6 Materialchemie
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- Laser-induced periodic surface structures (LIPSS) (13)
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- ToF-SIMS (8)
- Hydrogen (7)
- Oxidation (7)
- Tribology (7)
- Wear (7)
- AISI 304L (4)
- Atomic Forc Microscopy (4)
- Deuterium (4)
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During the past few years significantly increasing research activities in the field of laser-induced periodic surface structures (LIPSS, ripples) have been reported since the generation of LIPSS in a single-step process provides a simple way of surface nanostructuring towards a control of optical, mechanical or chemical surface properties. In this contribution the current research state in this field is reviewed. The formation of LIPSS upon irradiation of metals, semiconductors and dielectrics by multiple linearly polarized Ti:sapphire fs-laser pulses (30-150 fs) is studied experimentally and theoretically. Different types of LIPSS with periods even below 100 nm can be generated. Their dynamics and formation mechanisms are analyzed and identified in ultrafast optical experiments. Complementing theoretical calculations of the laser-induced carrier dynamics address transient changes of the optical properties of the irradiated materials and reveal the importance of surface plasmon polaritons in the early stage of LIPSS formation. Various applications of these nanostructures are outlined.
For almost 150 years it is known that hydrogen has a deleterious effect on the mechanical properties of metallic components. Nowadays, the problem of hydrogen assisted degradation is highly relevant in energy related fields due to the massive use of steel as a structural component in these applications and its sensitivity to hydrogen. Since the discovery of hydrogen assisted cracking (HAC), researchers studied intensively and suggested possible explanations and mechanisms in order to define how hydrogen is affecting the material. In general, it is considered that hydrogen changes the mechanical properties more in terms of ductility (deformation capacities) than in strength (load capacities). Hydrogen concentration is one of three crucial factors in the degradation process, together with the microstructure of the material and the internal/external mechanical load. The relatively high concentration of hydrogen resulting in this loss of ductility can originate during production or before service (e.g. welding processes) and during service (i.e. catholically protected systems to eliminate corrosion processes in sour environments).
In parallel to the theoretical work, tremendous efforts were, and are still, invested in searching for a proper method to elucidate, map and quantify the hydrogen in the microstructure, which is the basis for this work. For steels, the focus is mainly on the observations of diffusion processes and the interaction of hydrogen with the microstructure
in regions with high local stresses/strains (for example around evolving cracks). The challenge for reaching this goal arises from the fact that accurate indication of hydrogen by means of position, unlike heavier atoms, can be made only by mass spectrometry or by interaction with another element (e.g. silver decoration, special coating and resonant nuclear reaction by nitrogen). In addition to this, the difficulty recording the hydrogen behavior while it rapidly diffuses through the material, leaving only the unpredicted failure, should be taken into account.
Although using powerful characterization methods, models and computational simulations, the key to defining the mechanisms behind HAC is still under debate and not fully understood. The relationship between material and hydrogen is determined by three factors, i.e., the material structure and microstructure – determining the physical properties, the mechanical load applied on the material and the hydrogen concentration. It is well known that in order to have a complete definition of HAC these three factors must be examined locally with the minimal scale and the maximal resolution reachable. The major gap is the lack in such a characterization method or a technique by which one has the ability to detect and observe the hydrogen in the metallic microstructure. The commonly used techniques nowadays are capable of characterization of the microstructure without the ability to observe the hydrogen distribution. Global hydrogen concentration and localized hydrogen observation are possible by some techniques which are incapable of indicating a change in the structure or microstructure therefore a comprehensive overview can be gained only by combining several methods.
In the presented research, secondary ion mass spectrometry (SIMS) was adopted as the main tool to detect and locally map the hydrogen distribution in two types of duplex stainless steel grades: EN 1.4462 (standard 2205 duplex stainless steel) and EN 1.4162 (2101 lean duplex stainless steel). The term duplex stainless steel (DSS) refers to the austenitic-ferritic microstructure of the steel where the combination of physical and mechanical properties of the two phases is achieved. The DSS was selected as a case study for this work due to the wide use of this grade in many energy and the lack of knowledge on hydrogen behavior in two-phase containing microstructures. ToFSIMS was exploited in-situ and ex-situ in three experimental approaches during or following
an electrochemical charging procedure. This type of hydrogen charging was selected as it simulated a procedure of cathodic protection of most sub-water oil and gas extraction and delivery systems. The experimental procedures were:
1. Ex-situ charging followed by ToF-SIMS imaging for basic understanding of hydrogen distribution.
2. Ex-situ charging followed by in-situ mechanical loading to obtain information on hydrogen behavior around a propagating crack.
3. In-situ permeation of hydrogen through a steel membrane inside the ToF-SIMS to obtain information on diffusion behavior of hydrogen in a two-phase microstructure.
The comprehensive view of the effect of hydrogen on steel was gained by using supplementary methods, such as high resolution scanning electron microscopy (HR-SEM), focused ion beam (FIB) and electron back-scattered diffraction (EBSD). The state of the art in this work lies in applying both: in-situ experimental approaches and data treatment of the ToF-SIMS raw data. The data treatment includes the combination of data from several sources (data fusion).
The results for the ex-situ charging followed by static sample imaging and data fusion showed that when the analyzed surface is directly exposed to the electrolyte the degradation is pronounced differently in the ferrite, austenite and interface. The degradation mechanisms in the ferrite and austenite were reflected by the formation of cracks on the surface of both, where a high concentration of hydrogen was obtained. This result supports the assumption that hydrogen is attracted to highly deformed regions. The advantage of using in-situ charging/permeation in comparison to ex-situ charging is that the effect of hydrogen on the ferrite and austenite phases when the hydrogen is evolving from within the microstructure is realized, in comparison to when the analyzed surface is initially exposed directly to the electrolyte. In both experiments the ferrite was observed as a fast diffusion path for the hydrogen. The faster diffusion of hydrogen through the ferrite is expected due to the higher diffusion coefficient, however, a direct proof for the diffusion sequence in this scale was never shown. Most significant results were achieved by the ‘core’ experiments of this research. These experiments included the design of a novel dynamic mechanical loading device to apply an external load during SIMS imaging of a hydrogen precharged-notched sample. For the first time it was shown that plastic deformation induced by applying a mechanical load is resulting in a redistribution of hydrogen locally around the notch.
The accurate EDS microanalysis of light elements such as boron and carbon by spectrum imaging will be demonstrated using a sintered hard ceramic material composed of the three major phases titanium boride (TiB2), titanium carbide (TiC), silicon carbide (SiC) and minor phases, sub-μm in size.
The combination of these three materials leads to improved mechanical and tribological properties. Silicon carbide is a material used for mechanical seals. It has the disadvantage of reduced failsafe running functions, causing increased wear when running dry. The added titanium components (TiC and TiB2) improve the failsafe running functions. This technology has already been transferred to industrial applications.
Laser texturing is an emerging technology for generating surface functionalities on basis of optical, mechanical, or chemical properties. Taking benefit of laser sources with ultrashort (fs) pulse durations features outstanding precision of machining and negligible rims or burrs surrounding the laser-irradiation zone. Consequently, additional mechanical or chemical post-processing steps are usually not required for fs-laser surface texturing (fs-LST). This work aimed to provide a bridge between research in the field of tribology and laser materials processing. The paper reviews the current state-of-the-art in fs-LST, with a focus on the tribological performance (friction and wear) of specific self-organized surface structures (so-called ripples, grooves, and spikes) on steel and titanium alloys. On the titanium alloy, specific sickle-shaped hybrid micro-nanostructures were also observed and tribologically tested. Care is taken to identify accompanying effects affecting the materials hardness, superficial oxidation, nano- and microscale topographies, and the role of additives contained in lubricants, such as commercial engine oil.
Duplex (DSS) and austenitic stainless steels (ASS) are frequently used in many energy related applications. The duplex grade is considered to have outstanding mechanical properties as well as good corrosion resistance. The austenitic phase combines high ductility, even at low temperatures, with sufficient strength, and therefore such materials are applied in storage and transport of high-pressure hydrogen. During service in acidic environments large amounts of hydrogen can ingress into the microstructure and induce many changes in the mechanical properties of the steel. Embrittlement of steels by hydrogen remains unclear even though this topic has been intensively studied for several decades. The reason for that lies in the inability to validate the proposed theoretical models in the sub-micron scale. Among the very few available methods nowadays, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) enables a highly accurate mapping of hydrogen in the microstructure in a spatial resolution below 100 nm. In the present work ToF-SIMS was used as a main tool in order to investigate the effect of deuterium on a duplex microstructure of lean and standard DSSs during and after the electrochemical charging process. Electrochemical charging simulates the service of a component in acidic environments under conditions of cathodic protection that are commonly applied to prevent corrosion reactions. ToF-SIMS after multivariate data analysis (MVA) was combined with high resolution topographic images and electron back-scattered diffraction (EBSD) data to characterize the structural changes. It was observed that the ferritic phase was affected almost identical in all steels whereas in the austenitic phase significant differences were obtained in the lean duplex in comparison to the standard DSS. The obtained results have been compared to similar investigations on a AISI 304L austenitic stainless steel. The advantage of the combined techniques is reflected by the ability to correlate the hydrogen distribution in the microstructure and the resulted phase transformation.
In this contribution the mechanisms of formation and current applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting properties, the mimicry of the natural texture of animal integuments, the tailoring of surface colonization by bacterial biofilms, and the improvement of the tribological performance of nanostructured metal surfaces.
Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon that can be observed on almost any material after the irradiation by linearly polarized laser beams, particularly when using ultrashort laser pulses with durations in the femtosecond to picosecond range.
During the past few years significantly increasing research activities have been reported in the field of LIPSS, since their generation in a single-step process provides a simple way of nanostructuring and surface functionalization towards the control of optical, mechanical, biological, or chemical surface properties. In this contribution the mechanisms of formation and current applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting properties, the mimicry of the natural texture of animal integuments, the tailoring of surface colonization by bacterial biofilms, the advancement of medical pacemakers, and the improvement of the tribological performance of nanostructured metal surfaces.
The effects of weathering exposure on unfilled and filled thermoplastic polyurethanes (TPU) materials are described as performed under different humidity conditions. For this purpose, a weathering device was used with UV-A 340 nm lamps at a constant temperature of 40 °C. The effects of environmental (UV and humidity condition) degradation on the frictional properties of TPU materials are presented along with surface analyses to characterize the chemistry of the degradative process. Photooxidative degradation of unfilled polymer leads to deterioration of physical and mechanical properties, which affects its tribological behavior significantly. Due to crosslinking, the stiffness of the material increases, reducing drastically the friction coefficient of unfilled TPUs. The frictional behavior of glass fiber reinforced TPU is less affected by radiation.
In the presented research, the high potential and abilities of secondary ion mass spectrometry (ToF-SIMS) to detect and locally map the hydrogen distribution in two types of duplex stainless steels are shown. The research validates certain proposed mechanisms by combining ToF-SIMS with high-resolution scanning electron microscopy and electron-backscattered diffraction. The combination of data from several techniques on the same region was conducted in this field for the first time by applying data treatment of the ToF-SIMS raw data and data fusion approach. This powerful combination of methods allows reviewing of the occurring processes related to hydrogen assisted cracking. The step beyond the state of the art in this field was gained here by developing permeation and mechanical loading experiments within the ToF-SIMS during chemometric imaging of the hydrogen distribution in the microstructure. The research presents the necessary correlation between the hydrogen distribution and the resulted structural changes, the diffusion behavior in a duplex microstructure and stress induced diffusion of hydrogen by applying external load at the microscale.
Due to its low mass and high diffusivity in presence of compositional, thermal and mechanical gradients, hydrogen within a metallic microstructure can result in severe loss in ductility even at low concentrations and might lead eventually to a catastrophic and unpredictable failure of structural components during service. In this context, hydrogen mapping at the microscale is still considered among the most important challenges on the pathway towards a better understanding of the hydrogen transport and assisted cracking phenomena in metals, specifically in structural components, e.g. steels.
Among the very few available techniques to localize hydrogen at the microscale, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. Based on the assumption that deuterium influence the microstructure similarly to hydrogen, in the following contribution ToF-SIMS was applied as the main technique to detect and locally map the deuterium distribution in several alloys: lean 2101 and standard 2205 duplex stainless steel (DSS), AISI 304L austenitic stainless steel and titanium 6Al-4V alloy. These alloys were selected as case studies in this work due to the wide use of them in many applications and environments which frequently provide critical conditions for hydrogen absorption and assisted degradation.
The innovative design of in-situ and ex-situ experiments enabled us to elucidate the permeation, transport and trapping of deuterium in the microstructure in sub-micron resolution for the first time. In addition to the novel experimental setups, further progress was gained by applying computational multivariate data analysis (MVA) on the raw data and data fusion with high resolution structural characterization methods (scanning electron microscopy and electron back-scattered diffraction – SEM/EBSD). This combination allowed us to correlate the deuterium distribution and the influence on the microstructure.
The processing of laser-induced periodic surface structures (LIPSS, ripples) on metals and semiconductors in ambient air is usually accompanied by superficial oxidation effects - widely neglected in the current literature. In this contribution, chemical, structural, and mechanical alterations in the formation of femtosecond LIPSS are characterized by a variety of surface analytical techniques, including energy dispersive X-ray analyses (EDX), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy (µ-RS), and depth-profiling Auger electron microscopy (AEM). Alternative routes of electrochemical and thermal oxidation allow to qualify the relevance of superficial oxidation effects on the tribological performance in oil lubricated reciprocating sliding tribological tests (RSTT). It is revealed that the fs-laser processing of near-wavelength sized LIPSS on metals leads to the formation of a few hundreds of nanometer thick graded oxide layer, consisting mainly of amorphous oxides.
Regardless of its reduced hardness and limited thickness, this nanostructured surface layer can effciently prevent a direct metal-metal contact in the RSTT and may also act as an anchor layer for specific wear-reducing additives contained in the engine oil involved
Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.
Among the very few techniques to localize hydrogen (H) at the microscale in steels, Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a reliable tool. The necessity to detect hydrogen stems from its deleterious effects in metals, that are often used as structural components and to obtain better understanding of the underlying metallurgical mechanisms of hydrogen embrittlement (HE) which are still unclear.
Austenitic stainless steels are nowadays commonly used in a wide variety of application, from hydrogen transport and storage facilities to petrochemical and offshore applications where they are exposed to aggressive environments and therefore prone to HE. One of the greater risks in the austenitic class is the embrittlement of the material due to the instability of the γ austenite and its transformation into a brittle α martensitic phase. This transformation takes place due to the local stresses that are induced by the uptake of hydrogen during service. Nonetheless, it was shown that this transformation can occur as an artefact during SIMS analysis itself where Cs-sputtering is necessary not only to remove surface contaminations but mainly to enhance H/D secondary ion yield.
In the following contribution we show the influence of different sputtering conditions on AISI 304L austenitic stainless steel in order to distinguish the artefact from the hydrogen induced transformation. The material was charged electrochemically in a deuterium based electrolyte. Deuterium (D) must be in these experiments as a replacement for hydrogen which cannot be used because adsorbed hydrogen superimposes hydrogen originating from charging the sample in the SIMS images. ToF-SIMS analyses were conducted by ToF SIMS IV (IONTOF GmbH, Münster, Germany). The experiments were carried out on deuterium charged and non-charged samples. The structural characterization was carried out by SEM and EBSD examinations before and after charging, both with a Leo Gemeni 1530VP field-emission scanning electron microscope and a Zeiss Supra 40 instrument (Carl Zeiss Microscopy GmbH, Oberkochen, Germany). The results showed that the use of 1keV Cs+ beam induces stacking faults while higher sputter beam energies results in γ→α transformation.
The reduction of harmful emissions to the environment is one of the most urgent challenges of our time. To achieve this goal, it is inevitable to shift from using fossil fuels to renewable energy sources. Within this transition, hydrogen can play a key role serving as fuel in transportation and as means for energy storage.
The storage and transport of hydrogen using austenitic stainless steels as the infrastructure, as well as the use of these grades in hydrogen containing aggressive environments, remains problematic. The degradation of the mechanical properties and the possibility of phase transformation by ingress and accumulation of hydrogen are the main drawbacks. Advanced studies of the behaviour of hydrogen in austenite is necessary to fully understand the occurring damage processes. This knowledge is crucial for the safe use of components in industry and transportation facilities of hydrogen.
A powerful tool for depicting the distribution of hydrogen in steels, with high accuracy and resolution, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). We here present a comprehensive research on the hydrogen degradation processes in AISI 304L based on electrochemical charging and subsequent ToF-SIMS experiments. To obtain furthermore information about the structural composition and cracking behaviour, electron-backscattered diffraction (EBSD) and scanning electron microscopy (SEM) were performed afterwards. All the gathered data was treated employing data fusion, thus creating a thorough portrait of hydrogen diffusion and its damaging effects in AISI 304L.
Specimens were charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and traces existing in the material or adsorbed from the rest gas in the analysis chamber. Similar diffusion and permeation behaviour, as well as solubility, allow nonetheless to draw onclusions from the experiments.
During the energy transformation from fossil fuels to renewable energy sources, the use of hydrogen as fuel and energy storage can play a key role. This presents new challenges to industry and the scientific community alike. The storage and transport of hydrogen, which is nowadays mainly realized by austenitic stainless steels, remains problematic, which is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. The development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behavior of hydrogen in austenitic steel contributes to an understanding of the damage processes, which is crucial for both life assessment and safe use of components in industry and transportation. As one of the few tools that is capable of depicting the distribution of hydrogen in steels, time-of-flight secondary ion mass spectrometry was conducted after electrochemical charging. To obtain further information about the structural composition and cracking behavior, electron-backscattered diffraction and scanning electron microscopy were performed. Gathered data of chemical composition and topography were treated employing data fusion, thus creating a comprehensive portrait of hydrogen-induced effects in the austenite grade AISI 304L. Specimens were electrochemically charged with deuterium instead of hydrogen. This arises from the difficulties to distinguish between artificially charged hydrogen and traces existing in the material or the rest gas in the analysis chamber. Similar diffusion and permeation behavior, as well as solubility, allow nonetheless to draw conclusions from the experiments.
Due to their excellent combination of ductility, strength and corrosive resistance, austenitic stainless steels (ASS) are widely used in many industrial applications. Thus, these steel grades can be found as structural components in the (petro-)chemical industry, in offshore applications and more recent for storage and transport of hydrogen fuel. Steels employed for these applications are exposed to aggressive environments and hydrogen containing media. The ingress and accumulation of hydrogen into the microstructure is commonly observed during service leading to a phenomenon called “hydrogen embrittlement”. A loss in ductility and strength, the formation of cracks and phase transformations are typical features of this hydrogen-induced degradation of mechanical properties.
Although, great efforts are made to understanding hydrogen embrittlement, there is an ongoing debate of the underlying mechanisms. This knowledge is crucial for the safe use and durability of components on the one side and the development of new materials on the other.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was proven to be a powerful tool for depicting the distribution of the hydrogen isotope deuterium in the microstructure of austenitic and duplex steels. The combination with imaging techniques such as electron backscatter diffraction (EBSD) and scanning electron microscopy (SEM), delivering structural and morphological information, creates a comprehensive picture of the hydrogen/deuterium-induced effects in the materials. All the gathered data is treated with principal component analysis (PCA) and data fusion to enhance the depth of information.
The mobility of hydrogen and deuterium in a steel microstructure is affected by external mechanical stress. To investigate the behaviour of deuterium in a strained microstructure, a new in situ experimental approach was developed. This gives the possibility of analysing samples in the SIMS instrument simultaneously to four-point-bending-tests.
Specimens made from ASS AISI 304L were electrochemically charged with deuterium instead of hydrogen. This necessity stems from the difficulty to separate between artificially charged hydrogen and hydrogen existing in the pristine material or adsorbed from the rest gas in the analysis chamber. Nonetheless, similar diffusion, permeation and solubility data allow to draw qualitative conclusions from the experiments, which are relevant for the application addressed.
Chemical effects during the formation of femtosecond laser-induced periodic surface structures
(2019)
The processing of laser-induced periodic surface structures (LIPSS, ripples) on metals and semiconductors in ambient air is usually accompanied by superficial oxidation effects – a fact that is widely neglected in the current literature. In this contribution, chemical, structural, and mechanical alterations in the formation of femtosecond LIPSS are characterized by a variety of surface analytical techniques, including energy dispersive X-ray analyses (EDX), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy (µ-RS), and depth-profiling Auger electron microscopy (AEM). Alternative routes of electrochemical and thermal oxidation allow to qualify the relevance of superficial oxidation effects on the tribological performance in oil lubricated reciprocating sliding tribological tests (RSTT). It is revealed that the fs-laser processing of near-wavelength sized LIPSS on metals leads to the formation of a few hundreds of nanometers thick graded oxide layers, consisting mainly of amorphous oxides. Regardless of reduced hardness and limited thickness, this nanostructured surface layer efficiently prevents a direct metal-to-metal contact in the RSTT and may also act as an anchor layer for specific wear-reducing additives contained in the used engine oil.
Laser-induced periodic surface structures (LIPSS, ripples) with ~500–700 nm period were produced on titanium alloy (Ti6Al4V) surfaces upon scan processing in air by a Ti:sapphire femtosecond laser. The tribological performance of the surfaces were qualified in linear reciprocating sliding tribological tests against balls made of different materials using different oilbased lubricants. Extending our previous work, we studied the admixture of the additive 2-ethylhexyl-zinc-dithiophosphate to a base oil containing only anti-oxidants and temperature stabilizers. The presence of this additive along with the variation of the chemical composition of the counterbodies allows us to explore the synergy of the additive with the laseroxidized nanostructures.
Oxidation effects on the functionality and formation of laser-induced periodic surface structures
(2019)
In the last decades, the formation of laser-induced periodic surface structures (LIPSS) has been widely studied, not only to stablish a general understanding of the main mechanisms present during the irradiation with ultrashort laser pulses, but also to identify the main processing parameters for its fabrication on various technical materials. However, an important and almost always present effect that is typically set aside is the material oxidation during or after the laser processing. Usually, this leads to optical, chemical, structural and mechanical alterations that are seldomly studied in detail. Therefore, in this work we present a study that includes the formation of LIPSS on Ti6Al4V alloy for tribological applications were different oxidations layers are involved.
The material characterization using different techniques, such as energy dispersive X-ray analyses (EDX), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy (µ-RS), and depth-profiling Auger electron microscopy (AEM), and other techniques, confirms the formation of a non-negligible superficial oxide layer – strongly dependent on the specific processing parameters. We perform tribological experiments on laser irradiated samples oxidized by alternative ways to have a comparison on its friction performance. The obtained results show significant differences that depend directly on the thickness and the quality of the oxidized layer. This may open a fertile research area until now barely explored with clear impact on LIPSS based applications.
The damaging impact of hydrogen on the austenitic stainless steel AISI 304 L was analysed.
To this aim, samples were charged electrochemically with the hydrogen isotope deuterium (2H, D) and examined with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and electron backscatter diffraction (EBSD). The fusion of the obtained chemical and structural information revealed local enrichment of deuterium in austenite, transformation into martensite, crack formation and severe roughening of the specimen surface. The results indicated that martensite was not only formed during charging but also during Desorption and ToF-SIMS examinations. Furthermore, cross-sections of deuterium-charged samples revealed that in preferred deformation bands a g/ε/a 0 evolution is taking place.
By means of microscopic analyses and carrier gas hot extraction (CGHE), it was found that the use of NaAsO2 as recombination poison decreased the uptake of hydrogen significantly and resulted in severe precipitation on the specimen surfaces. This is in contrast to the popular presumption that NaAsO2 enhances the uptake of hydrogen (and
deuterium) during electrochemical charging by hampering its recombination from Atoms to molecules.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize some of our results on the mechanistical aspects of the observed high corrosion resistance.
Hochentropie-Legierungen (HEAs) zeichnen sich durch einen Mischkristall-System aus mindestens fünf und Mittelentropie-Legierungen (MEAs) durch mindestens drei Hauptlegierungselemente aus, in äquiatomarer Zusammensetzung. Sie zeigen außergewöhnliche Anwendungseigenschaften, wie z.B. hohe Festigkeit, Duktilität oder Korrosionsbeständigkeit. Zukünftige HEA/MEA-Komponenten aufgrund ihrer Eigenschaften für wasserstoffhaltige Umgebungen (wie Behälter für kryogene oder Hochdruckspeicherung) von Interesse. Daher ist die Bewertung der Wasserstoffabsorption und die Diffusion in diesen Materialien von großer Bedeutung. Dazu wurden in unserer Studie eine CoCrFeMnNi-HEA und eine CoCrNi-MEA untersucht. Die Proben wurden elektrochemisch mit Wasserstoff beladen. Für die Ermittlung des Wasserstoffdiffusionsverhaltens wurde die thermische Desorptionsanalyse (TDA) mit unterschiedlichen Heizraten bis zu 0,250 K/s angewandt. Die nachfolgende Peakentfaltung der Signale führte zu Hochtemperatur-Desorptionsspitzen und Wasserstofftrapping auch über 280°C. Eine resultierende Gesamtwasserstoffkonzentration > 40 ppm wurde für den MEA ermittelt und > 100 ppm für den HEA. Dies deutet auf zwei wichtige Effekte hin:
(1) verzögerte Wasserstoffdiffusion und (2) eine beträchtliche Menge an getrapptem Wasserstoff auch bei hoher Temperatur. Beide Effekte können hinsichtlich einer wasserstoffunterstützten Rissbildung kritisch werden, dies erfordert jedoch weitere Untersuchungen. Zusätzlich erfolgte die Bestimmung des lokalen Volta-Potentials mittels hochauflösender Kelvin-Sonden-Kraft-Mikroskopie (SKPFM). Die ermittelten Scans zeigen einen bestimmten Einfluss der Wasserstoffbeladung auf die Potentiale.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
Laser material processing is an emerging technology that generates surface functionalities on the basis of optical, mechanical, or chemical properties. In the form of laser surface texturing (LST), it has attracted a remarkable amount of research to tailor surface properties towards various tribological applications. The main advantages of this single-step, laser-based technology are the contactless machining, featuring a high flexibility, efficiency, and speed, along with the excellent quality of the processed products. LST can be applied precisely localized to sub-micrometric areas, but, via laser beam scanning, it is also feasible for structuring large surface areas at the square meter size.
This Special Issue focuses on the latest developments concerning the tribological performance of laser-generated periodic surface nano- and microstructures and their applications. This includes the laser-based processing of different surface patterns, such as “self-organized” laser-induced periodic surface structures (LIPSS, ripples), grooves, micro-spikes, hierarchical hybrid nano-/micro-structures, microfeatures generated by direct laser interference patterning (DLIP), or even dimples or other topographic geometries shaped by direct laser modification or ablation. The applications of these periodically nano- and micro-patterned surfaces may improve the lubricated or non-lubricated tribological performance of surfaces in conformal and even non-conformal contact through a reduction of wear, a variation of the coefficient of friction, altered load carrying capacity, etc., resulting in energy saving, improved reliability, increased lifetimes as well as durability, leading in turn to extended maintenance intervals/reduced down-time. This can be beneficial in terms of bearings, gears, engines, seals, cutting tools, or other tribological components. Fundamental aspects addressed may involve the investigation of the relevant physical and chemical effects accompanying the laser-generated nano- and microscale topographies, such as alterations of the material structures, the hardness, superficial oxidation, the role of additives contained in lubricants, surface wettability, micro-hydrodynamic effects, etc.
For this Special Issue we aim to attract both academic and industrial researchers and would like to provide a bridge between research in the fields of tribology and laser material processing in order to foster the current knowledge and present new ideas for future applications and new technologies.
Laser material processing is an emerging technology that generates surface functionalities on the basis of optical, mechanical, or chemical properties. In the form of laser surface texturing (LST), it has attracted a remarkable amount of research to tailor surface properties towards various tribological applications. The main advantages of this single-step, laser-based technology are the contactless machining, featuring a high flexibility, efficiency, and speed, along with the excellent quality of the processed products. LST can be applied precisely localized to sub-micrometric areas, but, via laser beam scanning, it is also feasible for structuring large surface areas at the square meter size.
This Special Issue focuses on the latest developments concerning the tribological performance of laser-generated periodic surface nano- and microstructures and their applications. This includes the laser-based processing of different surface patterns, such as “self-organized” laser-induced periodic surface structures (LIPSS, ripples), grooves, micro-spikes, hierarchical hybrid nano-/micro-structures, microfeatures generated by direct laser interference patterning (DLIP), or even dimples or other topographic geometries shaped by direct laser modification or ablation. The applications of these periodically nano- and micro-patterned surfaces may improve the lubricated or non-lubricated tribological performance of surfaces in conformal and even non-conformal contact through a reduction of wear, a variation of the coefficient of friction, altered load carrying capacity, etc., resulting in energy saving, improved reliability, increased lifetimes as well as durability, leading in turn to extended maintenance intervals/reduced down-time. This can be beneficial in terms of bearings, gears, engines, seals, cutting tools, or other tribological components. Fundamental aspects addressed may involve the investigation of the relevant physical and chemical effects accompanying the laser-generated nano- and microscale topographies, such as alterations of the material structures, the hardness, superficial oxidation, the role of additives contained in lubricants, surface wettability, micro-hydrodynamic effects, etc.
For this Special Issue we aim to attract both academic and industrial researchers and would like to provide a bridge between research in the fields of tribology and laser material processing in order to foster the current knowledge and present new ideas for future applications and new technologies.
In this contribution, chemical, structural, and mechanical alterations in various types of femtosecond laser-generated surface structures, i.e., laser-induced periodic surface structures (LIPSS, ripples), Grooves, and Spikes on titanium alloy, are characterized by various surface analytical techniques, including X-ray diffraction and glow-discharge optical emission spectroscopy. The formation of oxide layers of the different laser-based structures inherently influences the friction and wear performance as demonstrated in oil-lubricated reciprocating sliding tribological tests (RSTTs) along with subsequent elemental mapping by energy-dispersive X-ray analysis. It is revealed that the fs-laser scan processing (790 nm, 30 fs, 1 kHz) of near-wavelength-sized LIPSS leads to the formation of a graded oxide layer extending a few hundreds of nanometers into depth, consisting mainly of amorphous oxides. Other superficial fs-laser-generated structures such as periodic Grooves and irregular Spikes produced at higher fluences and effective number of pulses per unit area present even thicker graded oxide layers that are also suitable for friction reduction and wear resistance. Ultimately, these femtosecond laser-induced nanostructured surface layers efficiently prevent a direct metal-to-metal contact in the RSTT and may act as an anchor layer for specific wear-reducing additives contained in the used engine oil.
The impact of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on tribological properties was investigated for metal-reinforced ceramic composites (Al2O3-ZrO2-Nb). For this purpose, the metallic niobium (Nb) phase was selectively structured with LIPSS in an air environment with different values of the fs-laser peak fluence by near-infrared fs-laser radiation (λ = 1025 nm, τ = 300 fs, frep = 1 kHz), taking advantage of the different light absorption behavior of ceramic and metal. The tribological performance was evaluated by reciprocating sliding tests in a ball-on-disc configuration using Ringer's solution as lubricant. The surfaces were characterized before and after laser irradiation by optical microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy and by measuring the contact angle with Ringer's solution. The LIPSS formation resulted in an increased wetting of the surface with the lubricant. Moreover, the selectively structured composite surfaces revealed a coefficient of friction significantly reduced by a factor of ~3 when compared to the non-irradiated surface. Furthermore, the formation of a laser-induced oxidation layer was detected with NbO as the most prominent oxidation state. Selectively structured composites with outstanding mechanical properties and enhanced tribological performance are of particular interest for biomedical applications.
Hydrocarbons fuel our economy. Furthermore, intermediate goods and consumer products are often hydrocarbon-based. Beside all the progress they made possible, hydrogen-containing substances can have severe detrimental effects on materials exposed to them. Hydrogen-assisted failure of iron alloys has been recognised more than a century ago. The present study aims to providing further insight into the degradation of the austenitic stainless steel AISI 304L (EN 1.4307) exposed to hydrogen. To this end, samples were electrochemically charged with the hydrogen isotope deuterium (2H, D) and analysed by scanning electron microscopy (SEM), electron back-scatter diffraction (EBSD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). It was found that deuterium caused a phase transformation from the original γ austenite into ε- and α’-martensite. Despite their low solubility for hydrogen, viz. deuterium, the newly formed phases showed high deuterium concentration which was attributed to the increased density of traps. Information about the behaviour of deuterium in the material subjected to external mechanical load was gathered. A four-point-bending device was developed for this purpose. This allowed to analyse in-situ pre-charged samples in the ToF-SIMS during the application of external mechanical load. The results indicate a movement of deuterium towards the regions of highest stress.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in two different electrolyte systems (NaCl and H2SO4 c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively. To analyze the semiconducting properties of the passive film Mott-Schottky analysis was conducted.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX, ICP-MS and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of Chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance due to the higher concentration of Chromium in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize our results on the mechanistical aspects of the observed high corrosion resistance.
Different types of laser-generated surface structures, i.e., Laser-induced Periodic Surface Structures (LIPSS, ripples), Grooves, and Spikes are generated on titanium and Ti6Al4V surfaces by means of femtosecond (fs) laser scan processing (790 nm, 30 fs, 1 kHz) in ambient air. Morphological, chemical and structural properties of the different surface structures are characterized by various surface analytical techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), Glow discharge optical emission spectroscopy (GD-OES), and depth-profiling Auger electron spectroscopy (AES). It is revealed that the formation of near-wavelength sized LIPSS is accompanied by the formation of a graded oxide extending several tens to a few hundreds of nanometers into depth. GD-OES performed on other superficial fs-laser generated structures produced at higher fluences and effective number of pulses per spot area such as periodic Grooves and irregular Spikes indicate even thicker graded oxide layers. These graded layers may be suitable for applications in prosthetics or tribology.
Influence of oxygen vacancies on core-shell formation in solid solutions of (Na,Bi)TiO3 and SrTiO3
(2021)
Solid solutions of (Na,Bi)TiO3 (NBT) and SrTiO3 (ST) are materials of interest for high-strain or high-energy density capacitor applications. Often, they exhibit chemical heterogeneity and develop core-shell structures during regular solid-state synthesis with an NBT-rich core. In this case, the NBT forms first so that the strontium needs to diffuse into the material to reach chemical homogeneity. Depending on the presence of core-shell structures, the electrical properties can vary drastically. In this work, we rationalize the effect of variations in oxygen vacancy concentration by Fe-acceptor and Nb-donor doping. It can be shown that a diffusion couple of strontium and oxygen is responsible for chemical homogenization and that the oxygen vacancy content can control the formation of a core-shell structure.
Zinc oxide - polymer interfaces are known to exhibit interesting properties regarding molecular adhesion. This work is aimed at the investigation of the effect of the morphology and surface chemistry on the macroscopic adhesion of a model epoxy-based adhesive to nanorod (ZnO NR) and nanocrystalline (ZnO NC) ZnO-modified surfaces. Both ZnO films have been prepared using hydrothermal synthesis on hot-dip galvanized steel (HDG) surfaces by varying the precursor chemistry in order to control the film morphology. Poly (acrylic acid) (PAA) was used to improve the interfacial adhesion by modifying the morphology and surface chemistry of ZnO nanostructured films. The strong interaction of PAA from a dilute and neutral aqueous solution with the ZnO nanocrystallites was shown to significantly improve the interfacial adhesion by means of a nanoetching process.
It was shown that the wet peel-forces correlate well with the considered morphology and surface chemistry.
The impact of the microstructure of Fe-16Cr-0.2C on high-temperature oxidation – sulphidation in SO2
(2021)
This study elucidates the impact of the microstructure of Fe-16Cr-0.2C on oxide layer formation at 650 ◦C in Ar-0.5 % SO2. A cold-rolled and two heat-treated states of the alloy were exposed for up to 1000 h. The samples were characterised in detail from microstructural and chemical perspectives using scanning electron microscopy (SEM), X-ray diffraction (XRD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural modification of the alloy by heat-treatment was advantageous. It was found that Cr-carbides support chromia formation and reduce sulphidation when their area fraction is low and diameter is small.
Die Reduktion von Reibung und Verschleiß in technischen Systemen bietet ein großes Potenzial zur Reduktion von CO2-Emissionen. Dieser Beitrag diskutiert die Erzeugung und tribologische Charakterisierung von Ultrakurzpuls-generierten Nano- und Mikrostrukturen auf Metallen (Stahl, Titan). Besonderes Augenmerk wird dabei auf die Rolle der laserinduzierten Oxidschicht im Zusammenspiel mit verschleißreduzierenden Additiven in ölbasierten Schmiermitteln gerichtet.
Influence of oxidation in the formation and performance of laser-induced periodic surface structures
(2022)
The fabrication of laser-induced periodic surface structures (LIPSS) has been reported for metallic, semiconductor and dielectric materials when irradiated with linearly polarized ultrashort laser pulses. Different sets of processing parameters have been identified and extensively studied, allowing the use of LIPSS for applications in medicine, tribology and surface wetting to name a few. One important parameter that is often not considered is the laser-induced oxidation that is produced especially when oxidation prone materials are irradiated in air environment. This surface oxidation can potentially influence the final structures
size, shape and orientation and modify their functionality in some specific applications.
In this work, we first study the influence of the laser-induced oxidation layer on the formation of LIPSS by characterizing the response of the oxidation prone
hard-coating material chromium nitride. Moreover, we employ complementary surface and depth-profiling analytic techniques to reveal morphological, chemical and structural features of different types of surface structures and LIPSS produced on titanium-based substrates. Finite-difference time-domain (FDTD) calculations finally explain how this superficial oxidation layer promotes the formation of a new type of low spatial frequency LIPSS. Also, we measure the depth-extent of the different oxides formed and demonstrate its beneficial influence for friction reduction and wear resistance applications.
In this study the so-called laser-induced periodic surface structures (LIPSS, ripples) were produced on titanium alloy (Ti6Al4V) surfaces upon scan processing in air by a Ti:sapphire femtosecond (fs) laser. The tribological performance of the resulting surfaces was qualified in linear reciprocating sliding tribological tests (RSTT) against balls made of different materials (100Cr6 steel/Al2O3/Si3N4) using different oil-based lubricants. The admixture of the additive 2-ethylhexylzinc-dithiophosphate (ZDDP) to a base oil containing only anti-oxidants and temperature stabilizers disclosed the synergy of the additive with the laser-oxidized nanostructures. This interplay between the laser-textured sample topography and the local chemistry in the tribological contact area reduces friction and wear.
Antibiotic resistance is a growing global problem which poses a massive threat to human health. Although human activity contributes to the acceleration of the process, bacteria have a self-driven stabilisation mechanism to protect themselves from such and other external threats: biofilm formation. Nonetheless, it is the adhesion of a single bacterial cell to a surface that triggers the formation of such network of biomolecules and microorganisms, as well as its hazardous consequences. The main objective of this work was to quantify the adhesion force of a single E. coli cell on a Ti substrate via the AFM-related single-cell force spectroscopy, with both the cell and the substrate material being of high clinical relevance. A set of 25 x 25 force displacement curves was acquired with a maximum force of 3.2 nN without dwell time, yielding a topography map and an adhesion force map that showed to be correlated. A mean adhesion force of 0.85 ± 0.175 nN was measured and the presence of cell appendages on the bacterial cell wall was verified through individual force-displacement curves. Bacterial viability was assessed after the measurements via live/dead staining.
Design and construction of a rainfall simulator to test metal runoff at atmospheric conditions
(2023)
A rainfall simulator was presented as an environmental assessment tool to quantify wash-off concentrations from metallic materials. It is part of the RUNOFF-project, which studies and re-assesses the durability of roofing and facade materials under current atmospheric conditions in Germany.
Studying building materials is important as they have a significant impact on achieving a variety of goals and targets within the sustainable developments goals (SDGs). The durability of materials is essential to reach sustainability. However, the durability of metallic materials is strongly depended on climate conditions, which have changed as a result of technical measures in industry, climate change and increasing urbanisation. In Germany at least, the data base is not up-to-date leading to prediction models regarding corrosion resistance and durability of metallic materials which can no longer be trusted and therefore need to be re-assessed and updated. Also, not only the demand for sustainable but also environmentally friendly building materials has increased dramatically. A number of construction materials produce chemical hazards, and therefore have negative impacts on water quality, soils health and ecosystems. To limit these impacts, environmental assessment methods and tools are needed to measure and quantify the inputs and outputs of building materials throughout their lifetime.