance than PS in water resistance, fire resistance and mechanical properties. Moreover, the Tg of PT increased with increasing TEOS content, while that of PS decreased.     

Surface analytical characterisation of Nd:YAG-laser pre-treated Al Mg3 as a preparation for bonding

The contribution summarises results of the surface pre-treatment of Al Mg3 (EN-AW-5754) for bonding applications. Mainly the sheet samples were irradiated with a pulsed solid-state laser in different atmospheres. Afterwards the pre-treated surfaces were analysed by quantitative topographic measurements, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and electrochemical impedance spectroscopy (EIS). The effect of surface pre-treatment on the strength of adhesively bonded specimens was evaluated by tensile lap-shear strength tests. The results were compared with conventional pre-treatment methods, such as anodic oxidation and others.     

Determination of thermal oxidation of high density polyethylene pipes using differential scanning calorimetry

Fifteen high density polyethylene pipes were investigated by differential scanning calorimetry. The internal surface layer of thermal oxidized pipes was found to have a lower melting temperature and lower crystallinity compared with the material in a similar position in nonoxidized pipes. Analysis of the radial gradient of melting temperature and crystallinity showed significant differences between oxidized and nonoxidized pipes. This is expected since thermal oxidation decreases the regularity of the chemical structure by bond scission, branching and cross-linking of molecules, and thereby reduces crystallinity and melting temperature.     

Effects of different sterilization processes on the properties of a novel 3D‐printed polycaprolactone stent

Bioresorbable stents (BRS) offer the potential to improve long‐term patency rates by providing support just long enough for the artery to heal itself. While manufacturing methods to produce BRS using the appropriate architecture, material and mechanical studies, etc., have received much attention, the effects subsequent sterilization methods have on BRS properties are overlooked. Sterilization process can change a device's properties. This work presents the effects ethanol, ultraviolet light (UV), and antibiotic sterilization processes at 0.5, 1, 2, 4, 8, and 16 hours have on a novel 3D‐printed polycaprolactone stent. The stents were analysed using sterility tests, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, mass spectrometry, for molecular weight, and degradation tests. Results have shown ethanol to be an effective sterilization treatment as it barely affected the material's properties. On the other hand, UV had a considerable influence (mainly produced by the photodegradation of UV irradiation) on crystallinity and molecular weight. Lastly, while antibiotic sterilization did not affect crystallinity to the same degree, it did substantially reduce the molecular weight of the samples. Ethanol results in being the best sterilization method for the high material requirements that medical devices such as stents have.     

金属的电化学微区刻蚀方法

本文概述了现行的金属微区刻蚀方法并详细地介绍几种电化学刻蚀方法 ,比较了掩膜法、扫描电化学显微镜法、约束刻蚀剂层法、电化学扫描隧道显微镜法和超短电位脉冲法各自的特点 .从加工精度 (能否进行微米和纳米级加工 )、加工效率 (工序复杂程度 ,能否批量制造或复制 )、可用范围 (主要是能否加工复杂三维立体结构 )等各项因素进行了综合分析 ,结果表明 ,各种加工方法各有其优缺点 ,从总的效果来看 ,约束刻蚀剂层技术在微加工方面具有较大优势     

World of nanostructures - nanotechnology,surface properties of chosen nanomaterials

Summary The paper presents the basic information on nanotechnology and the recent results of studies of physicochemical properties of chosen nanomaterial surfaces (montmorillonites, carbon nanotubes, smart surfaces) by means of complex measuring methods. Physicochemical properties of nanomaterial surfaces by means of the special thermogravimetry Q-TG, sorptometry, porosimetry, atomic force microscopy (AFM) and scanning electron micrograph (SEM) methods were investigated. A numerical and analytical procedure for the evaluation of total heterogeneous properties (desorption energy distribution and pore-size distribution functions) on the basis of liquid thermodesorption from the sample surfaces under the quasi-equilibrium conditions and sorptometry techniques are presented. The evaluation of the fractal dimensions of nanotubes using the sorptometry, porosimetry, thermogravimetry Q-TG and AFM data are presented. The comparison of fractal coefficients calculated based on them with the results from Q-TG, sorptometry, porosimetry and AFM gave good agreement.     

A new method for the detection of thermal oxidation in polyethylene pipes

Dumb-bell shaped specimens containing the inner wall surface of the pipe cut from 12 polyethylene pipes of different origin were subjected to constant uniaxial tensile loads at 313 K in air. The brittleness of the inner wall surface layer of the thermally oxidized pipes manifested itself in a shift of the unstable/stable necking transition to lower stresses and longer times. With the aid of optical and scanning electron microscopy, the brittleness of the inner wall surface layer of the oxidized pipes was demonstrated in distinctive surface cracks, which were the dominant feature of the drawn samples of the oxidized pipes. No such surface cracks were observed in the non-oxidized samples. The surface crack patterns were characterized in terms of crack frequency (longitudinal and transverse), width of fragments of cracked top layer (l_B), plastic strain of the fragments of the cracked top layer (ε_pl) and thickness of the cracked top layer (H). Correlations were found that can be interpreted according to basic principles of fracture mechanics. Through knowledge of, for example, ε_pl and l_B the values of the other variables can be predicted. The thickness of the cracked top layer corrected for the reduction in thickness due to plastic deformation is approximately equal to the thickness of the oxidized layer as determined by polarized microscopy. Drawing in an Instron Tensile Testing Machine at an elongation rate of 10 mm/min at 298 K also revealed the distinctive surface cracks in the oxidized samples. On the basis of these results, a new method for the detection of thermal oxidation in polyethylene pipes is proposed.     

Hybrid Cements with ZnO Additions: Hydration,Compressive Strength and Microstructure

The effect of ZnO has already been studied for Portland cement, but the study of its impact on hybrid pastes is scarce. Thus, in this investigation, the influence of ZnO addition on hydration, compressive strength, microstructure, and structure of hybrid pastes is presented. The analyses were made by setting time tests, compressive strength tests, X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis with differential scanning calorimetry, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The results indicate that the setting time of the cements was delayed up to 39 min with additions of 3 wt% ZnO. Alternatively, the higher values of compressive strength were observed when 0.5 wt% ZnO was added to the cements for all curing days. In addition, no important differences in the microstructure of samples with different additions of ZnO were observed after 28 days of curing. It is expected that the use of ZnO contributes to the delay of the setting time and the increase of the compressive strength without negatively modifying the microstructure of hybrid pastes.     

LiFePO_4新型正极材料电化学性能的研究

采用固相反应结合高速球磨法,合成了锂离子电池新型正极材料LiFePO4,并对该材料进行碳包覆处理;采用XRD、SEM、元素分析以及价态化学分析等方法对样品进行表征.实验表明,LiFePO4具有3.4V的放电电压平台,而且包覆碳后的磷酸铁锂具有更好的电化学性能,首次放电容量达147mAh/g,充放电循环100次后容量只衰减9.5%.     

Amyloidosis of Alzheimer's Abeta peptides: solid-state nuclear magnetic resonance, electron paramagnetic resonance, transmission electron microscopy, scanning transmission electron microscopy and atomic force microscopy studies

Aggregation cascade for Alzheimer's amyloid-beta peptides, its relevance to neurotoxicity in the course of Alzheimer's disease and experimental methods useful for these studies are discussed. Details of the solid-phase peptide synthesis and sample preparation procedures for Alzheimer's beta-amyloid fibrils are given. Recent progress in obtaining structural constraints on Abeta-fibrils from solid-state NMR and scanning transmission electron microscopy (STEM) data is discussed. Polymorphism of amyloid fibrils and oligomers of the 'Arctic' mutant of Abeta(1-40) was studied by (1)H,(13)C solid-state NMR, transmission electron microscopy (TEM) and atomic force microscopy (AFM), and a real-time aggregation of different polymorphs of the peptide was observed with the aid of in situ AFM. Recent results on binding of Cu(II) ions and Al-citrate and Al-ATP complexes to amyloid fibrils, as studied by electron paramagnetic resonance (EPR) and solid-state (27)Al NMR techniques, are also presented.     

Microscopy in the studies of polymer biodegradation

The goal of the paper is to overview different possibilities of microscopy, which can be helpful in estimating some of the changes undergoing in the materials exposed to the action of micro-organisms. The types of microscopic techniques and methods discussed in the paper are; optical transmission microscopy (OTM), optical transmission microscopy with polarised light (OPTM), optical reflected microscopy (ORM), optical reflected microscopy with polarised light (OPRM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The above methods allow to follow the changes of the surface view, the changes inside the polymer and the changes in birefringence (in the case of semi-crystalline polymers). The results can be compared with other techniques used for monitoring of polymer biodegradation or biostability. The examples from author's studies on different types of polyurethanes and the blends of polyethylene with starch are also described in the paper.     

Characterization and theory of electrocatalysts based on scanning electrochemical microscopy screening methods

A strategy for finding new electrocatalysts for the oxygen reduction reaction (ORR) in acidic solutions is outlined and illustrated with results for Pd-Co catalysts. This is based on establishing guidelines for selecting test systems, rapid preparation of arrays, and rapid screening by scanning electrochemical microscopy. Promising candidates are further tested as supported electrocatalysts by larger scale electrochemical methods and in fuel cells, with optimization of the composition and structure. Those that emerge are characterized by a variety of methods, including X-ray diffraction, scanning electron microscopy, and X-ray photoemission spectroscopy. Finally, density functional theory is used for detailed calculations of oxygen adsorption and dissociation on the material and provides better guidelines for further testing.