Filtern
Dokumenttyp
- Vortrag (15)
- Zeitschriftenartikel (12)
- Buchkapitel (1)
- Beitrag zu einem Tagungsband (1)
- Posterpräsentation (1)
- Forschungsdatensatz (1)
Sprache
- Englisch (31)
Schlagworte
- X-ray photoelectron spectroscopy (31) (entfernen)
Organisationseinheit der BAM
Paper des Monats
- ja (1)
We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using
these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.
(1) First results show the suitability of IL as reference for quantification of XPS (at least for organic materials).
(2) Different quantification methods lead to similar results (with a slight advantage for “background method”).
(3)Promising reference material for a better understanding and traceable protocols for the quantification of organic materials with XPS.
X-ray photoelectron spectroscopy (XPS) is widely used for characterising the chemistry of graphene-related two-dimensional materials (GR2M), however the careful preparation of the sample for analysis is important in obtaining representative quantifications. We report an investigation by three laboratories showing that the preparation method for oxygen-functionalised graphene nanoplatelet (GNP) powders has a significant effect on the homogeneous-equivalent elemental composition measured in XPS. We show that pressing GNP powders onto adhesive tapes, into recesses, or into solid pellets results in inconsistencies in the XPS quantification. The measured oxygen-to-carbon atomic ratio from GNP pellets depends upon the die pressure used to form them and the morphology of the GNPs themselves. We recommend that powder samples of GR2Ms are pelletised prior to XPS analysis to improve repeatability and reproducibility of measurements.
The principles of (Hard) X-ray photoelectron spectroscopy and some application in the field of (core-shell) nanoparticles will be presented. The presentation should answer hoe to get reliable results. Furthermore, examples of the correlation between physical-chemical measurments and toxicological results are given which are crucial for the risk assessment of nanoparticles.
International standards describing reliable protocols will facilitate the commercialization of graphene and related 2D materials. One physico-chemical key property next to flake size and thickness is the chemical composition of the material. Therefore, an ISO standard is under development with X-ray photoelectron spectroscopy having a prominent role. With its information depth of around 10 nm which is the similar length scale as the thickness as of particles of 2D materials consisting of a few monolayer XPS seems to be highly suitable for this purpose. Different sample preparation methods like pressing the powders onto adhesive tapes, into recesses, or into solid pellets result in inconsistencies in the quantification. For the validation of the quantification with XPS an interlaboratory comparison was initiated under the auspice of the “Versailles Project on Advanced Materials and Standards” (VAMAS). First results confirm that the sample preparation method (pellet vs. powder) influences the quantification results clearly.
The passivation behavior of alloy 31 was investigated as a function of passivation potential in a green-death solution at 40 °C. The alloy 31 surface is in a stable passive state during cyclic potentiodynamic polarization. In potentiostatic polarization of alloy 31, passive current density increases with an increase in the passivation potential. Electrochemical impedance spectroscopy (EIS) and Mott–Schottky (M–S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The increase of the applied potential is considered to be a reason for the change in passive film stability.
Lead(II) is a toxic pollutant often found in metalcontaminated soils and wastewaters. In acidic aqueous environments, Pb(II) is highly mobile. Chemical treatment strategies of such systems therefore often include neutralization agents and metal sorbents. Since metal solubility and the retention potential of sorbents depend on the redox state of the aqueous system, we tested the efficiency of the naturally occurring redox-sensitive ferrous iron carbonate mineral siderite to remove Pb(II) from acidic aqueous solutions in batch experiments under oxic and anoxic conditions over a total of 1008 h. Siderite dissolution led to an increase in reactive solution pH from 3 to 5.3 and 6.9, while 90 and 100% of the initial aqueous Pb(II) (0.48 × 10−3 mol kg−1) were removed from the oxic and anoxic systems, respectively.
Scanning and transmission electron microscopy, combined with X-ray absorption and photoelectron spectroscopy, indicated that under oxic conditions, Pb(II) was consumed by cerussite precipitation and inner-sphere surface complexation to secondary goethite.
Under anoxic conditions, Pb(II) was removed by the rapid precipitation of cerussite. This efficient siderite dissolution-coupled sequestration of Pb(II) into more stable solid phases demonstrates this potential method for contaminated water Treatment regardless of the redox environment.
The recent development of x-ray photoelectron spectroscopy using excitation sources different from the usual lab-source Mg Kα and Al Kα and spectrometers with more sophisticated lens systems requires flexible approaches for determining the transmission function. Therefore, the approach using quantified peak areas (QPA) was refined.1 A new algorithm allows a more precise estimation of the transmission function which could be shown by comparing the results obtained with the new version with former calculations. Furthermore, next to the established reference materials Cu, Ag and Au, ionic liquids can be used for estimating the transmission function at beamlines with variable excitation energies. Comparison between the measured and stoichiometric composition shows that a transmission function was determined which allows a reasonable quantification.
The composition of thin films of polymer blends in vertical direction is still under discussion. For explaining the thickness dependence of some properties like the thermal glass transition temperature, a three-layer model has been introduced consisting of an adsorbed layer with a reduced segmental mobility at the substrate, a bulk-like layer in the middle of the film and an outermost surface layer with a higher molecular mobility. X-ray photoelectron spectroscopy (ER-XPS) measurements with a varying excitation energy from 400 eV to 1486.6 eV and, herewith, an information depth from 1.5 nm to 10 nm were performed at PVME/PS films with compositions of 25/75 wt% and 50/50 wt% and thicknesses between 15 nm and 190 nm. As expected, it was found that the PVME concentration decreases with increasing information depth. Secondly, a complex correlation between the PVME concentration at the surface and the film thickness was found. The PVME concentration increases with decreasing film thickness until a maximum at 30 nm. For thinner films, the PVME concentration decreases. These data agree with previous investigations obtained with specific heat spectroscopy.
We thank BESSY II (HZB) for the allocation of beamtime at the HE-SGM beamline and for technical support. DFG (Project number 124846229) is acknowledged for financial support.
XPS of GR2M
(2022)
Recent publications indicate that the order of electrochemical anodization (before or after the laser processing step) plays an important role for the response of bone-forming osteoblasts—an effect that can be utilized for improving permanent dental or removable bone implants. For exploring these different surface functionalities, multimethod morphological, structural, and chemical characterizations are performed in combination with electrochemical pre- and postanodization for two different characteristic microspikes covered by nanometric laser-induced periodic surface structures on Ti–6Al–4V upon irradiation with near-infrared ps-laser pulses (1030 nm wavelength, ≈1 ps pulse duration, 67 and 80 kHz pulse repetition frequency) at two distinct sets of laser fluence and beam scanning parameters. This work involves morphological and topographical investigations by scanning electron microscopy and white light interference microscopy, structural material examinations via X-ray diffraction, and micro-Raman spectroscopy, as well as near-surface chemical analyses by X-ray photoelectron spectroscopy and hard X-ray photoelectron spectroscopy. The results allow to qualify the mean laser ablation depth, assess the spike geometry and surface roughness parameters, and provide new detailed insights into the near-surface oxidation that may affect the different cell growth behavior for pre- or postanodized medical implants.
Since its isolation, graphene has received growing attention from academia and industry due to its unique properties. However, the “what is my material” barrier hinders further commercialization. X-ray photoelectron spectroscopy (XPS) is considered as a method of choice for the determination of the elemental and chemical composition. In this work the influence of the morphology of graphene particles on the XPS results is studied and investigated as a function of X-ray energy, using conventional XPS with Al K𝜶 radiation and hard X-ray photoemission spectroscopy (HAXPES) using Cr K𝜶 radiation. Thereby, the information depth is varied between 10 and 30 nm. For this purpose, two commercial powders containing graphene nanoplatelets with lateral dimensions of either ≈100 nm or in the micrometer range are compared. These larger ones exist as stack of graphene layers which is inspected with scanning electron microscopy. Both kinds of particles are then functionalized with either oxygen or fluorine. The size of the graphene particles is found to influence the degree of functionalization. Only the combination of XPS and HAXPES allows to detect the functionalization at the outermost surface of the particles or even of the stacks and to provide new insights into the functionalization process.
Nanoparticles have gained increasing attention in recent years due to their potential and application in different fields including medicine, cosmetics, chemistry, and their potential to enable advanced materials. To effectively understand and regulate the physico-chemical properties and potential adverse effects of nanoparticles, validated measurement procedures for the various properties of nanoparticles need to be developed. While procedures for measuring nanoparticle size and size Distribution are already established, standardized methods for analysis of their surface chemistry are not yet in place, although the influence of the surface chemistry on nanoparticle properties is undisputed. In particular, storage and preparation of nanoparticles for surface analysis strongly influences the analytical results from various methods, and in order to obtain consistent results, sample preparation must be both optimized and standardized. In this contribution, we present, in detail, some standard procedures for preparing nanoparticles for surface analytics. In principle, nanoparticles can be deposited on a suitable substrate from suspension or as a powder. Silicon (Si) Wafers are commonly used as substrate, however, their cleaning is critical to the process. For sample preparation from suspension, we will discuss drop-casting and spin-coating, where not only the cleanliness of the substrate and purity of the suspension but also its concentration play important roles for the success of the preparation methodology.
For nanoparticles with sensitive ligand shells or coatings, deposition as powders is more suitable, although this method requires particular care in fixing the sample.
The lead authors failed to name two collaborators as co-authors. The authors listed should include:
Miss Claudia L. Compean-Gonzalez (ORCID:
0000-0002-2367-8450) and Dr. Giacomo Ceccone (ORCID:
0000-0003-4637-0771).
These co-authors participated in VAMAS project A27, provided data that were analyzed and presented in this publication (and supporting information), and reviewed the manuscript before submission.
The electrochemical behavior of UNS(1) N08031 was investigated as a function of electrode potential in Green-Death(2) solution at 40 °C. The UNS N08031 surface is in a stable passive state during cyclic potentiodynamic polarization without an initiation and/or propagation of localized corrosion. In potentiostatic polarization of UNS N08031 for 3600 s, passive current density increases with an increase in the passivation potential from 0.7 to 1.0 VSSE (silver/silver chloride reference electrode in saturated potassium chloride) Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The mechanism of the defective passive film formation is discussed. The increase of the applied potential is considered to be a reason for the change in passive film stability.