5 Werkstofftechnik
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Organisationseinheit der BAM
- 5.6 Glas (30) (entfernen)
Eingeladener Vortrag
- nein (5)
The system Na2O.B2O3-SiO2 (NBS) is the basis of many industrial glass applications and therefore one of the most studied systems at all. Glass formation is possible over a wide compositional range, but the system also contains ranges of pronounced phase separation and crystallization tendency. Despite its importance, experimental data are limited to few compositional areas. The general understanding and modelling of glass formation, phase separation, and crystallization in this system would therefore be easier if small step melt series could be studied. The efficient melting of such glass series is now possible with the new robotic glass melting system at the Federal Institute for Materials Research and Testing (BAM, Division Glasses). Using three exemplary joins within this NBS system, the small step changes of glass transition temperature (Tg), crystallization behavior as well as glass density (Roh) was studied. Additionally, experimental Tg and Roh data were compared with their modeled counterparts using SciGlass and a newly developed DFT model, respectively.
Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography
(SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands.
To explore the impact of ambient and structural water on static fatigue, the initiation and growth of 3279 Vickers induced median radial cracks were automatically recorded and analyzed. We find that humidity is more efficient in initiating cracks and promoting their growth than water, which is dissolved in the glass structure. In particular for slow crack growth (< 3x10-6 m s-1), tests in dry nitrogen showed a considerable decrease in the crack growth exponent with increasing water content of the glasses. On the other hand, if tests were performed in humid air, the crack growth exponent was independent of the water content of the hydrous glasses, while stress intensity decreased slightly. These observations indicate that water promotes the processes at the crack-tip regardless of its origin. However, ambient water is more efficient.
Stable crack growth was measured for nominal dry and water-bearing (6 wt%) soda-lime silicate glasses in double cantilever beam geometry and combined with DMA studies on the effects of dissolved water on internal friction and glass transition, respectively. In vacuum, a decreased slope of logarithmic crack growth velocity versus stress intensity factor is evident for the hydrous glass in line with an increase of b-relaxation intensity indicating more energy Dissipation during fracture. Further, inert crack growth in hydrous glass is found to be divided into sections of different slope, which indicates different water related crack propagation mechanism. In ambient air, a largely extended region II is observed for the hydrous glass, which indicates that crack growth is more sensitive to ambient water.
The effect of structural water on density, elastic constants and microhardness of water-bearing soda-lime-silica glasses of up to 21.5 mol% total water is studied. It is found that the Poisson ratio and the water content are positively correlated, while density and the elastic moduli decrease with increasing water content. Vickers hardness decreases by approximately 27% from the dry to the most hydrous glass. For water fractions <3 mol%, the dependencies are non-linear reflecting the non-linear change in the concentrations of OH and H2O molecules dissolved, whereas for water fractions >3 mol% linear dependencies are found. To distinguish the effect of structural water and environmental water, indentations were performed in toluene, nitrogen gas and air. Timedependent softening was evident for testing dry glasses in humid atmospheres as well as for tests of hydrous glasses in dry atmospheres. This indicates that the response times of dissolved water species are effectively equal in both scenarios.
Barium silicate glass powders 4 h milled in CO2 and Ar and sintered in air are studied with microscopy, total carbon analysis, differential thermal Analysis (DTA), vacuum hot extraction mass spectroscopy (VHE-MS), Fourier-transformed infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary-ion mass spectrometry (TOF-SIMS). Intensive foaming of powder compacts is evident, and VHE studies prove that foaming is predominantly caused by carbonaceous species for both milling gases. DTA Shows that the decomposition of BaCO3 particles mix-milled with glass powders occurs at similar temperatures as foaming of compacts. However, no carbonate at the glass surface could be detected by FTIR spectroscopy, XPS, and TOF-SIMS after heating to the temperature of sintering. Instead, CO2 molecules unable to rotate identified by FTIR spectroscopy after milling, probably trapped by mechanical dissolution into the glass bulk. Such a mechanism or microencapsulation in cracks and particle aggregates can explain the contribution of Ar to foaming after intense milling in Ar atmosphere. The amount of CO2 molecules and Ar, however, cannot fully explain the extent of foaming. Carbonates mechanically dissolved beneath the surface or encapsulated in cracks and micropores of particle aggregates are therefore probably the major foaming source.
Glass
(2019)
Overview about the key activities of division 5.6 glass and the diversity of the material glass. For the vacuum hot extraction method (VHE-MS) some examples are presented e. g. for the measurement of water content or the determination of diffusion coefficient of hydrogen in glasses. Finally, an outlook is shown on the robot controlled glass screening device which will be available next year.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
The permeation of hydrogen gas was studied in meta-aluminous (tectosilicate) glass powders of Li2O×Al2O3×SiO2 (LAS), Na2O×Al2O3×SiO2 (NAS) and MgO×Al2O3×SiO2 (MAS) systems by pressure loading and vacuum extraction in the temperatures range 210–310 °C. With this method, both the solubility S and the diffusivity D were determined, while the permeability was given by the product SD. For all glasses, S was found to decrease with temperature, while D increased. Since the activation energy of diffusion of H2 molecules exceeded that of dissolution, permeation increased slightly with temperature. When extrapolated to standard conditions (25 °C), the permeability of tectosilicate glasses was found to be only 10-22–10-24 mol H2 (m s Pa)-1, which is 8–10 magnitudes lower than most polymers. Thin glass liners of these compositions are expected to be the most effective barrier for tanks of pressurised hydrogen.
Physical storage of gaseous hydrogen under high-pressure in glassy micro-containers such as spheres and capillaries is a promising concept for enhancing safety and the volumetric capacity of mobile hydrogen storage systems. As very low permeation through the container wall is required for storage of compressed hydrogen, development of glasses of minimal hydrogen permeability is needed. For this purpose, one has to understand better the dependence of hydrogen permeability on glass structure. The paper points out that minimizing the accessible free volume is as one strategy to minimize hydrogen permeability. Based on previously measured and comprehensive literature data, it is shown that permeation is independently controlled by ionic porosity and network modifier content. Thus, ionic porosity in modified and fully polymerized networks can be decreased equally to the lowest hydrogen permeability among the glasses under study. Applying this concept, a drop of up to 30,000 with respect to the permeation of hydrogen molecules through silica glass is attainable.
Increasing Exposed Metal Site Accessibility in a Co-MOF-74 Material With Induced Structure-Defects
(2019)
Metal-organic frameworks (MOFs) are promising nanoporous materials with many practical applications. This owes largely to their remarkable porosity and the presence of specific chemical functionalities, such as exposed metal sites (EMS). The MOF-74 structure is known for exhibiting one of the highest EMS densities among porous materials. Moreover, the inclusion of structural defects has been proposed to enhance activity further. This was previously achieved by mixing the original linker together with a second one, having lower topology. The presence of structural defects was evidenced by the resulting crystalline properties and thermal stability. In this work, different mixtures of tetratopic 2,5-dihydroxyterephthalic acid with up to 60% of the tritopic hydroxyterephtalic acid were used to synthesize crystalline Co-MOF-74-like materials. Materials synthesized from higher proportions than 30% of hydroxyterephtalic acid in the synthesis media collapse upon partial removal of the solvent molecules. This indicates the presence of structural defects and the importance of the solvent molecules in stabilizing the crystalline structures. Electron microscope images show that crystal size reduces with inclusion of hydroxyterephtalic acid as the second linker. The presence of coordinated solvent molecules at the EMS was evaluated by Fourier-transform infrared spectra (FTIR) spectroscopy, so that a higher degree of solvent-exchange was observed during washing for defective structures. Furthermore, TG analysis suggests defective structures exhibit lower desolvation temperatures than the defect-free structures. Finally, N2 adsorption-desorption analyses at −196°C showed an enhanced accessibility of the gas to the inner porosity of the defective structures and therefore, the EMS of the material. All these finding make this pathway interesting to enhance the potential interest of these materials for an industrial application because of both a facilitated activation and a better access to the active sites.
Iron aluminides, already reported in the late 19th century, did not cease to attract the interest of scientists and engineers ever since. Besides good oxidation resistance, low density and resource availability, potentials for hightemperature strengths that compete with high-alloy steels were unlocked by low alloy contents. Still, research on alloy design continues, as alloying usually comes at the price of brittleness in low-temperature regimes. A potential candidate is the quinary Fe–Al–Mo–Ti–B system which is strengthened by solid solution and eutectic borides. It was shown to have good strength and outstanding creep resistance under compressive loading up to elevated temperatures. Although the individual effect of alloy additions is well understood in iron aluminides, little is known about the combined effects of alloying concentrations on microstructure, phase stability and mechanical properties. Therefore a systematic study of two Ti-doped near-Fe3Al alloys with varying contents of Mo (2–4 at.%) and B (0.5–1 at.%) was conducted. In total eight different alloys were fabricated by investment casting into ceramic shell molds. Alloys were characterized and compared by grain size, phase transitions, microstructure evolution as well as elemental compositions and volume fractions of phases. For mechanical characterization, macrohardness and microhardness tests as well as tensile tests at ambient and high tempera tures were conducted. Independent of alloy additions, alloys with 24–25 at.% Al exhibit superior proof strength due to a higher matrix hardness. Decreasing B content generally decreases strength by lower secondary phase fractions which contribute via particle hardening. Reducing Mo content decreases both the solute concentration in the matrix and secondary phase fractions. Surprisingly, strength is similar or even superior to alloys with higher Mo content. Strength relations are discussed with a focus on solid-solution hardening theory and other competing strengthening mechanisms.
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 crystallization proceeds by the advance of the crystal faces into the disordered phase at the expense of the material excess, the supersaturation. Using a conservation constraint for the transformation ratio α∈[0,1] as complementing the rescaled supersaturation to 1 and a kinetic law for the normal growth velocity as function of the supersaturation raised to power g, the growth order, we derive an equation for the rate of transformation dα/dt. We integrate it for the six combinations of the three spatial dimensions D = 1, 2, 3 and the two canonical values of g = 1, 2 towards obtaining expressions for αDg. The same equation, with g = 1 and D = n (n is the so called Avrami exponent) is obtained when taking only the linear in α term from the Taylor’s expansion around α = 0 of the model equation of Johnson-Mehl-Avrami-Kolmogorov (JMAK). We verify our model by fitting datasets of α21 and α31 (from α = 0 to αupper = 0.999) with JMAK to obtain from the fit n = 1.725, 2.43, resp. We show
further how the values of n depend on the value of αupper to which the fit is performed starting always from 0. Towards building a validation protocol, we start with validating α21 with published results.
The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO4 3−) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+−PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.
Up to now, oriented surface crystallization phenomena are discussed controversially, and related studies are restricted to few glasses. The vast majority of previous work does not consider possible effects of surface preparation and surrounding atmosphere. Moreover, very few observations of surface crystal orientation were made on separately grown crystals.
The aim of our project is to advance the basic understanding of oriented surface crystallization, e.g. whether preferred orientation of surface crystals results from oriented nucleation or reorientation mechanisms during early crystal growth. In both cases, crystal orientation may reflect the orientation of the glass surface or that of anisotropic active surface nucleation sites. Therefore, we focus on orientation of surface crystals separately growing under controlled conditions.
First results on diopside (MgCaSi2O6) and walstromite (BaCa2Si3O9) crystals growing from 18BaO·22CaO·60SiO2 and MgO·CaO·2SiO2 glass surfaces, respectively, indicate that different orientation mechanisms may occur.
Neighbored walstromite crystals were found to gradually reorient themselves when they are going to impinge each other during stepwise isothermal treatments (log η = 4,5 Pa*s) of polished glass samples. Nevertheless, no preferred crystal orientation was evident for separate crystals.
For diopside crystals growing from polished glass surfaces (1 μm diamond lapping foil), strong preferred orientation was observed for 3.5 to 85 min annealing at 850 °C. Electron Backscatter Diffraction (EBSD) studies showed that the c-axis of surface crystals is oriented parallel to the glass surface and that separated diopside crystals as small as 600 nm are already oriented. Studies on glass surfaces, polished with diamond lapping foils starting from 16 μm down to 1 μm grain, revealed that crystal orientation may scatter arround this preferential orientation and that this scatter progressively decreases with decreasing polishing grain size.
A glass of the composition 37BaO·16CaO·47SiO2 wt% produced on an industrial scale is crystallized at 970 °C for times ranging from 15 min to 2 h. The crystallization at the immediate surface as well as the crystal growth into the bulk are analyzed using scanning electron microscopy (SEM) including energy dispersive X-ray spectroscopy (EDXS) and electron backscatter diffraction (EBSD) as well as X-ray diffraction in the Θ–2Θ setup (XRD). The immediate surface shows the oriented nucleation of walstromite as well as the formation of wollastonite and an unknown phase of the composition BaCaSi3O8. All three phases also grow into the bulk where walstromite ultimately dominates the kinetic selection and grows throughout the bulk due to a lack of bulk nucleation. Walstromite shows systematic orientation changes as well as twinning during growth. A critical analysis of the XRD-patterns acquired from various crystallized samples indicates that their evaluation is problematic and that phases detected by XRD in this system should be verified by another method such as EDXS.
Oriented surface crystallization on polished diopside glass surfaces has been studied with scanning electron microscopy, electron backscatter diffraction, transmission electron microscopy and laser scanning microscopy.
An orientation preference of [001] parallel to the glass surface was detected for separately growing diopside crystals even as small as 700 nm in size. This finding shows that crystal orientation occurs in the outermost surface layer without crystal-crystal interaction and indicates that the crystal orientation is a result of oriented nucleation. Depending on surface preparation, monomodal crystal orientation distributions with [100] perpendicular to the surface or bimodal distributions with [100] and [010] perpendicular to the glass Surface were detected. It was also shown that the degree of crystal orientation increases with decreasing Surface roughness. The observed orientation of diopside crystals could be explained in terms of the interfacial energies of different crystal faces.
Sample preparation for analytical scanning electron microscopy using initial notch sectioning
(2021)
A novel method for broad ion beam based sample sectioning using the concept of initial notches is presented. An adapted sample geometry is utilized in order to create terraces with a well-define d step in erosion depth from the surface. The method consists of milling a notch into the surface, followed by glancing-angle ion beam erosion, which leads to preferential erosion at the notch due to increased local surface elevation. The process of terrace formation can be utilized in sample preparation for analytical scanning electron microscopy in order to get efficient access to the depth-dependent microstructure of a material. It is demonstrated that the method can be applied to both conducting and non-conducting specimens. Furthermore, experimental parameters influencing the preparation success are determined. Finally, as a proof-of-concept, an electron backscatter diffraction study on a surface crystallized diopside glass ceramic is performed, where the method is used to analyze orientation dependent crystal growth phenomena occurring during growth of surface crystals into the bulk.