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Iron-based catalysts are employed in CO2-FTS due to their ability to convert CO2 into CO in a first step and their selectivity towards higher hydrocarbons in a second CO hydrogenation step. According to the literature, iron carbides represent the active phase for hydrocarbon formation and are claimed to emerge in the presence of CO. We propose nanostructured FeOx films as model systems to assess information about the complex phase transformations during CO2-FTS. Mesoporous hematite, ferrihydrite, maghemite, maghemite/magnetite films were exposed to CO2-FTS atmospheres at 20 bar and 300°C. Up to three distinct phases were observed depending on the timeon-stream (TOS): a sintered maghemite/magnetite phase, a carbidic core-shell structure, and a low-crystalline, needle-type oxide phase. Our findings indicate that the formation of an intermediary maghemite/magnetite phase, predominant after short TOS (30 h), precedes the evolution of the carbide phase.
Yet, even after prolonged TOS (185 h), no full conversion into a bulk carbide is observed.
In a laboratory test, transparent high‐density polyethylene (HDPE) jerrycans have been exposed to both UV radiation and 55 wt‐% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The damages are compared with FTIR spectroscopy in ATR and HT‐gel permeation chromatography(GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. This is caused by the decomposition of nitric acid into nitrous gases by UV radiation, which is also observed at lower concentrations (28 wt‐%). After 6 days of laboratory exposure, this is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. The gradual increase in oxidative damage shows the reproducibility of the test.
Flexible organic crystals (elastic and plastic) are important materials for optical waveguides, tunable optoelectronic devices, and photonic integrated circuits. Here, we present highly elastic organic crystals of a Schiff base, 1-((E)-(2,5-dichlorophenylimino)methyl)naphthalen-2-ol (1), and an azine molecule, 2,4-dibromo-6-((E)-((E)-(2,6-dichlorobenzylidene)hydrazono)methyl)phenol (2). These microcrystals are highly flexible under external mechanical force, both in the macroscopic and the microscopic regimes. The mechanical flexibility of these crystals arises as a result of weak and dispersive C−H⋅⋅⋅Cl, Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and π⋅⋅⋅π stacking interactions. Singly and doubly-bent geometries were achieved from their straight shape by a micromechanical approach using the AFM cantilever tip. Crystals of molecules 1 and 2 display a bright-green and red fluorescence (FL), respectively, and selective reabsorption of a part of their FL band. Crystals 1 and 2 exhibit optical-path-dependent low loss emissions at the termini of crystal in their straight and even in extremely bent geometries. Interestingly, the excitation position-dependent optical modes appear in both linear and bent waveguides of crystals 1 and 2, confirming their light-trapping ability.
We demonstrate here using a disulfide system the first example of reversible, selective, and quantitative transformation between three crystalline polymorphs by ball mill grinding. This includes the discovery of a previously unknown polymorph. Each polymorph is reproducibly obtained under well-defined neat or liquid-assisted grinding conditions, revealing subtle control over the apparent thermodynamic stability. We discovered that the presence of a contaminant as low as 1.5% mol mol−1 acting as a template is required to enable all these three polymorph transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different conditions and by surface interactions with small amounts of added solvent. For the first time, we show evidence that each of the three polymorphs is obtained with a unique and reproducible crystalline size. This mechanochemical approach gives access to bulk quantities of metastable polymorphs that are inaccessible through recrystallisation.
We report a new sequence selective terpolymerisation in which three monomers (butylene oxide (BO) A, PhNCS B and phtalic thioanhydride (PTA) C) are selectively enchained into an (ABA′C)n sequence. PTA/PhNCS/BO ring-opening terpolymerisation ROTERP can be coupled with CS2 ROTERP to generate tetrapolymers and with εDL ROP in switchable catalysis for blockpolymer synthesis.
Till now application of printed magnetoelectronics is hindered by lack of large area exchange coupled metallic multilayers required to produce printable magneto-sensory inks. Large-scale roll-to-roll (R2R) fabrication process is an attractive approach owing to its capabilities for high volume, high throughput, and large area manufacturing. Precise and high performance R2R sputtering technology is developed to fabricate large area giant magnetoresistive (GMR) thin-films stacks that contain 30 metallic bilayers prepared by continuous R2R sputtering of Co and Cu sequential on a hundred meters long polyethylene terephthalate (PET) web. The R2R sputtered Co/Cu multilayer on a 0.2 × 100 m2 PET web exhibits a GMR ratio of ≈40% achieving the largest area exchange coupled room temperature magneto-sensitive system demonstrated to date. The prepared GMR thin-film is converted to magnetosensitive ink that enables printing of magnetic sensors with high performance in a cost-efficient way, which promotes integration with printed electronics. An average GMR ratio of ≈18% is obtained for 370 printed magnetic sensors. The realized precise R2R sputtering approach can also be extended to a wide range of hybrid thin-film material systems opening up a path for new functional inks applied with printing technologies.
n this work, three classes of fatigue models are reviewed according to the fatigue regimes commonly considered in the current components design. Particular attention is devoted to the so-called Class III fatigue models, covering the three fatigue regimes, namely, LCF, HCF and VHCF. The applicability and limitations of the pro-posed analytical sigmoidal solutions are discussed from the viewpoint of practical design. The compatible Weibull S-N model by Castillo and Canteli is revisited and improved by considering a new reference parameter GP = E⋅σM ⋅(dε/dσ)|M as the driving force alternative to the conventional stress range. In this way, the requirement, σM ≤ σu, according to the real experimental conditions, is fulfilled and the parametric limit number of cycles, N0, recovers its meaning. The probabilistic definition of the model on the HCF and VHCF regimes is maintained and extended to the LCF regime. The strain gradients may be calculated from the monotonic or cyclic stress–strain curve of the material although a direct derivation from the hysteresis loop is recommended. Some Class III fatigue models from the literature and another one improved by the authors are applied to the assessment of one experimental campaign under different stress ratios conditions and the results compared accordingly. Finally, the new probabilistic GP-N field is evaluated. The results confirm the practical confluence of the stress- and the strain-based approaches into a single and advantageous unified methodology.
Statement of problem
The design of the implant-abutment connection has been widely researched, but the impact of different crown-abutment geometries remains unclear.
Purpose
The purpose of this in vitro study was to evaluate the effect of different crown-abutment margin geometries on the mechanical behavior and fit of screw-retained implant-supported single-crown restorations by using mechanical static and fatigue tests and mastication simulation.
Material and methods
A total of 45 cobalt-chromium premolar-shaped metal frameworks were fabricated for single-unit implant-supported screw-retained restorations on stock abutments and internal hexagon Ø4.25×11-mm cylindrical implants. They were divided into 3 groups according to margin geometry: S, shoulder; C, chamfer; and F, feather-edge. Three static load until fracture and 24 dynamic load tests were performed by using the International Organization for Standardization 14801:2016 standard (ISO 14801:2016) (number of cycles limit: 5×106 cycles, frequency: 6 Hz). The ProFatigue software program was used to optimize the procedure (S, n=12 specimens; C, n=7 specimens; and F, n=5 specimens). Six additional specimens from each group were subjected to a mastication simulation (limit number of cycles: 1×106 cycles, cyclic loading from Pmin=30 N to Pmax=300 N, frequency: 6 Hz). Results from the fatigue tests were reported descriptively, and the Fisher exact test was used to analyze the difference in failure modes. Data from maximum misfit were evaluated by photogrammetry and statistically analyzed with the Anderson-Darling test and the Kruskal-Wallis and Dunn multiple comparison tests (α=.05).
Results
The fatigue limit was 456 N for group S, 512 N for group C, and 514 N for group F. The mean ±standard deviation misfit was 2.6 ±0.1 μm for group S, 3.8 ±1.1 μm for group C, and 3.6 ±0.8 μm for group F. Differences in misfit between groups S and C and between groups S and F were statistically significant (P<.05).
Conclusions
Crown-abutment connections with chamfer and feather-edge margins showed better mechanical behavior, while shoulder margin exhibited better fit. However, high levels of fit were achieved for all the evaluated geometries.
L-lactide (LA) was polymerized in toluene by means of neat tin(II) 2-ethylhexanoate (SnOct2). Concentration, time and temperature were varied. The isothermally crystallized polyLAs (PLA) were characterized in the virgin state with regard to topology, molar mass, melting temperature (Tm), crystal modification, high or low Tm morphology, crystallinity and crystal thickness. Even a small amount of solvent favored cyclization relative to polymerization in bulk, so that cyclic polylactides were obtained at 115 ◦C and even at 95 ◦C. At all temperatures the α-modification of PLA was obtained along with crystallinities up to 90%. With 6 M solution the high Tm morphology with Tm’s > 190 ◦C was obtained at 115 ◦C. The crystal thickness of crystallites grown from solution at 115 ◦C was on the average 10–20% higher than that of PLA polymerized in bulk. At a polymerization temperature of 75 ◦C cyclization was incomplete and fewer perfect crystallites were formed. A new hypothesis for the crystal growth of cyclic polyLAs is proposed.
Industrial and agricultural waste streams (waste water, sludges, tailings, etc.) which contain high concentrations of NH4+, PO43–, and transition metals are environmentally harmful and toxic pollutants. At the same time, phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate independently from each other. Investigations on the simultaneous removal of multiple components have been carried out only to a limited extent. Here, we report the synthesis routes for Ni- and Co-struvites (NH4MPO4·6H2O, M = Ni2+ and Co2+), which allow for P, ammonia, and metal co-precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites as well as their crystal morphologies and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal amorphous nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the involved metal cation in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size makes precipitation of transition metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially up-cycled as precursor powders for electrochemical or (electro)catalytic applications, which require transition metal phosphates.
In the present work, electron backscatter diffraction was used to determine the microscopic dislocation structures generated during creep (with tests interrupted at the steady state) in pure 99.8% aluminium. This material was investigated at two different stress levels, corresponding to the power-law and power-law breakdown regimes. The results show that the formation of subgrain cellular structures occurs independently of the crystallographic orientation. However, the density of these cellular structures strongly depends on the grain crystallographic orientation with respect to the tensile axis direction, with <111> grains exhibiting the highest densities at both stress levels. It is proposed that this behaviour is due to the influence of intergranular stresses, which is different in <111> and <001> grains.
It is already known that the laser beam welding (LBW) or hybrid laser-arc welding (HLAW) processes are sensitive to manufacturing tolerances such as gaps and misalignment of the edges, especially at welding of thick-walled steels due to its narrow beam diameter. Therefore, the joining parts preferably have to be milled. The study deals with the influence of the edge quality, the gap and the misalignment of edges on the weld seam quality of hybrid laser-arc welded 20-mm-thick structural steel plates which were prepared by laser and plasma cutting. Single-pass welds were conducted in butt joint configuration. An AC magnet was used as a contactless backing. It was positioned under the workpiece during the welding process to prevent sagging. The profile of the edges and the gap between the workpieces were measured before welding by a profile scanner or a digital camera, respectively. With a laser beam power of just 13.7 kW, the single-pass welds could
be performed. A gap bridgeability up to 1 mm at laser-cut and 2 mm at plasma-cut samples could be reached respectively.
Furthermore, a misalignment of the edges up to 2 mm could be welded in a single pass. The new findings may eliminate the need for cost and time-consuming preparation of the edges.
The robust determination of the threshold against fatigue crack propagation DKth is of paramount importance in fracture mechanics based fatigue assessment procedures. The standards ASTM E647 and ISO 12108 introduce operational definitions of DKth based on the crack propagation rate da/dN and suggest linear fits of logarithmic DK– da/dN test data to calculate DKth. Since these fits typically suffer from a poor representation of the actual curvature of the crack propagation curve, a method for evaluating DKth using a nonlinear function is proposed. It is shown that the proposed method reduces the artificial conservativeness induced by the evaluation method as well as the susceptibility to scatter in test data and the influence of test data density.
Molecularly imprinted polymers (MIPs) against sialic acid (SA) have been developed as a detection tool to target cancer cells. Before proceeding to in vivo studies, a better knowledge of the overall effects of MIPs on the innate immune system is needed. The aim of this study thus was to exemplarily assess whether SA-MIPs lead to inflammatory and/or cytotoxic responses when administered to phagocytosing cells in the innate immune system. The response of monocytic/macrophage cell lines to two different reference particles, Alhydrogel and PLGA, was compared to their response to SA-MIPs. In vitro culture showed a cellular association of SA-MIPs and Alhydrogel, as analyzed by flow cytometry. The reference particle Alhydrogel induced secretion of IL-1b from the monocytic cell line THP-1, whereas almost no secretion was provoked for SA-MIPs. A reduced number of both THP-1 and RAW 264.7 cells were observed after incubation with SA-MIPs and this was not caused by cytotoxicity. Digital holographic cytometry showed that SA-MIP treatment affected cell division, with
much fewer cells dividing. Thus, the reduced number of cells after SA-MIP treatment was not linked to SA-MIPs cytotoxicity. In conclusion, SA-MIPs have a low degree of inflammatory properties, are not cytotoxic, and can be applicable for future in vivo studies.
Sintering, crystallization, and foaming of 44.8SiO2–2.5P2O3–36.5CaO–6.6Na2O–6.6K2O–3.0CaF2 (F3) and 54.6SiO2–1.7P2O3–22.1CaO–6.0Na2O–7.9K2O–7.7MgO (13–93) bioactive glass powders milled in isopropanol and CO2 were studied via heating microscopy, differential thermal analysis, vacuum hot extraction (VHE), Infrared spectroscopy, and time-of-flight secondary ion mass spectrometry. Full densification was reached in any case and followed by significant foaming.
VHE studies show that foaming is driven by carbon gases and carbonates were detected by Infrared spectroscopy to provide the major foaming source. Carbonates could be detected even after heating to 750◦C, which hints on a thermally very stable species or mechanical trapping. Otherwise, dark gray compact colors for milling in isopropanol indicate the presence of residual carbon as well. Its significant contribution to foaming, however, could not be proved and might be
limited by the diffusivity of oxygen needed for carbon oxidation to carbon gas.
Here, we present a study on agarose thin-film samples that represent a model system for the exopolysaccharide matrix of biofilms. Povidone-iodide (PVP-I) was selected as an antibacterial agent to evaluate our x-ray photoelectron spectroscopy (XPS)-based methodology to trace specific marker elements, here iodine, commonly found in organic matrices of antibiotics. The in-depth distribution of iodine was determined by XPS analyses with variable excitation energies and in combination with argon gas cluster ion beam sputter cycles. On mixed agarose/PVP-I nanometer-thin films, both methods were found to solve the analytical task and deliver independently comparable results. In the mixed agarose/PVP-I thin film, we found the outermost surface layer depleted in iodine, whereas the iodine is homogeneously distributed in the depth region between this outermost surface layer and the interface between the thin film and the substrate. Depletion of iodine from the uppermost surface in the thin-film samples is assumed to be caused by ultrahigh vacuum exposure resulting in a loss of molecular iodine (I2) as reported earlier for other iodine-doped polymers.
For the development of selective and sensitive chemical sensors, we have developed a new family of poly(etherphosphoramide) polymers. These polymers were obtained with satisfactory yields by nucleophilic aromatic polycondensation using isosorbide as green resources, and bisphenol A with two novel difluoro phosphinothioic amide monomers. Unprecedented, the thiophosphorylated aminoheterocycles monomers, functionalized with two heterocyclic amine, N-methylpiperazine and morpholine were successfully obtained by nucleophilic substitution reaction of P(S)–Cl compound. The resulting polymers were characterized by different analytical techniques (NMR, MALDI–ToF MS, GPC, DSC, and ATG). The resulting partially green polymers, having tertiary phosphine sulfide with P–N side chain functionalities along the main chain of polymers are the sensitive film at the surface of a gold electrode for the impedimetric detection of Cd, Ni, Pb and Hg. The bio-based poly(etherphosphoramide) functionalized with N-methylpiperazine modified sensor showed better analytical performance
than petrochemical based polymers for the detection of Ni2+. A detection limit of 50 pM was obtained which is very low compared to the previously published electrochemical sensors for nickel detection.
Recently, additive manufacturing of ceramics has achieved the maturity to be transferred from scientific laboratories to industrial applications. At the same time, research is progressing to expand the boundaries of this field into the territory of novel materials and applications. This feature issue addresses current progress in all aspects of additive manufacturing of ceramics, from parts design to feedstock selection, from technological development to characterization of printed components.
The detection of internal irregularities is crucial for quality assessment in metal-based additive manufacturing (AM) technologies such as laser powder bed fusion (L-PBF). The utilization of in-process thermography as an in situ monitoring tool in combination with post-process X-ray micro computed tomography (XCT) as a reference technique has shown great potential for this aim. Due to the small irregularity dimensions, a precise registration of the datasets is necessary as a
requirement for correlation. In this study, the registration of thermography and XCT reference datasets of a cylindric specimen containing keyhole pores is carried out for the development of a porosity prediction model. The considered datasets show variations in shape, data type and dimensionality, especially due to shrinkage and material elevation effects present in the manufactured part. Since the resulting deformations are challenging for registration, a novel preprocessing methodology is introduced that involves an adaptive volume adjustment algorithm which is based on the porosity distribution in the specimen. Thus, the implementation of a simple three-dimensional image-to-image registration is enabled. The results demonstrate the influence of the part deformation on the resulting porosity location and the importance of registration in terms of irregularity prediction.
Aim of this study is to provide information about moisture dependent material behaviour of unstabilised loadbearing earth blocks and mortars. Compressive strength and Young’s modulus were investigated after conditioning in varying relative humidity reaching from 40 % up to 95 %. The material composition and physical properties were investigated to understand the influence of relative humidity onto the mechanical properties. A normalisation of strength and stiffness by the values obtained at 23 ◦C and 50 % relative humidity reveals a linear dependence of compressive strength and Young’s modulus that is regardless of the material composition.
Thus, it is possible to describe the influence of relative humidity onto the load-bearing behaviour of unstabilised earth masonry materials in a generally valid formulation.
Alkali-silica reaction (ASR) is a chemical reaction within concrete which can lead over time to cracking and spalling. Due to the complexity of the problem, it still causes damage to concrete constructions worldwide.
The publication aims to illustrate the interdisciplinary research of the German Federal Institute for Materials Research and Testing (BAM) within the last 20 years, considering all aspects of ASR topics from the macro to the micro level. First, methods for characterization and assessment of ASR risks and reaction products used at BAM are explained and classified in the international context. Subsequently the added value of the research approach by combining different, preferably nondestructive, methods across all scales is explained using specific examples from a variety of research projects. Aspects covered range from the development of new test-setups to assess aggregate reactivity, to analysis of microstructure and reaction products using microscopical, spectroscopical and X-ray methods, to the development of a testing methodology for existing concrete pavements including in-depth analysis of the visual damage indicator and the de-icing salt input using innovative testing techniques. Finally, research regarding a novel avoidance strategy that makes use of internal hydrophobization of the concrete mix is presented.
We study the molecular mobility and electrical conductivity of a homologous series of linear shaped columnar ionic liquid crystals ILCn, (n = 8, 10, 12, 14, 16) using broadband dielectric spectroscopy (BDS), specific heat spectroscopy (SHS), and X-ray scattering. We aim to understand how the alkyl chain length influences the dynamics and electric conductivity in this system. Two dielectrically active relaxation modes are observed, the γ and the αcore process, that correspond to the localized fluctuations of the alkyl chains and cooperative motions of the aromatic core in the columns, respectively. Both the γ relaxation and the αcore process slow down with increasing alkyl chain length. SHS reveals one relaxation process, the αalkyl process that has a similar temperature dependence as that of the αcore process for ILC12, 14, and 16 but shifts to higher temperature for ILC8 and 10. For ILC12, 14, and 16, the absolute values of DC conductivity increase by 4 orders of magnitude at the transition from the plastic crystalline to hexagonal columnar phase. For ILC8 and 10, the DC conductivity behavior is similar to ionic liquids, where the conductivity is coupled with structural relaxation. Small-angle X-ray investigations reveal that both the intercolumnar distance and the disorder coherence length increase with alkyl chain length; conversely, the DC conductivity decreases monotonically.
To enhance the biological effects of radiation damage in cancerous cells, we present an alternative approach to the use of gold nanoparticles (AuNP), focusing on the synthesis and characterization of highly monodisperse, spherical radioactive gold nanoparticles 198AuNP. The size of the AuNP size was optimized with the help of Geant4/TOPAS particle scattering simulations, and energy deposition per nm3 per decay for varying radii (2–10 nm) was evaluated. This work is the foundation for ongoing experimental work to evaluate cell death induced by 198AuNP which aims for the use of radioactive gold nanoparticles in cancer treatment.
High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion (UC) nanocrystals (UCNC) like NaYF4:Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC. UC luminescence (UCL) is, however, controlled not only by dopant concentration, yet by an interplay of different parameters including size, crystal and shell quality, and excitation power density (P). Thus, identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy. Here, we quantify the dopant concentration dependence of the UCL quantum yield (ΦUC) of solid
NaYF4:Yb,Er/NaYF4:Lu upconversion core/shell nanocrystals of varying Yb3+ and Er3+ concentrations (Yb3+ series: 20%‒98% Yb3+; 2% Er3+; Er3+ series: 60% Yb3+; 2%‒40% Er3+). To circumvent other luminescence quenching processes, an elaborate synthesis yielding OH-free UCNC with record ΦUC of ~9% and ~25 nm core particles with a thick surface shell were used. High Yb3+ concentrations barely reduce ΦUC from ~9% (20% Yb3+) to ~7% (98% Yb3+) for an Er3+ concentration of 2%, thereby allowing to strongly increase the particle absorption cross section and UCNC brightness. Although an increased Er3+ concentration reduces ΦUC from ~7% (2% Er3+) to 1% (40%) for 60% Yb3+. Nevertheless, at very high P (> 1 MW/cm2) used for microscopic studies, highly Er3+-doped UCNC display a high brightness because of reduced saturation. These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials.
Automated bonding analysis software has been developed based on Crystal Orbital Hamilton Populations to facilitate high-throughput bonding analysis and machine-learning of bonding features. This work presents the software and discusses its applications to simple and complex materials such as GaN, NaCl, the oxynitrides XTaO2N (X=Ca, Ba, Sr) and Yb14Mn1Sb11.
Recent developments of X-ray photoelectron spectroscopy using excitation energies different from the usual lab-sources Mg Kα and Al Kα, thus covering larger and different kinetic energy ranges, require more flexible approaches for determining the transmission function than the well-established ones using reference spectra. Therefore, the approach using quantified peak areas (QPA) was refined allowing a more precise estimation of the transmission function. This refinement was tested by comparing the results obtained with the new version with former calculations. Furthermore, the obtained transmission function was validated by comparing the results with a transmission function using the reference spectrum of polyethylene. Additionally, an ionic liquid was used as reference for estimating the transmission function at the energy resolved HE-SGM beamline at BESSY II. Comparison between the measured and stoichiometric composition shows that a transmission function was determined, which allows a reasonable quantification.
This paper is focused on the approximation of absorbed Charpy impact energy-temperature curves (KV-T) and the management of sub-size test piece results in Charpy pendulum impact tests. Both subjects are frequently underestimated but may have a strong impact on the assessment of product quality and structural integrity. The status of related test standards, product standards, structural integrity assessment procedures and corresponding research is reviewed.
It is concluded that the state of regulation is partly insufficient and wrong. There is a wide gap between the state of knowledge in the field of materials testing and the requirements of product standards and structural integrity assessment procedures. The present paper aims at boosting and supporting the necessary discussion among the parties involved to raise the level of technical safety. Correspondingly, a large experimental database was created by Charpy impact testing of popular modern structural Steels with nominal yield strength from 235 MPa to 960 MPa. KV-T data were generated using test pieces with thicknesses between 2.5 mm and 10 mm. Different strategies for KV-T curve fitting, definition of transition temperatures, as well as upper and lower shelf energy levels were followed, and different scaling procedures were applied to the sub-size test piece results. The results show that proportional scaling of sub-size to full-size test piece results in terms of KV should be disallowed because it is a wrong approach.
Regulations still incorporating such procedures should be revised as soon as possible. Existing nonproportional scaling and conversion procedures were applied. The results obtained illustrate that neither an overall nor consistent conservatism nor an adequate conservatism level can be achieved. In summary, the standardizing bodies should enforce the discussion to revise relevant test standards considering more precise specifications on Charpy data fitting. Furthermore, proposals are made for an improved management of sub-size test piece results.
Catalysts are important components in chemical processes because they lower the activation energy and thus determine the rate, efficiency and selectivity of a chemical reaction. This property plays an important role in many of today’s processes, including the electrochemical splitting of water. Due to the continuous development of catalyst materials, they are becoming more complex, which makes a reliable evaluation of physicochemical properties challenging even for modern analytical measurement techniques and industrial manufacturing.
We present a fast, vacuum-free and non-destructive analytical approach using multi-sample spectroscopic ellipsometry to determine relevant material parameters such as film thickness, porosity and composition of mesoporous IrOx–TiOy films. Mesoporous IrOx–TiOy films were deposited on Si wafers by sol–gel synthesis, varying the composition of the mixed oxide films between 0 and 100 wt%Ir. The ellipsometric modeling is based on an anisotropic Bruggeman effective medium approximation (a-BEMA) to determine the film thickness and volume fraction of the material and pores. The volume fraction of the material was again modeled using a Bruggeman EMA to determine the chemical composition of the materials. The ellipsometric fitting results were compared with complementary methods, such as scanning electron microscopy (SEM), electron probe microanalysis (EPMA) as well as environmental ellipsometric porosimetry (EEP).
Poly (ether ether ketone) (PEEK) has a high continuous service temperature, excellent mechanical properties, and good solvent and abrasion resistance, which can be further improved through the addition of carbon nanotubes (CNTs). CNT-PEEK nanocomposites are promising matrices for continuous carbon fibre composites; powder processing can mitigate the high melt viscosities in these systems. In this study, model single fibre (hierarchical) composites were produced by embedding sized and desized carbon fibres in nanocomposite CNTPEEK powders followed by single fibre pull-out tests to assess interfacial characteristics. Carbon fibre-PEEK interfacial shear strength is typically 40–45 MPa. Increasing CNT loadings increased fibre-matrix interfacial shear strength linearly up to ~70 MPa at 5.0 wt%, which was attributed to the CNT-based mechanical modification of the PEEK matrix. Apparent interfacial shear strength was inversely correlated with the embedded fibre length irrespective of carbon fibre sizing or CNT loading, indicating brittle fracture of the fibre-matrix interface.
Pulled out carbon fibres were still coated with the matrix, which indicated strong adhesion at the interface in all samples, likely related to a transcrystalline region. Adhesion was, however, negatively affected by the presence of epoxy sizings. Frictional shear strength was independent of embedded fibre length and CNT content for all samples.
Asymmetrically bridged aroyl-S,N-ketene acetals and aroyl-S,N-ketene acetal multichromophores can be readily synthesized in consecutive three-, four-, or five-component syntheses in good to excellent yields by several successive Suzuki-couplings of aroyl-S,N-ketene acetals and bis(boronic)acid esters. Different aroyl-S,N-ketene acetals as well as linker molecules yield a library of 23 multichromophores with substitution and linker pattern-tunable emission properties. This allows control of different communication pathways between the chromophores and of aggregation-induced emission (AIE) and energy transfer (ET) properties, providing elaborate aggregation-based fluorescence switches.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
Biofilms are ubiquitous in nature and in the man-made environment. Given their harmful effects on human health, an in-depth understanding of biofilms and the monitoring of their formation and growth are important. Particularly relevant for many metabolic processes and survival strategies of biofilms is their extracellular pH. However, most conventional techniques are not suited for minimally invasive pH measurements of living biofilms. Here, a fluorescent nanosensor is presented for ratiometric measurements of pH in biofilms in the range of pH 4.5–9.5 using confocal laser scanning microscopy. The nanosensor consists of biocompatible polystyrene nanoparticles loaded with pH-inert dye Nile Red and is surface functionalized with a pH-responsive fluorescein dye. Its performance was validated by fluorometrically monitoring the time-dependent changes in pH in E. coli biofilms after glucose inoculation at 37 °C and 4 °C. This revealed a temperature-dependent decrease in pH over a 4-h period caused by the acidifying glucose metabolism of E. coli. These studies demonstrate the applicability of this nanosensor to characterize the chemical microenvironment in biofilms with fluorescence methods.
This paper presents the results concerning monotropic nematic liquid crystals 4-pentylphenyl 40-alkyl benzoate (5PnB) (n = 3 or 5 carbon atoms in the alkyl chain). Their mesophase properties were supported by images of the polarized optical microscopy. Molecular dynamics in the bulk samples or in the composites prepared with aerosil A380 was investigated by broadband dielectric spectroscopy in a large temperature range, appropriately chosen. Thermo gravimetric and infrared investigations were additionally performed. The data were compared with those of structurally related nematics like cyanophenyl pentyl benzoates, which have a cyan group instead of the pentyl chain. The dielectric spectra of the bulk 3P5B and 5P5B demonstrate a dielectric behavior with several relaxation processes as expected for nematic liquid crystals. The temperature dependence of the relaxation rates (and of the dielectric strength) seems to have two distinguished regimes. Thus, in the isotropic state, at higher temperatures the data obey the Vogel–Fulcher–Tammann law, whereas an Arrhenius law is fitted at lower temperature, in a close similarity to the behavior of a constrained dynamic glass transition. Samples with a high density of silica (larger than 7 g aerosil/1 g of 5PnB) were prepared to observe a thin layer adsorbed on the particle surface; it was estimated that almost each guest 5PnB molecule interacts with the aerosil surface. For the composites only one main relaxation process is observed at frequencies much lower than those for the corresponding bulk, which was assigned to the dynamics of the molecules in the surface layer. Infrared spectroscopy shows that these molecules interact with the surface by the ester carbonyl group leading to the monolayer self-assembly at liquid–solid interface. We note once more the importance of the functional unit(s) for the interaction with the hydroxyl groups on the aerosil surface.
We present an easy-to-apply method to predict structural trends in the internal nucleation tendency of oxide glasses. The approach is based on calculated crystal fracture surface energies derived from easily accessible diatomic bond energy and crystal lattice data. The applicability of the method is demonstrated on literature nucleation data for isochemically crystallizing oxide glasses.
The symmetry or structural stability of ABO3-type perovskite oxides depends largely on the size of ‘A’ and ‘B’ cations, which determines the material properties. The partial substitution of these cations may be used to tune these properties. The ionic sizes and valence states of the cations play an important role in improving the prop- erties of perovskite. In this study, the substitution of La3+ with Sr2+ with a larger ionic radius and Mn3+ with Fe3+ with a similar ionic radius favored both the crystal symmetry and the mixed ionic–electronic conductivity of the perovskite. Electrodes based on La0.7Sr0.3Mn0.5Fe0.5O3 (LSMFO55) exhibited a faradaic behavior with a specific capacity of 330 C g−1 (92 mAh g−1 ) at 12C rate, while this electrode maintained a capacity of 259 C g−1 at 240C (charge or discharge in 15 s). Additionally, exohedral carbon nano-onions (CNO) were introduced as a negative electrode to design an asymmetric hybrid supercapacitor (AHS) with a widened cell voltage. The use of CNO as a negative electrode in the AHS improved the rate capability drastically compared to the use of rGO. This device maintained a good energy density even at an extra-high charging rate (600C) owing to its outstanding rate capability. The high-rate performance of the LSMFO55//CNO AHS can be elucidated by successful fabrication with a mixed ionic–electronic conductive positive electrode and a CNO negative electrode. Tuning the electronic and ionic conductivities by cationic substitution and adopting an appropriate carbon-derived negative electrode (such as CNO) can provide a practical high-rate hybrid device using various perovskites.
Nickel tungsten alloy tapes (Ni—5 at% W, 10 mm wide, 80 µm thick, biaxially textured) used in second-generation high temperature superconductor (2G-HTS) technology were laser-processed in air with ultraviolet ps-laser pulses (355 nm wavelength, 300 ps pulse duration, 250–800 kHz pulse repetition frequency). By employing optimized surface scan-processing strategies, various laser-generated periodic surface structures were generated on the tapes. Particularly, distinct surface microstructures and nanostructures were formed. These included sub-wavelength-sized highly-regular hexagonally-arranged nano-protrusions, wavelength-sized line-grating-like laser-induced periodic surface structures (LIPSS, ripples), and larger irregular pyramidal microstructures. The induced surface morphology was characterized in depth by electron-based techniques, including scanning electron microscopy (SEM), electron back scatter diffraction (EBSD), cross-sectional transmission electron microscopy (STEM/TEM) and energy dispersive X-ray spectrometry (EDS). The in-depth EBSD crystallographic analyses indicated a significant impact of the material initial grain orientation on the type of surface nanostructure and microstructure formed upon laser irradiation. Special emphasis was laid on high-resolution material analysis of the hexagonally-arranged nano-protrusions. Their formation mechanism is discussed on the basis of the interplay between electromagnetic scattering effects followed by hydrodynamic matter re-organization after the laser exposure. The temperature stability of the hexagonally-arranged nano-protrusion was explored in post-irradiation thermal annealing experiments, in order to qualify their suitability in 2G-HTS fabrication technology with initial steps deposition temperatures in the range of 773–873 K.
Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point. Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools.
Nanofibers are drawing the attention of engineers and scientists because their large surface-to-volume ratio is favorable for applications in medicine, filter technology, textile industry, lithium-air batteries, and optical sensors. However, when transferring nanofibers to a technical product in the form of a random network of fibers, referred to as nonwoven fabric, the stickiness of the freshly produced and thus fragile nanofiber nonwoven remains a problem. This is mainly because nanofibers strongly adhere to any surface because of van der Waals forces. In nature, there are animals that are actually able to efficiently produce, process, and handle nanofibers, namely cribellate spiders. For that, the spiders use the calamistrum, a comb-like structure of modified setae on the metatarsus of the hindmost (fourth) legs, to which the 10–30 nm thick silk nanofibers do not stick due to a special fingerprint-like surface nanostructure. In this work, we present a theoretical model of the interaction of linear nanofibers with a sinusoidally corrugated surface. This model allows for a prediction of the adhesive interaction and, thus, the design of a suitable surface structure to prevent sticking of an artificially nonwoven of nanofibers. According to the theoretical prediction, a technical analogon of the nanoripples was produced by ultrashort pulse laser processing on different technically relevant metal surfaces in the form of so-called laser-induced periodic surface structures (LIPSS). Subsequently, by means of a newly established peel-off test, the adhesion of an electrospun polyamide fiber-based nonwoven was quantified on such LIPSS-covered aluminium alloy, steel, and titanium alloy samples, as well as on polished (flat) control samples as reference and, additionally, on samples with randomly rough surfaces. The latter revealed that the adhesion of electrospun nanofiber nonwoven is significantly lowered on the nanostructured surfaces compared with the polished surfaces.
he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F.
Co-Cr alloys are frequently used for highly stressed components, especially in turbine and plant construction, due to their high resistance to thermal and mechanical stress, as well as to corrosive and abrasive loads. Furthermore, they are classified as difficult-to-cut materials because of their high strength and toughness as well as their low thermal conductivity. However, for Co, an increased cost and supply risk can be observed in recent years. Therefore, additive manufacturing (AM) offers significant economic advantages due to higher material efficiency regarding repair, modification, and manufacturing of such components. Concerning inhomogeneity and anisotropy of the microstructure and properties as well as manufacturing-related stresses, a lot of knowledge is still necessary for the economic use of additive welding processes in SMEs. In addition, subsequent machining, particularly contour milling, is essential to generate the required complex contours and surfaces. Hence, additive and machining manufacturing processes need to be coordinated in a complementary way, especially due to additional challenges arising in milling of heterogeneous hard-to-cut microstructures. Recently, it has been shown that modern, hybrid cutting processes, such as ultrasonic-assisted milling (US), can improve the cutting situation. In this investigation, the Co-Cr initial alloy is additionally modified with Ti and Zr up to 1 wt% with the aim to enhance the homogeneity of the microstructure and, thus, the machinability. Hence the investigation includes finish milling tests of the AM components and the comparison of US and conventional machining. Both the modifications and the ultrasonic assistance exhibit a significant effect on the machining situation; for example US causes a higher surface integrity of the finish milled surfaces compared to conventional milling.
ADAMTS4-specific MR-probe to assess aortic aneurysms in vivo using synthetic peptide libraries
(2022)
The incidence of abdominal aortic aneurysms (AAAs) has substantially increased during the last 20 years and their rupture remains the third most common cause of sudden death in the cardiovascular field after myocardial infarction and stroke. The only established clinical parameter to assess AAAs is based on the aneurysm size. Novel biomarkers are needed to improve the assessment of the risk of rupture. ADAMTS4 (A Disintegrin And Metalloproteinase with ThromboSpondin motifs 4) is a strongly upregulated proteoglycan cleaving enzyme in the unstable course of AAAs. In the screening of a one-bead-one-compound library against ADAMTS4, a low-molecular-weight cyclic peptide is discovered with favorable properties for in vivo molecular magnetic resonance imaging applications. After identification and characterization, it’s potential is evaluated in an AAA mouse model. The ADAMTS4-specific probe enables the in vivo imaging-based prediction of aneurysm expansion and rupture.
block and mortar types is analysed with particular regard to the influence of varying relative humidity. The uniaxial compressive strength and deformation characteristics of unstabilised earth blocks and mortars as well as of unstabilised earth block masonry are studied in detail and compared to conventional masonry to evaluate whether the structural design can be made accordingly. An increase of 30 % points in relative humidity leads to a reduction of the masonry´s compressive strength between 33 % and 35 % whereas the Young´s modulus is reduced by 24–29 %. However, the ratio between the Young´s modulus and the characteristic compressive strength of earth block masonry ranges between E33/fk = 283–583 but is largely independent of the relative humidity. The results show that the mechanical properties of the investigated unstabilised earth block masonry are sufficient for load-bearing structures, yielding a masonry compressive strength between 2.3 MPa and 3.7 MPa throughout the range of moisture contents
investigated. In general, the design concept of conventional masonry can be adapted for unstabilised earth masonry provided that the rather low Young´s modulus as well as the moisture dependence of both, compressive strength and Young´s modulus, are sufficiently taken into
account.
An accurate and efficient description of the spatial distribution of laser energy is a crucial factor for the modeling of laser material processing, e.g., laser welding, laser cutting, or laser-based additive manufacturing. In this study, a 3D heat transfer and fluid flow model coupled with the volume-of-fluid algorithm for free surface tracking is developed for the simulation of molten pool dynamics in high-power laser beam welding. The underlying laser-material interactions, i.e., the multiple reflections and Fresnel absorption, are considered by a raytracing method. Two strategies of free surface reconstruction used in the ray-tracing method are investigated: a typical piecewise linear interface calculation (PLIC)-based method and a novel localized level-set method. The PLIC-based method is discrete, resulting in noncontinuous free surface reconstruction. In the localized level-set method, a continuous free surface is reconstructed, and, thus, the exact reflection points can be determined. The calculated spatial laser energy distribution and the corresponding molten pool dynamics from the two methods are analyzed and compared. The obtained numerical results are evaluated with experimental measurements to assure the validity of the proposed model. It is found that distinct patterns of the beam multiple reflections are obtained with the different free surface reconstructions, which shows significant influence not only on the molten pool behaviors but also on the localized keyhole dynamics.
Directed energy deposition (DED) has been in industrial use as a coating process for many years. Modern applications include the repair of existing components and additive manufacturing. The main advantages of DED are high deposition rates and low energy input. However, the process is influenced by a variety of parameters affecting the component quality. Artificial neural networks (ANNs) offer the possibility of mapping complex processes such as DED. They can serve as a tool for predicting optimal process parameters and quality characteristics. Previous research only refers to weld beads: a transferability to additively manufactured three-dimensional components has not been investigated. In the context of this work, an ANN is generated based on 86 weld beads. Quality categories (poor, medium, and good) are chosen as target variables to combine several quality features. The applicability of this categorization compared to conventional characteristics is discussed in detail. The ANN predicts the quality category of weld beads with an average accuracy of 81.5%. Two randomly generated parameter sets predicted as “good” by the network are then used to build tracks, coatings,walls, and cubes. It is shown that ANN trained with weld beads are suitable for complex parameter predictions in a limited way.
Prognose von Qualitätsmerkmalen durch Anwendung von KI-Methoden beim Directed 10 Energy Deposition
(2022)
Dieser Beitrag enthält die Ergebnisse eines im Rahmen der DVS Forschung entwickelten Ansatzes zur Qualitätssicherung im Directed Energy Deposition. Es basiert auf der Verarbeitung verschiedener während des Prozesses gesammelter Sensordaten unter Anwendung Künstlicher Neuronale Netze (KNN). So ließen sich die Qualitätsmerkmale Härte und Dichte auf der Datenbasis von 50 additiv gefertigten Probenwürfel mit einer Abweichung < 2 % vorhersagen. Des Weiteren wurde die Übertragbarkeit des KNN auf eine Schaufelgeometrie untersucht. Auch hier ließen sich Härte und Dichte hervorragend prognostizieren (Abweichung < 1,5 %), sodass der Ansatz als validiert betrachtet werden kann.
Influence of the Composition on the Compressive Behaviour of a Semi-Metallic Brake-Pad Material
(2022)
The contact interface between the rotation and static part of a friction brake is central to the optimal functioning of the brake system due to the occurrence of heat dissipation, mechanical interaction and thermal exchanges. Generally, braking performances are evaluated by the energetic efficiency and wear rates of the contact surface. However, the compressive behaviour of the contact materials has also a significant contribution to the overall performances. In this work, the meso- and microscopic compressive behaviour of a sintered semi-metallic brake-pad material is investigated mainly via compression testing coupled with Digital Image Correlation (DIC) technique, as well as optical and scanning electron microscopy (SEM) analysis. The composition of a reference material (RM) is simplified to a selection of nine components, as opposed to up to thirty components typically used in commercial brake-pad materials. The retained components are considered as the most crucial for safe-operating performances. At the studied stress levels, the RM material is flexible (E = 5330 MPa), deformable (Ezz−plastic = −0.21%), and exhibits hysteresis loops. Subsequently, the contribution to the mechanical response of each individual component is investigated by producing the so-called dissociated materials, where the number of components is, at a time, further reduced. It is observed that the macroscopic behaviour is mainly controlled by the content (i.e., size distribution, shape and nature) of graphite particles, and that the hysteresis is only related to one of the two types of graphite used (G2 particles). Moreover, RM containing 13 wt% of G2 particles embedded in a relatively soft matrix (10.86 GPa) is able to increase the hysteresis (by 35%) when compared to the dissociated material containing 20 wt% of G2 particles which is embedded in a stiffer matrix (E = 106 GPa).
Carbon nanomembranes are synthetic two-dimensional sheets with nanometer thickness, macroscopic lateral dimensions, and high structural homogeneity. They have great application potential in various branches of nanotechnology. Because of their full carbon structure, it is not clear whether macromolecules like poly(methyl methacrylate) (PMMA) can be irreversibly adsorbed on their surface. Here, irreversible adsorption means that the polymer chains cannot be removed by a leaching process, which is assumed in technological transfer processes. However, if polar defects are present on the carbon nanomembranes (CNMs), it may occur that polymers can be irreversibly adsorbed. To address this question, PMMA was spin-coated on top of CNMs, annealed for a specific time at different temperatures, and then tried to be removed by a acetone treatment in a leaching approach. The samples were investigated in detail by atomic force microscopy, X-ray photoelectron spectroscopy, and broadband dielectric spectroscopy, where the latter method has been applied to CNMs for the first time. Unambiguously, it was shown that PMMA can be adsorbed on the surface of CNMs after annealing the sample above the glasstransition temperature of PMMA. The general occurrence of polar defects on the surface of CNMs and the adsorption of polymers open opportunities for advanced innovative hybrid materials combining the properties of the CNM with those of the polymer.
Metastable austenitic stainless steel (304L) samples with a rectangular cross-section were plastically deformed in torsion during which they experienced multiaxial stresses that led to a complex martensitic phase distribution owing to the transformation induced plasticity effect. A three-dimensional characterization of the phase distributions in these cm-sized samples was carried out by wavelength-selective neutron tomography. It was found that quantitatively correct results are obtained as long as the samples do not exhibit any considerable preferential grain orientation. Optical microscopy, electron backscatter diffraction, and finite element modeling were used to verify and explain the results obtained by neutron tomography. Altogether, neutron tomography was shown to extend the range of microstructure characterization methods towards the meso- and macroscale.
In recent years, the design and development of materials are strongly interconnected with the development of digital technologies. In this respect, efficient data management is the building block of material digitization and, in the field of materials science and engineering (MSE), effective solutions for data standardization and sharing of different digital resources are needed. Therefore, ontologies are applied that represent a map of MSE concepts and relationships between them. Among different ontology development approaches, graphical editing based on standard conceptual modeling languages is increasingly used due to its intuitiveness and simplicity. This approach is also adopted by the Materials-open-Laboratory project (Mat-o-Lab), which aims to develop domain ontologies and method graphs in accordance with testing standards in the field of MSE. To suit the actual demands of domain experts in the project, Ontopanel was created as a plugin for the popular open-source graphical editor diagrams.net to enable graphical ontology editing. It includes a set of pipeline tools to foster ontology development in diagrams.net, comprising imports and reusage of ontologies, converting diagrams to Web Ontology Language (OWL), verifying diagrams using OWL rules, and mapping data. It reduces learning costs by eliminating the need for domain experts to switch between various tools. Brinell hardness testing is chosen in this study as a use case to demonstrate the utilization of Ontopanel.
The printability of artificial defects inside the additively manufactured laser powder bed fusion (LPBF) 316L stainless steel is investigated. The printing parameters of the LPBF process are optimized to produce artificial defects with reproducible sizes at desired positions while minimizing redundant porosity. The smallest obtained artificial defect is 90 μm in diameter. The accuracy of the geometry of the printed defect depends on both the height and the diameter in the input model. The effect of artificial defects on the very-high-cycle fatigue (VHCF) behavior of LPBF 316L stainless steel is also studied. The specimens printed with artificial defects in the center are tested under VHCF using an ultrasonic machine. Crack initiation is accompanied by the formation of a fine granular area (FGA), typical of VHCF. Despite the presence of relatively large artificial defects, FGA formation is observed around accidental natural printing defects closer to the surface, which can still be considered as internal. The causes for this occurrence are discussed.
The efficient design of hypergolic-ionic-liquid (HIL) fuels with attractive features, (e.g., short ignition delay and high specific impulse) can be achieved by fine-tuning the molecular organization comprising both cations with appropriate alkyl chains and cyanoborohydride-based hydrogen-rich anions. Attractive features of the presented derivatives were attained by combining cations with various substituents (substituted 1H-1,2,4-triazol-4-ium, pyrrolidinium, ammonium and pyridinium cations) and the cyanoborohydride anion. All shown HILs display high thermal stabilities with thermal decomposition temperatures over 154 °C and possess higher densities (from 0.82 to 1.02 g cm−3) compared to the unsymmetrical dimethylhydrazine (UDMH, 0.793 g cm−3). The hypergolic ignition behavior of the propellant combination was evaluated by a drop test setup using white fuming nitric acid (WFNA) as an oxidizer and recorded using a high-speed camera. All compounds feature ignition delay times (ID) under 50 ms, while the 1-hexyl-1-methylpyrrolidin-1-ium cyanotrihydroborate congener (17) exhibited the shortest ID time (5 ms), which is comparable to the ID time of UDMH (4.8 ms with WFNA as an oxidizer). In addition, these HILs exhibit higher heats of formation (187.6 to 392.6 kJ mol−1), heats of combustion (34.39 to 47.15 kJ g−1) and specific impulse (176 to 205 s) compared to UDMH.
In an interdisciplinary collaboration, restorers, art historians, and scientists examined Guilio Romano’s The Madonna with the Wash-Basin of 1525 (Dresden State Art Collections). Insights into the painting technique along with art historical comparisons provided the opportunity for a better understanding of the painting’s genesis, in particular concerning an early reworking of the background by the artist. A recovery and reconstruction of the earlier version of the background is now possible. The discovery of zinc in distinct passages of the painting, as well as the grey-black pigment stibnite and glass particles used as a supplement in paint layers are of special interest. The technological investigation initiated a discussion about the circumstances of the revision, as well as the painting’s relation to Vasari’s Lives of Artists.
Gold films coated with a graphene sheet are being widely used as sensors for the detection of label-free binding interactions using surface plasmon resonance (SPR). During the preparation of such sensors, it is often essential to subject the sensor chips to a high-temperature treatment in order to ensure a clean graphene surface. However, sensor chips used currently, which often use chromium as an adhesion promoter, cannot be subjected to temperatures above 250 °C, because under such conditions, chromium is found to reorganize and diffuse to the surface, where it is easily oxidized, impairing the quality of SPR spectra. Here we present an optimized preparation strategy involving a three-cycle tempering coupled with chromium (oxide) etching, which allows the graphene-coated SPR chips to be annealed up to 500 °C with little deterioration of the surface morphology. In addition, the treatment delivers a surface that shows a clear enhancement in spectral response together with a good refractive index sensitivity. We demonstrate the applicability of our sensors by studying the kinetics of avidin–biotin binding at different pH repeatedly on the same chip. The possibility to anneal can be exploited to recover the original surface after sensing trials, which allowed us to reuse the sensor for at least six cycles of biomolecule adsorption.
Filigree structures can be manufactured via two-photon-polymerization (2PP) operating in the regime of non-linear light absorption. For the first time it is possible to apply this technique to the powder processing of ceramic structures with a feature size in the range of the critical defect size responsible for brittle fracture and, thus, affecting fracture toughness of high-performance ceramics. In this way, tailoring of advanced properties can be achieved already in the shaping process. Traditionally, 2PP relies on transparent polymerizable resins, which is diametrically opposed to the usually completely opaque ceramic resins and slurries. Here we present a transparent and photocurable suspension of nanoparticles (resin) with very high mass fractions of yttria-stabilized zirconia particles (YSZ). Due to the extremely well dispersed nanoparticles, scattering of light can be effectively suppressed at the process-relevant wavelength of 800 nm. Sintered ceramic structures with a resolution of down to 500 nm were obtained. Even at reduced densities of 1 to 4 g/cm³, the resulting compressive strength with 4,5 GPa is equivalent or even exceeding bulk monolithic yttria stabilized zirconia. A ceramic metamaterial is born, where the mechanical properties of yttria stabilized zirconia are altered by changing geometrical parameters and gives access to a new class of ceramic materials.
Motivated by the loss of tensile strength in 9%Ni steel arc-welded joints performed using commercially available Ni-based austenitic filler metals, the viability of retaining tensile strength using an experimentally produced matching ferritic filler metal was confirmed. Compared to the austenitic Ni-based filler metal (685 MPa), higher tensile strength in gas metal arc (GMA) welded joints was achieved using a ferritic filler metal (749 MPa) due to its microstructure being similar to the base metal (645 MPa). The microstructure of hard martensite resulted in an impact energy of 71 J (-196 °C), which was two times higher than the specified minimum value of _>34 J. The
tensile and impact strength of the welded joint is affected not only by its microstructure, but also by the degree of its mechanical mismatch depending on the type of filler metal. Welds with a harder microstructure and less mechanical mismatch are important for achieving an adequate combination of tensile strength and notched impact strength. This is achievable with the cost-effective ferritic filler metal. A more desirable combination of mechanical properties is guaranteed by applying low preheating temperature (200 °C), which is a more practicable and economical solution compared to the high post-weld heat treatment (PWHT) temperature (580 °C) suggested by other research.
The thermal expansion of polymeric parts can be an issue in many applications where the available space is limited, or exact dimensions of the part are required. For this study, a device was designed and built that allowed measuring the thermal expansion simultaneously in all three spatial directions on cubic samples with real-scale dimensions (78 mm edge length). The results are shown between 25 °C and 125 °C for two PE materials, one HMWPE and one tempered UHMWPE, for non-irradiated samples as well as cubes that have been irradiated with 100 and 400 kGy. The results measured with the new device were very similar to those measured with conventional thermo-mechanical analysis equipment and to literature data of UHMWPE. The HMWPE material shows a much larger thermal expansion coefficient in one direction compared to the other two directions during the first heating due to frozen stresses from the pressing step during material manufacturing. These stresses are mostly released by the expansion during the first heating, so that the expansion during the second heating is more uniform. The overall volumetric expansion is the same for both heating runs. By contrast, the tempered UHMWPE material shows no significant difference between first and second heating run, as the stresses from processing could already relax in the tempering step. The irradiation treatment does not affect the values significantly for the given test set-up.
Martensitic 9% Cr steels like P91 and P92 can show an increased susceptibility to delayed hydrogen-assisted cracking. The focus of this study was the microstructure and heat treatment efect on the mechanical properties of P92 base material and P91 multi-layer weld metal in both as-welded and post weld heat treated (PWHT) condition. Tensile tests with hydrogen free reference samples and electrochemically hydrogen charged samples were carried out; the mechanical properties were assessed and supported by detailed fractographic analysis. Finally, a hydrogen and microstructure-dependent fracture criterion is established. All investigated microstructures showed a hydrogen-infuenced degradation of the mechanical properties compared to the hydrogen-free reference samples. The as-welded martensitic P91 weld metal had the highest degree of degradation in the presence of hydrogen. The P91 PWHT weld metal and the P92 base material had comparable properties. From that point of view, a signifcantly increased risk for hydrogen-assisted cold cracking during welding fabrication of P91 weld joints must be considered before any heat treatment is conducted.
Multimaterial structures are a promising solution to reduce vehicle weight and save fuel or electric energy in automotive design. However, thermal joining of steel and aluminum alloys is a challenge to overcome due to different material properties and the formation of brittle intermetallic phases. In this study, a new joining approach for producing overlap line-shaped joints is presented. The lower joining partner (EN AW 5754) is melted by a laser beam, and this melt is displaced into a line-shaped cavity of the upper joining partner (1.0330) by induced Lorentz forces. The melt solidifies in the cavity to a material and form-fitting joint. This approach needs no auxiliary joining elements or filler materials. Previous investigation to produce spot-shaped joints by using this approach showed that quality and reproducibility were limited by known melt pool dynamics of aluminum alloys (keyhole collapses). For line-shaped joints, the melt displacement can take place behind the keyhole. This allows the displacement process to be spatially uncoupled from the influence of keyhole collapses. The study shows that this improved the process stability and the quality of the joint. The created line-shaped joints were microstructurally characterized by transversal sections. Intermetallic phases were identified by electron backscatter diffraction and EDX analysis. The detected intermetallic phases consist of a 5–6 μm compact phase seam of Al5.6Fe2 and a needle-shaped phase of Al13Fe4. Tensile shear tests were carried out to quantify the load capacity. It was possible to create a joint with a load capacity of about 2 kN.
The need for new solutions for electrical insulation is growing due to the increased electrification in numerous industrial sectors, opening the door for innovation. Plasma spraying is a fast and efficient way to deposit various ceramics as electrical insulators, which are used in conditions where polymers are not suitable. Alumina (Al2O3) is among the most employed ceramics in the coating industry since it exhibits good dielectric properties, high hardness, and high melting point, while still being cost-effective. Various parameters (e.g., feedstock type, spray distance, plasma power) significantly influence the resulting coating in terms of microstructure, porosity, and metastable phase formation. Consequently, these parameters need to be investigated to estimate the impact on the dielectric properties of plasma-sprayed alumina coatings. In this work, alumina coatings with different spray distances have been prepared via atmospheric plasma spray (APS) on copper substrates. The microstructure, porosity, and corresponding phase formation have been analyzed with optical microscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Moreover, we present an in-depth analysis of the fundamental dielectric properties e.g., direct current (DC) resistance, breakdown strength, dielectric loss tangent, and permittivity. Our results show that decreasing spray distance reduces the resistivity from 6.31 × 109 Ωm (130 mm) to 6.33 × 108 Ωm (70 mm), while at the same time enhances the formation of the metastable δ-Al2O3 phase. Furthermore, space charge polarization is determined as the main polarization mechanism at low frequencies.
Rapid solidification leads to unique microstructural features, where a less studied topic is the formation of various crystalline defects, including high dislocation densities, as well as gradients and splitting of the crystalline orientation. As these defects critically affect the material’s mechanical properties and performance features, it is important to understand the defect formation mechanisms, and how they depend on the solidification conditions and alloying. To illuminate the formation mechanisms of the rapid solidification induced crystalline defects, we conduct a multiscale modelling analysis consisting of bond-order potential-based molecular dynamics (MD), phase field crystal-based amplitude expansion simulations, and sequentially coupled phase field–crystal plasticity simulations. The resulting dislocation densities are quantified and compared to past experiments. The atomistic approaches (MD, PFC) can be used to calibrate continuum level crystal plasticity models, and the framework adds mechanistic insights arising from the multiscale analysis.
This article is part of the theme issue ‘Transport phenomena in complex systems (part 2)’.
The formation of pores in CMSX-4 nickel based superalloys is detrimental to the service life of the material. A way to avoid the problem is to treat the superalloys under Hot Isostatic Pressing (HIP), which enables a large volume fraction of pores to be annihilated. This paper aims to understand the contribution of plastic activity related to the gliding of dislocations on the pore annihilation. Simulations based on a phase-field model of dislocation are performed and make it possible to consider the strong anisotropy of the CMSX-4 under HIP conditions in conjunction to the strong elastic heterogeneity introduced by the pore. For pores with a radius of few micrometers, it is shown that edge parts of dislocation lines that present an extra half atomic plane oriented towards the pore are stacked above and under it in the direction which is perpendicular to their slip-planes, causing an increase of the number of dislocation along the four octahedral directions of the FCC single crystal which intersect the pore center. Results are streamlined within the isotropic elastic theory of dislocations. Effects of elastic anisotropy and dislocation reactions are also investigated in order to specify what would be the dislocation configuration around a pore in CMSX-4 under HIP conditions. Notably, the elastic anisotropy is shown to significantly modify the arrangement of dislocations close to the pore equator. Simulations also allow for the characterization of pore/dislocation interactions when dislocations are involved in Low Angle Boundaries as experimentally observed.
Anear-infrared (NIR) light-triggered release method for nitric oxide (NO) was developed utilizing core/shell NaYF4: Tm/Yb/Ca@NaGdF4:Nd/Yb up-conversion nanoparticles (UCNPs) bearing a mesoporous silica (mSiO2) shell loaded with theNOdonor S-nitroso-N-acetyl-DL-penicillamine (SNAP). To avoid overheating in biological samples, Nd3+ was chosen as a sensitizer, Yb3+ ions as the bridging sensitizer, andTm3+ ions as UV-emissive activator while co-doping with Ca2+ was done to enhance the luminescence of the activatorTm3+.NOrelease from SNAP was triggered by an NIR-UV up-conversion process, initiated by 808nmlight absorbed by the Nd3+ ions.NOrelease was confirmed by the Griess method. Under 808nmirradiation, the viability of the liver cancer cell line HepG2 significantly decreased with increasing UCNPs@mSiO2-SNAP concentration. For a UCNPs@mSiO2-SNAP concentration of 200 μgml−1, the cell survival probability was 47%. These results demonstrate that UCNPs@mSiO2-SNAP can induce the release of apoptosis-inducingNOby NIR irradiation.
The Gay-Berne model is studied numerically with a choice of parameters allowing for the formation of a discotic liquid crystal at low temperatures. We show that the model has strong virial potential-energy correlations in the isotropic phase at high temperatures, i.e., it obeys the criterion for the existence of isomorphs, which are curves of approximately invariant structure and dynamics. These properties are demonstrated to be approximately invariant in reduced units along the isomorph studied. The isomorph is described well by the constant density-scaling exponent 11.5, a number that is significantly larger than the density-scaling exponents of various Lennard-Jones models that are always below 6.
A catalyst-free Schiff base reaction was applied to synthesize two imine-linked covalent organic frameworks (COFs). The condensation reaction of 1,3,5-tris-(4-aminophenyl)triazine (TAPT) with 4,4′-biphenyldicarboxaldehyde led to the structure of HHU-COF-1 (HHU = Heinrich-Heine University). The fluorinated analog HHU-COF-2 was obtained with 2,2′,3,3′,5,5′,6,6′-octafluoro-4,4′-biphenyldicarboxaldehyde. Solid-state NMR, infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis confirmed the successful formation of the two network structures. The crystalline materials are characterized by high Brunauer–Emmett–Teller surface areas of 2352 m2/g for HHU-COF-1 and 1356 m2/g for HHU-COF-2. The products of a larger-scale synthesis were applied to prepare mixed-matrix membranes (MMMs) with the polymer Matrimid. CO2/CH4 permeation tests revealed a moderate increase in CO2 permeability at constant selectivity for HHU-COF-1 as a dispersed phase, whereas application of the fluorinated COF led to a CO2/CH4 selectivity increase from 42 for the pure Matrimid membrane to 51 for 8 wt% of HHU-COF-2 and a permeability increase from 6.8 to 13.0 Barrer for the 24 wt% MMM.
Changes in the global bulk and local structures, of three different barium compounds (BaZrO3, BaF2, and BaFCl),were induced by mechanical milling and followed using X-ray powder diffraction (PXRD), subsequent microstructure analysis, and 137Ba solid state NMR spectroscopy. Harder materials like BaZrO3 experience significantly higher structural changes upon milling than softer materials like BaF2. Moreover, soft materials with layered structures, like BaFCl, show a pronounced structural change during the milling process. By combining PXRD and solid state NMR, detailed information on the changes to the global and local structures were obtained, which are of interest for mechanochemical synthesis, mechanically treated catalysts or ionic conductors.
The micromechanical behavior of an annealed Ti-6Al-4V material produced by Laser Powder Bed Fusion was characterized by means of in-situ synchrotron X-ray diffraction during a tensile test. The lattice strain evolution was obtained parallel and transversal to the loading direction. The elastic constants were determined and compared with the conventionally manufactured alloy. In the plastic regime, a lower plastic anisotropy exhibited by the lattice planes was observed along the load axis (parallel to the building direction) than in the transverse direction.
Also, the load transfer from α to β phase was observed, increasing global ductility of the material. The material seems to accumulate a significant amount of intergranular strain in the transverse direction.
ABX3 metal halide perovskites revolutionized the research and development of new optoelectronics, including solar cells and light-emitting diodes. Processing polycrystalline thin films from precursor solutions is one of the core advantages of these materials since it enables versatile and cost-effective manufacturing. The perovskite film morphology, that is, continuous substrate coverage and low surface roughness, is of paramount importance for highly efficient solar cells and optoelectronic devices in general. Controlling the chemistry of precursor solutions is one of the most effective strategies to manage the perovskite film morphology. Herein, we show the fundamental influence of the A-site cation composition on the perovskite precursor arrangement and the consequent film formation. Extended X-ray absorption fine structure spectroscopy and small-angle X-ray scattering give unprecedented insights into the complex structural chemistry of the perovskite precursors and, in particular, their repulsive interactions as a crucial parameter for colloidal stability. Combining these techniques with in situ grazing incidence wide-angle X-ray scattering during thin-film formation allows us to identify the mechanism for using alkali metals as a decisive criterion to control the colloidal stability of the perovskite precursor and thus the thin-film morphology. We illustrate the fundamental principle behind the systematic use of alkali metals regardless of whether they are incorporated in the lattice or not. Hence, this work provides tools to selectively control the morphology and crystal growth in present and future systems
Next-generation thermal management requires the development of low lattice thermal conductivity materials, as observed in ionic conductors. For example, thermoelectric efficiency is increased when thermal conductivity is decreased. Detrimentally, high ionic conductivity leads to thermoelectric device degradation. Battery safety and design also require an understanding of thermal transport in ionic conductors. Ion mobility, structural complexity, and anharmonicity have been used to explain the thermal transport properties of ionic conductors. However, thermal and ionic transport are rarely discussed in direct comparison. Herein, the ionic conductivity of Ag+ argyrodites is found to change by orders of magnitude without altering the thermal conductivity. Thermal conductivity measurements and two-channel lattice dynamics modeling reveal that the majority of Ag+ vibrations have a non-propagating diffuson-like character, similar to amorphous materials. It is found that high ionic mobility is not a requirement for diffuson-mediated transport. Instead, the same bonding and structural traits that can lead to fast ionic conduction also lead to diffuson-mediated transport. Bridging the fields of solid-state ionics and thermal transport, it is proposed that a vibrational perspective can lead to new design strategies for functional ionic conducting materials. As a first step, the authors relate the so-called Meyer-Neldel behavior in ionic conductors to phonon occupations.
The ease with which an energetic material can be initiated by mechanical impact is a critical parameter directing material safety and application. While impact sensitivity metrics are traditionally derived experimentally, recent developments have highlighted that the phenomenon is amenable to first principles simulation. In this chapter, we will outline a fully ab initio approach to predict the relative impact sensitivities of energetic materials based on the mechanochemical principles that link the impact event to vibrational energy transfer.
This mechanism is key to rationalizing how a mechanical impact—which deposits energy into the low-frequency lattice vibrations—results in a molecular response. By simulating the vibrational energy levels (the so-called phonon density of states, PDOS) using first-principles computational methods (typically dispersion-corrected plane-wave density functional theory, PW-DFT) we can calculate the relative rate of energy propagation from the delocalized low-energy lattice vibrations through to the localized molecular modes. The latter traps the energy, which eventually results in bond rupture through heightened vibrational excitation.
This method, based on vibrational up-pumping, offers a route toward predicting the impact sensitivities of a broad range of energetic materials, provided the crystal structure of the compound (or salt or co-crystal) is known. While it does not offer insight into the sensitizing roles undoubtedly played by crystal defects or grain boundaries, it does provide a level of understanding at the molecular and crystal packing levels. Correspondingly, this approach offers a feedback mechanism to chemists and materials scientists to guide the design of new materials with desired impact sensitivity behavior.
Due to the rapidly increasing price of tungsten carbide and the significant health risks associated with the wear products of WC-Co (Co3O4 and Wo3), an alternative is required. Niobium carbide (NbC) is well suited as a cutting tool due to its high melting point and low solubility in iron. So far, NbC-Ni cermets best met the requirements of high hardness and toughness. Various secondary carbides such as VC, Mo2C, TiC, but also WC were added to further improve the hardness.
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n = 5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations probing the molecular mobility, a c-relaxation due to localized fluctuations as well as two glassy dynamics, the acore- and aalkyl-relaxation, were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n = 8 from a rigid constrained (n = 5,6) to a softer system (n = 10,12) was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene-like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition.
The typical experimental conditions inside a transmission electron microscope (TEM), such as ultra-high vacuum, high-energy electron irradiation, and surface effects of ultrathin TEM specimens, can be the origin of unexpected microstructural changes compared with that of bulk material during in situ thermal-annealing experiments. In this paper, we report on the microstructural changes of a Fe–15%Si alloy during in situ TEM annealing, where, in its bulk form, it exhibits an ordering transformation from D03 to B2 at 650 °C. Using a heating-pot type double tilt holder with a proportional–integral–differential control system, we observed the precipitation of α-Fe both at the sample surface and inside the sample. Surface precipitates formed via surface diffusion are markedly large, several tens of nm, whereas precipitates inside the specimen, which are surrounded by Fe-poor regions, reach a maximum size of 20 nm. This unexpected microstructural evolution could be attributed to vacancies on Si sites, which are induced due to high-energy electron irradiation before heating, as well as enhanced thermal diffusion of Fe atoms.
Core–shell nanoparticles have attracted much attention in recent years due to their unique properties and their increasing importance in many technological and consumer products. However, the chemistry of nanoparticles is still rarely investigated in comparison to their size and morphology. In this review, the possibilities, limits, and challenges of X-ray photoelectron spectroscopy (XPS) for obtaining more insights into the composition, thickness, and homogeneity of nanoparticle coatings are discussed with four examples: CdSe/CdS quantum dots with a thick coating and a small core; NaYF4-based upconverting nanoparticles with a large Yb-doped core and a thin Er-doped coating; and two types of polymer nanoparticles with a poly(tetrafluoroethylene) core with either a poly(methyl methacrylate) or polystyrene coating. Different approaches for calculating the thickness of the coating are presented, like a simple numerical modelling or a more complex simulation of the photoelectron peaks. Additionally, modelling of the XPS background for the investigation of coating is discussed. Furthermore, the new possibilities to measure with varying excitation energies or with hard-energy X-ray sources (hard-energy X-ray photoelectron spectroscopy) are described. A discussion about the sources of uncertainty for the determination of the thickness of the coating completes this review.
Highly anharmonic thermal vibrations may serve as a source of structural instabilities resulting in phase transitions, chemical reactions and even the mechanical disintegration of a material. Ab initio calculations model thermal motion within a harmonic or sometimes quasi-harmonic approximation and must be complimented by experimental data on temperature-dependent vibrational frequencies. Here multi-temperature atomic displacement parameters (ADPs), derived from a single-crystal synchrotron diffraction experiment, are used to characterize low-frequency lattice vibrations in the alpha-FOX-7 layered structure. It is shown that despite the limited quality of the data, the extracted frequencies are reasonably close to those derived from inelastic scattering, Raman measurements and density functional theory (DFT) calculations. Vibrational anharmonicity is parameterized by the Grüneisen parameters, which are found to be very different for in-layer and out-of-layer vibrations.
Duplex stainless steels (DSS) are used in all industries where corrosion problems play a major role. Examples include the chemical industry, the food industry and shipping industries. DSS have a balanced phase ratio of ferrite (α) and austenite (γ). Unlike single-phase stainless steels, DSS combine the advantages of these and can therefore fit many industry requirements, such as weight saving or high mechanical strength. When these steels are welded, alloying elements can burn off and condense as thin layers on cold surface regions. This loss of chemical elements can lead to changes in the microstructure. With the help of Laser-Induced Breakdown Spectroscopy (LIBS), chemical element distributions were visualized. The results were compared with those of conventional measurement methods, such as energy dispersive X-ray analysis (EDS) and X-ray fluorescence analysis (XRF), and the results from LIBS could be validated. LIBS is suitable as a fast, straightforward measurement method for producing line scans along the weld seam and provides spatially resolved information on accumulation phenomena of burned off alloying elements. LIBS is very well suited for the detection of sub-surface elements due to the exclusively superficial ablation of the material. In addition, the measurement method has been calibrated so that quantitative statements about element concentrations can also be made.
Friction at the microscale during reciprocal sliding tribotests was studied for the first time with self-mated steel (100Cr6/AISI 52100) taking advantage of an atomic force microscope (AFM). To this aim, microsized steel particles were glued to the AFM-cantilever and employed as colloidal tips to perform tribotests on a steel disc. The torsion of the cantilever, which correlates with the friction force, was measured during the tests. Few tests with the same load did not yield any wear and show that the load and adhesion contributions to friction stay constant when the shape of the test particle does not change. Most of the presented tribotests engendered wear. For those tests, the increase of friction during the tribotests was attributed to the emerging plowing contribution. Furthermore, analysis of both torsion and local slope gives information on the creation of wear particles and their influence on friction.
Iron nitride (Fe3N) and iron carbide (Fe3C) nanoparticles can be prepared via sol−gel synthesis. While sol−gel methods are simple, it can be difficult to control the crystalline composition, i.e., to achieve a Rietveld-pure product. In a previous in situ synchrotron study of the sol−gel synthesis of Fe3N/Fe3C, we showed that the reaction proceeds as follows:
Fe3O4 → FeOx → Fe3N → Fe3C. There was considerable overlap between the different phases, but we were unable to ascertain whether this was due to the experimental setup (side-on heating of a quartz capillary which could lead to thermal gradients) or whether individual particle reactions proceed at different rates. In this paper, we use in situ wide- and small-angle X-ray scattering (wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS)) to demonstrate that the overlapping phases are indeed due to variable reaction rates. While the initial oxide nanoparticles have a small range of diameters, the size range expands considerably and very rapidly during the oxide−nitride transition. This has implications for the isolation of Rietveld-pure Fe3N, and in an extensive laboratory study, we were indeed unable to isolate phasepure Fe3N. However, we made the surprising discovery that Rietveld-pure Fe3C nanoparticles can be produced at 500 °C with a sufficient furnace dwell time. This is considerably lower than the previous reports of the sol−gel synthesis of Fe3C nanoparticles.
Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD.
ZnO nanopillars were implanted with Au-400 keV and Ag-252 keV ions with ion fluences from 1 × 10^15 cm^2 to 1 × 10^16 cm^2. We compared ZnO nanopillars solely implanted with Au-ions and dually-implanted with Au and Ag-ions. Rutherford Back-Scattering spectrometry (RBS) confirmed Ag and Au embedded in ZnO nanopillar layers in a reasonable agreement with theoretical calculations. A decreasing thickness of the ZnO nanopillar layer was evidenced with the increasing ion implantation fluences. Spectroscopic Ellipsometry (SE) showed a decrease of refractive index in the nanopillar parts with embedded Au, Ag-ions. XRD discovered vertical domain size decreasing with the proceeding radiation damage accumulated in ZnO nanopillars which effect was preferably ascribed to Au-ions. SE and diffuse reflectance spectroscopy (DRS) showed optical activity of the created nanoparticles at wavelength range 500 – 600 nm and 430 – 700 nm for the Au-implanted and Au, Ag-implanted ZnO nanopillars, respectively. Photoluminescence (PL) features linked to ZnO deep level emission appear substantially enhanced due to plasmonic interaction with metal nanoparticles created by Ag, Au-implantation.
Photocatalytic activity seems to be more influenced by the nanoparticles presented in the layer rather than the surface morphology. Dual implantation with Ag, Au-ions enhanced optical activity to a larger extent without significant morphology deterioration as compared to the solely Au-ion implanted nanopillars.
Sialyl-Tn (STn or sialyl-Thomsen-nouveau) is a carbohydrate antigen expressed by more than 80% of human carcinomas. We here report a strategy for ratiometric STn detection and dual-color cancer cell labeling, particularly, by molecularly imprinted polymers (MIPs). Imprinting was based on spectroscopic studies of a urea-containing green-fluorescent monomer 1 and STn-Thr-Na (sodium salt of Neu5Acα2-6GalNAcα-O-Thr). A few-nanometer-thin green-fluorescent polymer shell, in which STn-Thr-Na was imprinted with 1, other comonomers, and a cross-linker, was synthesized from the surface of red-emissive carbon nanodot (R-CND)-doped silica nanoparticles, resulting in dual fluorescent STn-MIPs. Dual-color labeling of cancer cells was achieved since both red and green emissions were detected in two separate channels of the microscope and an improved accuracy was obtained in comparison with single-signal MIPs. The flow cytometric cell analysis showed that the binding of STn-MIPs was significantly higher (p < 0.001) than that of non-imprinted polymer (NIP) control particles within the same cell line, allowing to distinguish populations. Based on the modularity of the luminescent core–fluorescent MIP shell architecture, the concept can be transferred in a straightforward manner to other target analytes.
L-Lactide was polymerized in bulk at 140 °C with three different cyclic tin catalysts and the time was varied from 1 d up to 14 d. The MALDI TOF spectra confirmed the formation of cyclic polylactides (PLAs) and displayed a characteristic change of peak intensity distribution with formation of a “saw tooth pattern”. This pattern confirms a previous hypothesis that cyclic PLAs tend to form crystallites with extended ring conformation and relatively smooth surface. This type of crystallites is formed under thermodynamic control by transesterification on the surface of the crystallites. In this way PLAs with extraordinarily high melting temperatures (Tm's up to 200.6 °C) and extraordinarily high melting enthalpy were obtained (ΔHm's up to 105 J g−1). These ΔHm values require a revision of the maximum ΔHm value calculated in the literature for ideal PLA crystals.
Laserstrahlhybridschweissen von Türmen für Windkraftanlagen Ökonomische und ökologische Vorteile
(2022)
Das Laserstrahlhybridschweißen ist beim Schweißen von Türmen für Windkraftanlagen eine Alternative zum Unterpulverschweißen von Dickblechen in Mehrlagentechnik und bietet hier ökonomische und ökologische Vorteile. Der industrielle Einsatz des Verfahrens ist jedoch durch prozessspezifische Herausforderungen eingeschränkt. Die im Beitrag beschriebene kontaktlose elektromagnetische Badstütze dient zur Erweiterung des Verfahrenspotenzials im Dickblechbereich >15 mm.
The study deals with the influence of the heat input and the resulting cooling times on the microstructure and Charpy impact toughness of single-pass laser hybrid welded 20-mm thick high-strength steel S690QL. The main focus is on the change of the mechanical properties over the entire seam thickness. The cooling times were measured in-situ using a pyrometer and an optical fibre in three different depths of the seam where Charpy impact test specimens were also later taken. Thereby, three different heat inputs from 1.3 kJ/mm to 2 kJ/mm were investigated. Despite the observed decreased values of both t8/5-cooling time and the Charpy impact toughness in the root part of the seam, the required impact toughness of 38 J/cm2 could be reached in dependance on applied heat input, especially at the heat input of 1.6 kJ/mm.
With additive manufacturing in the powder bed, the component size is limited by the installation space. Joint welding of additively manufactured parts offers a possibility to remove this size limitation. However, due to the specific stress and microstructure state in the additively built material, it is unclear to what extent existing evaluation rules of joint welding are also suitable for welds on additive components. This is investigated using laser beam welding of additively manufactured pipe joints. The welds are evaluated by means of visual inspection, metallographic examinations as well as computed tomography. The types of defects found are comparable to conventional components. This is an indicator that existing evaluation regulations also map the possible defects occurring for weld seams on additive components.
Among the strategies to produce healable thermosetting systems is their modification by the addition of thermoplastic particles. This work investigates the influence of poly(ethylene-co-methacrylic acid) (EMAA) on fibermatrix interfacial properties of a glass fiber reinforced epoxy matrix composite. Epoxy-EMAA interactions were evaluated using differential scanning calorimetry (DSC) and infrared spectroscopy. The effects of EMAA on the epoxy network formation were evidenced by changes in glass transition temperature, cure kinetics and alteration of chemical groups during cure. Interfacial shear strength (IFSS) measurements obtained by single fiber pull-out tests indicate similar interfacial properties for pure and EMAA modified epoxy. Additionally, the potential for self-healing ability of an EMAA modified epoxy was demonstrated. However, IFSS after a healing cycle for the EMAA modified epoxy was lower as compared to the pure epoxy, because of the lower fiber-EMAA interfacial shear strength. So, thermoplastic healing agents has not only to fill cracks in the matrix material, but also have to be optimized regarding its interface properties to the reinforcing fibers.
Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide)
(2022)
The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(L-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75−80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.
Solidification cracking is still a serious problem in laser beam welding, especially in the welding of thick-walled plates. The influence of weld pool geometry on solidification cracking in partial penetration welding of thick plates is investigated within scope of this study. Therefore, a specific experimental setup of steel and quartz glass in butt configuration and on the side with high-speed camera were used to record the weld pool shape. In addition, the influence of laser inclination angle on the weld pool geometry and on solidification crack formation was investigated. The results show a bulge in the weld pool root, which is separated from an upper region by a necking region. This leads to a case where there are three different longitudinal region lengths with different solidification zones. This temporal sequence of solidification strongly promotes the formation of solidification cracks in the weld root.
Ring-expansion polymerizations (REPs) catalyzed by two cyclic tin catalysts(2-stanna-1.3-dioxa-4,5,6,7-dibenzazepine [SnBiph] and
2,2-dibutyl-2-stanna-1,3-dithiolane [DSTL) are performed at 140 °C in bulk.
Small amounts (4 vol%) of chlorobenzene or other solvents are added to facilitate transesterification reactions (ring–ring equilibration) in the solid poly(l-lactide)s. In the mass range up to m/z 13 000 crystalline PLAs displaying a so-called saw-tooth pattern in the MALDI-TOF mass spectra are obtained indicating the formation of extended-ring crystals. The characteristics of extended-ring crystallites and folded-ring crystallites are discussed. Furthermore, extremely high melting temperatures (Tm’s up to 201.2 °C) and melting enthalpies (𝚫Hm’s up to 106 J g−1)) are found confirming that 𝚫Hmmax, the 𝚫Hm of a perfect crystal, is around or above 115 J g−1 in contrast to literature data.
Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field.
The influence of temperature and stacking fault energy (SFE) on the strain-hardening behavior and critical resolved shear stress for twinning was investigated for three Fe–22/25/28Mn–3Al–3Si wt.% transformation- and twinning-induced plasticity (TRIP/TWIP) steels. The SFEs were calculated by two different methods, density functional theory and statistical thermodynamic modeling. The dislocation structure, observed at low levels of plastic deformation, transitions from “planar” to “wavy” dislocation glide with an increase in temperature, Mn content, and/or SFE. The change in dislocation glide mechanisms from planar to wavy reduces the strain hardening rate, in part due to fewer planar obstacles and greater cross slip activity. In addition, the alloys exhibit a large decrease in strength and ductility with increasing temperature from 25 to 200 °C, attributed to a substantial reduction in the thermally activated component of the flow stress, predominate suppression of TRIP and TWIP, and a significant increase in the critical resolved shear stress for mechanical twinning. Interestingly, the increase in SFE with temperature had a rather minor influence on the critical resolved shear stress for mechanical twinning, and other temperature dependent factors which likely play a more dominant role are discussed.
The corrosivity of atmospheres in Europe has changed significantly in recent decades. For the Federal Republic of Germany, no current values for the corrosion rate based on 1‐year atmospheric exposure of standard specimens can be found in the scientific literature after 2000. This paper presents results from a field exposure study in the Berlin metropolitan area and Helgoland in 2016. Based on standard specimens, values for the corrosion rate and the corresponding atmospheric corrosivity category are determined for open exposure and indirect weathering in a ventilated enclosure as sheltering after 1 year of exposure. The results prove that determined corrosivity categories are material‐specific. Sheltered exposure is a typical atmospheric situation for many building components. It allows statements on the effect of the concentration of airborne substances on the corrosivity beyond the normative requirements.
Influence of a 265 °C heat treatment on the residual stress state of a PBF-LB/M AlSi10Mg alloy
(2022)
Laser Powder Bed Fusion (PBF-LB/M) additive manufacturing (AM) induces
high magnitude residual stress (RS) in structures due to the extremely heterogeneous cooling and heating rates. As the RS can be deleterious to the fatigue resistance of engineering components, great efforts are focused on understanding their generation and evolution after post-process heat treatments. In this study, one of the few of its kind, the RS relaxation induced in an as-built PBF-LB/M AlSi10Mg material by a low-temperature heat treatment (265 °C for 1 h) is studied by means of X-ray and neutron diffraction. Since the specimens are manufactured using a baseplate heated up to 200 °C, low RS are found in the as-built condition. After heat treatment a redistribution of the RS is observed, while their magnitude remains constant. It is proposed that the redistribution is induced by a repartition of stresses between the a-aluminium matrix and the silicon phase, as the morphology of the silicon phase is affected by the heat treatment. A considerable scatter is observed in the neutron diffraction RS profiles, which is principally correlated to the presence (or absence) of pockets of porosity developed at the borders of the chessboard pattern.
Two isomorphous crystals are reported based on a naphthylvinylpyridine coformer. The crystals are mechanically flexible and exhibit photosalient response to UV irradiation. We therefore show how multiple mechanical phenomena can be simultaneously designed into a single material by cocrystallization.
Unintended Rate Enhancement in Mechanochemical Kinetics by Using Poly(methyl methacrylate) Jars
(2022)
Time-resolved in situ (TRIS) X-ray diffraction has changed how mechanochemical transformations are studied but requires the use of X-ray transparent jars often made from poly(methyl methacrylate) (PMMA). However, using PMMA jars can alter the apparent kinetics of mechanochemical polymorphism by an order of magnitude, questioning the interpretability of established TRIS methods. Our results suggest that rate enhancement in PMMA jars may not be dominated by chemical effects of the polymer, but rather a result of different equilibrium temperatures within the jar. These features must be better understood before control over mechanochemical reactions can be achieved.
Fluorescent plastically bendable crystals are a promising alternative to silicon-based materials for fabricating photonic integrated circuits, owing to their optical attributes and mechanical compliance. Mechanically bendable plastic organic crystals are rare. Their formation requires anisotropic intermolecular interactions and slip planes in the crystal lattice. This work presents three fluorescent plastically bendable crystalline materials namely, 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-chlorophenol (SB1), 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-bromophenol (SB2), and 2-((E)-(6-Bromopyridin-2-ylimino)methyl)-4-bromophenol (SB3) molecules. The crystal plasticity in response to mechanical stress facilitates the fabrication of various monolithic and hybrid (with a tip-to-tip coupling) photonic circuits using mechanical micromanipulation with an atomic force microscope cantilever tip. These plastically bendable crystals act as active (self-guiding of fluorescence) and passive waveguides both in straight and extremely bent (U-, J-, and O-shaped) geometries. These microcircuits use active and passive waveguiding principles and reabsorbance and energy-transfer mechanisms for their operation, allowing input-selective and direction-specific signal transduction.
Ultrashort pulse laser processing can result in the secondary generation of unwanted X-rays if a critical laser irradiance of about 10^13 W/cm^2 is exceeded. Spectral X-ray emissions were investigated during the processing of tungsten and steel using three complementary spectrometers (based on CdTe and silicon drift detectors) simultaneously for the identification of a worst-case spectral scenario. Therefore, maximum X-ray photon energies were determined, and corresponding dose equivalent rates were calculated. An ultrashort pulse laser workstation with a pulse duration of 274 fs, a center wavelength of 1030 nm, pulse repetition rates between 50 kHz and 200 kHz, and a Gaussian laser beam focused to a spot diameter of 33 µm was employed in a single pulse and burst laser operation mode. Different combinations of laser pulse energy and repetition rate were utilized, keeping the average laser power constant close to the maximum power of 20 W. Peak irradiances ranging from 7.3 × 10^13 W/cm^2 up to 3.0 × 10^14 W/cm^2 were used. The X-ray dose equivalent rate increases for lower repetition rates and higher pulse energy if a constant average power is used. Laser processing with burst mode significantly increases the dose rates and the X-ray photon energies. A maximum X-ray photon energy of about 40 keV was observed for burst mode processing of tungsten with a repetition rate of 50 kHz and a peak irradiance of 3 × 10^14 W/cm^2.
The cyclic R-curve describes the resistance of a material to fatigue crack propagation fromthe short to the long crack regimes and it is therefore an essential ingredient in any fracturemechanics-based fatigue assessment procedure. This work presents different testing proceduresemployed in the experimental determination of the cyclic R-curve, especially focusing onthe comparison with long fatigue crack propagation thresholds obtained by means of thecompression precracking load reduction (CPLR) procedure. The tests were performed on theEA4T steel considering different stress ratios. The results show a good reproducibility of thecyclic R-curves at every stress ratio and for any testing procedure. In addition, the cyclicR-curves were used in a fracture mechanics-based assessment to predict the fatigue limits ofspecimens containing micro-notches.
Determination of fatigue crack growth in the near-threshold regime using small-scale specimens
(2022)
A complete description of the experimental procedure for characterizing the intrinsic fatigue crack propagation threshold (ΔKth,eff) as well as the fatigue crack growth rate (FCGR) in the near-threshold regime using small-scale specimens is presented. A comparative study is carried out on the high strength steel S960QL considering different single edge notch bend (SENB) specimen geometries. On one hand, the reference dimensions of 6 mm thickness (B) and 19 mm width (W) are analysed and referred to as conventional specimens. On the other hand, small-scale specimens with B = 3 mm and W = 4 and 6 mm are also considered. Several loading configurations (3-, 4- and 8-point bending) are used and a load ratio R = 0.8 is applied to avoid crack closure effects. The direct current potential drop (DCPD) technique is used to monitor the crack length. The reduced dimensions of the small-scale specimens imply the necessity of implementing a modified testing procedure compared to the recommendations of current standards for the generation of FCGR data. The results show a good agreement between tests conducted on different specimen sizes, which opens new perspectives in the use of small-scale specimens for characterizing the fatigue crack growth properties in metallic materials. Recommendations and limitations of the procedure are provided and discussed.
Mussel-inspired polydopamine (PDA) initiated a multifunctional modification route that leads to the generation of novel advanced materials and their applications. However, existing PDA deposition techniques still exhibit poor spatial control, have a very limited capability of micropatterning and do not allow to locally tune PDA topography. Herein, we demonstrate PDA deposition based on Multiphoton Lithography (MPL) that enables full spatial and temporal control with nearly total freedom of patterning design. Using MPL, we achieve 2D microstructures of complex design with pattern precision of 0.8 μm without the need of a photomask or stamp. Moreover, this approach permits adjusting the morphology and thickness of the fabricated microstructure within one deposition step, resulting in a unique tunability of materials properties. The chemical composition of PDA is confirmed and its ability for protein enzyme immobilization is demonstrated. This work presents a new methodology for high precision and complete control of PDA deposition, enabling PDA incorporation in applications where fine and precise local surface functionalization is required. Possible applications include multicomponent functional elements and devices in microfluidics or lab-on-a-chip systems.