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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.
Sand erosion of solar glass: Specific energy uptake, total transmittance, and module efficiency
(2018)
Surface roughness, R Z , normal transmittance, Τ N , total transmittance, Τ T , and photovoltaic (PV) module efficiency, η S , were measured for commercial solar glass plates and PV test modules identically sandblasted with different loads of quartz sand (200 – 400 μ m), impact inclination angles, and sand particle speed. Measured data are presented versus the specific energy uptake during sand blasting, E (J/m2). Cracks, adhering particles, and scratch ‐ like textures probably caused by plastic flow phenomena could be observed after sand blasting. Their characteristic size was much smaller than that of sand particles.
After blasting and subsequent cleaning, the glass surface was still covered with adhering glass particles. These particles, cracks, and scratch ‐ like textures could not be removed by cleaning. For sand blasting with α = 30° inclination angle and E = 30 000 J/m2, normal transmittance, total transmittance, and relative module efficiency decreased by 29%, 2% and ∽ 2%, respectively. This finding indicates that diffusive transmission of light substantially contributes to PV module efficiency and that the module efficiency decrease caused by sand erosion can be better estimated from total than by normal transmittance measurements.
The crystallization behavior of sodium ion conductive Na2MnP2O7 glass was examined to clarify the crystallization mechanism. The formation of thermodynamically metastable phase, layered Na2MnP2O7, at the surface of the glass occurred. Heat treatment at 430 °C for 3 h lead to surface crystals of Na2MnP2O7 oriented with the (101) direction perpendicular to the sample surface. As the heat treatment temperature increased, the glass-ceramic samples deformed, and the presence numerous micro bubbles due to dissolved water was detected.
The suitability of an Al2O3 coating for corrosion protection on X20Cr13 was evaluated in various artificial geothermal brines, focusing on the influence of different pH (4, 6 and 8) and their chemical compositions on the coating properties. All experiments were performed in the laboratory using autoclaves at 150 ◦C and 1 MPa in deaerated condition for 1 and 7 days. Results showed that the pH of geothermal waters is the most detrimental factor in the transformation of ɣ-Al2O3 and its protective abilities. Delaminations were found in the Coating exposed to geothermal brines with pH 4. FTIR spectra indicated a transformation of ɣ-Al2O3 to boehmite AlOOH after exposure to pH 4 and 6, and bayerite Al(OH)3 was formed after exposure to pH 8. Different Crystal structures of the hydrated Al2O3 also contribute to the stability of the coatings, observed by the SEM- EDX of the surface and cross-section of coatings. This study indicated that ɣ-Al2O3 sol-gel coating presents a promising aspect of corrosion protection in geothermal environment with a neutral pH.
Al2O3 has been widely used as a coating in industrial applications due to its excellent chemical and thermal resistance. Considering high temperatures and aggressive mediums exist in geothermal systems, Al2O3 can be a potential coating candidate to protect steels in geothermal applications. In this study, γ-Al2O3 was used as a coating on martensitic steels by applying AlOOH sol followed by a heat treatment at 600 °C. To evaluate the coating application process, one-, two-, and three-layer coatings were tested in the artificial North German Basin (NGB), containing 166 g/L Cl−, at 150 °C and 1 MPa for 168 h. To reveal the stability of the Al2O3 coating in NGB solution, three-layer coatings were used in exposure tests for 24, 168, 672, and 1296 h, followed by surface and cross-section characterization. SEM images show that the Al2O3 coating was stable up to 1296 h of exposure, where the outer layer mostly transformed into boehmite AlOOH with needle-like crystals dominating the surface. Closer analysis of cross-sections showed that the interface between each layer was affected in long-term exposure tests, which caused local delamination after 168 h of exposure. In separate experiments, electrochemical impedance spectroscopy (EIS) was performed at 150 °C to evaluate the changes of coatings within the first 24 h. Results showed that the most significant decrease in the impedance is within 6 h, which can be associated with the electrolyte penetration through the coating, followed by the formation of AlOOH. Here, results of both short-term EIS measurements (up to 24 h) and long-term exposure tests (up to 1296 h) are discussed.
Al2O3 coatings are often used as protective layers on steels against electrochemical and high-temperature corrosion because they are chemically inert and stable at elevated temperatures. This study presents preliminary work on the possibilities of using Al2O3 sol-gel coatings for corrosion protection of martensitic stainless steels in geothermal environments. Al2O3 sol-gel coatings were applied on UNS S42000, which is known to be susceptible to uniform and localized corrosion. The coated steel specimens were then tested in two types of artificial geothermal water, which simulate the geothermal fluids found in Sibayak (SBY), Indonesia, and North German Basin (NGB), Germany, respectively. SBY has pH 4 and 1.5 g/L of chloride ions, whereas NGB has a pH of 6 and 166 g/L of chloride ions. All experiments were carried out in autoclaves at 150 °C and 1 MPa under the deaerated condition. Evaluations were performed by investigating the surface profiles of both uncoated and coated steels before and after the corrosion test using a Laser Scanning Microscope (LSM) and Scanning Electron Microscope (SEM). Finally, Electrochemical Impedance Spectroscopy (EIS) was performed to compare the corrosion resistance of Al2O3 coated steels in SBY and NGB solutions. It was observed from the corrosion test that Al2O3 coatings are more suitable for use in the geothermal water with a higher pH.
Dissolved water has major impact on the physical and chemical properties of phosphate glasses. In the present study we have investigated the structural response to water incorporation for glasses in the system Li2O–MgO–Al2O3–P2O5.
Glasses containing 0–8 wt% H2O were synthesised at 500 MPa confining pressure in internally heated gas pressure vessels at 1323 K (LMP, Al-poor glass) and 1423 K (LMAP, Al-enriched glass). Water contents of glasses were determined by pyrolysis and subsequent Karl-Fischer titration (KFT) and/or by infrared spectroscopy. Density varies nonlinearly with water content implying large structural changes when adding up to 2 wt% H2O to the dry glass. Glass Transition temperatures measured by differential thermal analysis (DTA) continuously decrease with water content. The trend can be explained by depolymerisation of the phosphate network. Near-infrared spectroscopy shows that even in Al poor glasses only a minority of dissolved water is present as H2O molecules, but the largest amount is present as OH Groups formed by hydrolysis of P–O–P bonds. The network is stabilised by aluminium which is predominantly six-coordinated in these glasses as shown by 27Al MAS NMR spectroscopy. With increase of Al in the glasses, breaking up of the Phosphate network through hydrolysis is depressed, i.e. much lower OH Contents are formed at same total water content.
Network depolymerisation upon addition of H2O is evident also from 31P MAS NMR spectroscopy. While Phosphate tetraheda are crosslinked by two to three bridging oxygen in dry glasses, diphosphate Groups are dominant in glasses containing 8 wt% H2O.
To understand the impact of dissolved water on structure and properties, four boron-rich glasses of molar compositions 15-x Na2O x CaO 15 SiO2 70 B2O3 (with x=0, 7.5, 10) and 10 Na2O 15 SiO2 75 B2O3 were prepared and subsequently hydrated (up to 8 wt% H2O). Density measurements show a non-linear trend upon hydration implying large structural changes in particular at water contents<2 wt%. Near-infrared spectroscopy shows hydroxyl groups are the dominant species in all glasses upon the entire range of water content. Molecular H2O is detectable only at total water contents>2 wt%. 11B MAS NMR spectra show that the abundance of BO4 species is mainly controlled by ratio of (Na2O+CaO)/B2O3 while incorporation of water plays a minor role.
Compared to borate glasses, the efficiency of formation of BO4 tetrahedra is favored by crosslinking of the network by SiO4-units. The glass transition temperatures, determined by differential thermal analysis, decreases continuously with water content due to breakage of B-O-B bonds by hydrolysis. However, compared to Silicates and aluminosilicates, the effect of dissolved water is less pronounced which can be explained by weaker B-O-B bonds in comparison to Si-O-Si bonds.
To understand the influence of water and alkalis on aluminosilicate glasses, three polymerized glasses with varying ratios of Na/K were synthesized [(22. 5-x)Na2O-xK2O-22.5 Al2O3-55 SiO2 with x = 0, 7.5, and 11.25]. Subsequently, these glasses were hydrated (up to 8 wt% H2O) in an internally heated gas pressure vessel. The density of hydrous glasses linearly decreased with water content above 1 wt%, consistent with the partial molar volume of H2O of 12 cm3/mol. Near-infrared spectroscopy revealed that hydroxyl groups are the dominant species at water content of <4 wt%, and molecular water becomes dominating at water content of >5 wt%. The fraction of OH is particularly high in the pure Na-bearing glass compared to the mixed alkali glasses. 27Al magic angle spinning-NMR spectroscopy shows that aluminum is exclusively fourfold coordinated with some variations in the local geometry. It appears that the local structure around Al becomes more ordered with increasing K/Na ratio. The incorporation of H2O reinforces this effect. The differential thermal analysis of hydrous glasses shows a significant mass loss in the range of glass transition already during the first upscan, implying the high mobility of water in the glasses. This observation can be explained by the open structure of the aluminosilicate network and by the low dissociation enthalpy of H2O in the glasses (≈ 8 kJ/mol). The effect of the dissolved H2O on the glass transition temperature is less pronounced than for other aluminosilicate glasses, probably because of the large fraction of Al in the glasses.
Borosilicate glasses (16Na2O–10B2O3–74SiO2, NBS) with water contents up to 22 mol% H2O were prepared to study the effect of water on structural relaxation using DTA, viscometry and internal friction measurements. The results show that the glass transition temperature Tg of DTA and the isokom temperature T12, of viscometry are in excellent agreement, confirming the equivalence of enthalpy and viscous relaxation for NBS glass. Combining Tg data with water speciation data demonstrates that OH groups are mainly responsible for the decrease of Tg with increasing hydration, while molecular water plays only a minor role. Internal friction spectra at 7.125 Hz confirm the decisive influence of water on mechanical relaxation. The temperature range of α-relaxation (glass transition) strongly decreases while two β-relaxation peaks (sub-Tg) progressively appear with increasing water content. A high temperature β-relaxation peak, attributed to the presence of OH groups, shifts from 670 to 450 K as total water content increases from 0.01 to 5 wt%. A low temperature β-relaxation peak, attributed to molecular water, appears at 380 K and 330 K in glasses containing 3 and 5 wt% H2O, respectively. These findings suggest that relaxation mechanism of different hydrous species at low temperature may contribute to fatigue of stressed glasses.
Artificial bone replacement by individual customized three-dimensional resorbable bioactive glass has not yet been widely established in the clinical use. This is mainly due to the antagonism of sintering ability and suitable bioactivity. Competitive crystallization often prevents the generation of dense sintered bodies, especially for additive manufactured 3D structures. Previous studies of the fluoride-containing glass F3 have shown its potential to combine both sintering ability and suitable bioactivity. Furthermore, the occurring sintering blockade by surface crystallization of Na2CaSi2O6 was tunable by glass particle size.
In this study the glasses F3, F3-Cu with 1 mol% CuO added at the expense of CaO and the well-known 13-93 were chosen to determine the influence of surface crystallization on 3D printed sinter bodies. For this purpose, grain size fractions in range of smaller 32 µm to 315 µm in fraction size of 6-20 µm were sieved from jaw crushed glass frit as well as glass cubes were cut from casted blocks for all glasses. Sintering behavior of both pressed and printed powder compacts was observed via heating microscopy. Crystallization was determined by DTA and crystallization progress was monitored on fractured sinter bodies and polished cubes via electron and laser scanning microscopy as well as with diffractometry.
Depending on grain size the formation of crystalline support framework along former grain boundaries shows the capability to stabilize fully densified sinter bodies before softening. Beside of this, the generation of complex hierarchic porosity was possible as well.
Um die Langzeitbeständigkeit von Hochtemperatur-Festoxidbrennstoffzellen (SOFC) sicherzustellen, ist das grundlegende Verständnis der viskosen Schließung oder Heilung von Rissen, als Folge wechselnder thermischer oder mechanischer Belastung, in Gläsern und teilkristallinen Materialien ein entscheidender Faktor. In Glas ist die Rissheilung hauptsächlich durch viskoses Fließen bestimmt. In teilkristallinen Schmelzen bewirkt der kristalline Volumenanteil die Erhöhung der effektiven Viskosität. Um die Auswirkungen des kristallinen Volumenanteils auf die Rissheilung zu ergründen, wurden Glasmatrixkomposite mit variierten inerten kristallinen Fülleranteilen, die während der Wärme-behandlung konstant blieben, hergestellt. Verwendet wurde ein kristallisationsträges Natrium-Calcium-Silicatglas und ZrO2 als inerter Füller. Komplexe, reproduzierbare Rissstrukturen wurden durch Vickers-Eindrücke erzeugt und die viskose Rissschließung während isothermer Wärmebehandlungs-schritte mittels Laser-Scanning-Mikroskopie verfolgt. Die Untersuchungen zeigen, dass, verglichen zum füllerfreien Glas, der kristalline Phasenanteil die effektive Viskosität erhöht und dadurch großräumiges Fließen verlangsamt. Dies verzögert das Aufweiten der Risse. Dieser Effekt erschwert die Rissverkürzung und führt oftmals zu großen gerundeten Kavitäten und dadurch zu einer verzögerten Rissschließung. Wird dieses Aufweiten verringert, ist zunächst ein lokales viskoses Fließen der Restglasphase weiterhin gegeben, sodass sich die Risse sogar schneller schließen. Für kristalline Anteile > 27 Vol% bildet sich dann ein stabiles Perkolationsgerüst aus, das die weitere Rissschließung auch lokal unterbindet. Nur innerhalb größerer glasiger Bereiche ist hierbei noch eine Rissschließung zu beobachten. Ein Optimum der Risslängenverkürzung konnte bei 17 Vol% beobachtet werden.
Sintered bioactive glass scaffolds of defined shape and porosity, e.g. made via additive manufacturing, must provide sufficient bioactivity and sinterability. As higher bioactivity is often linked to high corrosion and crystallization tendency, a certain compromise between sintering ability and bioactivity is therefore required. Groh et al. developed a fluoride-containing bioactive glass (F3), which allows fiber drawing and shows a bioactivity well comparable to that of Bioglass®45S5.
To study whether and to what extent the sinterability of F3 glass powder is controlled by particle size, coarse and fine F3 glass powders (300-310µm and 0-32µm) were prepared by crushing, sieving and milling. Sintering, degassing and phase transformation during heating were studied with heating microscopy, vacuum hot extraction (VHE), DTA, XRD, and SEM.
For the coarse glass powder, sintering proceeds slowly and is limited by surface crystallization of primary Na2CaSi2O6 crystals. Although the crystallization onset of Na2CaSi2O6 is shifted to lower temperature, full densification is attained for the fine powder. This finding indicate that certain porosity might be tuned via particle size variation. Above 900°C, intensive foaming is evident for the fine powder. VHE studies revealed that carbon species are the main foaming source.
Crack healing in glass ceramic solid oxide fuel cell (SOFC) sealants is of utmost importance as cracks caused by thermal cycling remain a bottleneck in developing durable SOFC. Whereas no or low crystal volume fraction seems most favorable for viscous crack healing, it does not for load bearing and undesired diffusion. On the other hand, crystals or filler particles can make the sealant less prone to these disadvantages but it could increase the effective composite viscosity and retard crack healing.
Against this background, the influence of crystal volume fraction, phi, on viscous crack healing in glass matrix composites prepared from soda lime silicate glass and zirconia filler particles was studied. Vickers indention induced radial cracks were healed isothermally during interrupted annealing steps and monitored with optical microscopy. Due to the slow crystallization of the glass under study, phi could be kept constant during crack healing.
For bulk glass samples (phi = =), the decrease in radial crack length was retarded by an initial increase in crack width due to crack rounding. Up to phi = 0.15 the increase in effective viscosity retarded this crack broadening thereby yielding faster crack healing. For phi > 0.15, crack broadening was progressively suppressed but the same was true for crack healing, which was fully prevented above phi = 0.3. Results indicate that optimum micro structures can prevent crack broadening limited by the global effective composite viscosity and this way promote crack healing limited by local glass viscosity.
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.
A novel method to generalize kinetic data of viscous crack healing in glasses is proposed. The method assumes that crack healing progress is proportional to the healing time, t, and indirect proportional to viscosity, n. This way, crack length and crack width data, normalized to the initial crack length and plotted versus t/n, allow to compare crack healing progress for different cracks and healing temperatures in a master curve. Crack healing experiments conducted in this study demonstrate the applicability of this method for a commercial microscope slide glass.
AbstractViscous healing of cracks induced by the Vickers indentation in a soda lime magnesium silicate, a soda borosilicate, and a soda aluminosilicate glass (NAS) was studied by laser scanning microscopy. Plots of the crack length, width, and depth normalized to the initial crack length versus time over viscosity merge into single master curves of each of these quantities for each glass. Despite glass properties do not differ strikingly from each other, however, these master curves strongly differ among the glasses. This finding was attributed to a different interplay of various crack healing phenomena. Lateral cracks were found to be responsible for the bulging of the sample surface around the Vickers imprint, which in turn promotes radial crack widening as the main cause of healing delay. The most rapid healing of lateral cracks was observed in NAS in which bulging and crack widening were least pronounced.
This study investigates the sintering and crystallization behavior and kinetic of the bioactive glass (BG) 13–93 with nominal composition (in mol%): 54.6 SiO2 - 1.7 P2O3 - 22.1 CaO - 6.0 Na2O - 7.9 K2O - 7.7 MgO. Sintering and crystallization were investigated non-isothermally for various particle size fractions smaller than 315 μm as well as for bulk samples. Densification was not hindered by the presence of crystalline phases across all particle size fractions. Afterwards, wollastonite was found as the dominant crystal phase at higher temperature which resorb primary surface precipitation-like quartz crystallites. The growth direction shifts into volume when the sample surface is nearly covered. The crystal growth rate of wollastonite was calculated from the crystalline surface layer thickness measured during heating. The findings of this study are relevant for the high temperature processing of BG 13–93.
The sintering of bioactive glasses allows for the preparation of complex structures, such as three‐dimensional porous scaffolds. Such 3D constructs are particularly interesting for clinical applications of bioactive glasses in bone regeneration, as the scaffolds can act as a guide for in‐growing bone cells, allowing for good Integration with existing and newly formed tissue while the scaffold slowly degrades. Owing to the pronounced tendency of many bioactive glasses to crystallize upon heat treatment, 3D scaffolds have not been much exploited commercially. Here, we investigate the influence of crystallization on the sintering behavior of several bioactive glasses. In a series of mixed‐alkali glasses an increased CaO/alkali metal oxide Ratio improved sintering compared to Bioglass 45S5, where dense sintering was inhibited.
Addition of small amounts of calcium fluoride helped to keep melting and sintering temperatures low. Unlike glass 13‐93, these new glasses crystallized during sintering but this did not prevent densification. Variation in bioactive glass particle size allowed for fine‐tuning the microporosity resulting from the sintering process.
Characterization of early crystallization stages in surface-crystallized diopside glass-ceramics
(2019)
Structure formation in glass-ceramics by means of surface crystallization is a challenging open question and remains elusive to definite answers. In several glass-ceramic systems, oriented crystal layers have been observed at the immediate surface, including diopside and some fresnoite systems. However, it is still open to debate, whether oriented surface crystallization is the result of oriented nucleation or growth selection effects. In the same vein, there is still discussion whether surface nucleation is governed by surface chemistry effects or by defects serving as active nucleation sites.
In order to help answer these questions, annealing experiments at 850°C have been performed on a MgO·CaO·2SiO2 glass, leading to the crystallization of diopside at the surface. Different annealing durations and surface treatment protocols (i.a. lapping with diamond slurries between 16 µm and 1 µm grain size) have been applied. Particular focus has been put on earliest crystallization stages, with crystal sizes down to about 200 nm. The resultant microstructure has been analyzed by electron backscatter diffraction (EBSD) and two different kinds of textures have been observed, with the a- or b-axis being perpendicular to the sample surface and the c-axis lying in the sample plane. Even at shortest annealing durations, a clear texture was present in the samples. Additionally, selected samples have been investigated with energy-dispersive x-ray spectroscopy in the scanning transmission electron microscope (STEM-EDX). The diopside crystals have been found to exhibit distinguished submicron structure variations and the glass around the crystals was shown to be depleted of Mg.
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.
A summery of previous research regarding surface crystallization is given as well as results regarding thecurrent DFG project are presented.
Glass-ceramics are noted for their unusual combination of properties and manifold commercialized products for consumer and specialized markets. Evolution of novel glass and ceramic processing routes, a plethora of new compositions, and unique exotic nano- and microstructures over the past 60 years led us to review the Definition of glass-ceramics. Well-established and emerging processing methods, such as co-firing, additive manufacturing, and laser patterning are analyzed concerning the core requirements of processing glass-ceramics and the Performance of the final products. In this communication, we propose a revised, updated definition of glass-ceramics, which reads “Glass-ceramics are inorganic, non-metallic materials prepared by controlled crystallization of glasses via different processing methods. They contain at least one type of functional crystalline phase and a residual glass. The volume fraction crystallized may vary from ppm to almost 100%”.
In this review article, the impact of dissolved water on the viscous properties of soda lime silicate melts is addressed against the background of the upcoming switch from natural gas to hydrogen combustion. This change will lead to an increase in the total water content of the glasses by up to 0.4 mol%. In order to better define possible influences of water speciation, water-rich glasses were synthesised under increasing pressure up to the kbar range. It is shown that a distinction must be made between the influence of dissolved OH-groups and H2Omolecules in order to accurately reflect the dependence of isokom temperatures on water content. In addition, an increase of one order of magnitude in the tolerance to higher deformation rates was observed for the range of expected increased water contents during isothermal deformation processes, which is based on the timetemperature superposition principle, i.e. congruent flow curves were determined under isokomal conditions.
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.
The coefficient of thermal expansion (CTE) and the thermomechanical properties of the polymers used in superconducting magnets need to be known in order to predict their stress state under the different magnet assembly and operating conditions.
We have measured Young’s moduli of typically used polymers during in situ heat cycles with the dynamic resonancemethod. The dynamic test results are compared with Young’s moduli determined from quasi-static stress–strain measurements at room temperature, 77 K and 4.2 K. A moderate elastic anisotropy is found for the fiber reinforced polymers. CTEs are compared based on dilation experiments. TheCTEs of the fiber reinforced polymers studied are similar to those of copper or steel. In contrast, the pure resins exhibit relatively larger CTEs.
Fresnoite glass with excess SiO2 exhibits oriented surface crystallization, in contrast to the stoichiometric glass composition. Recent EBSD studies documented that the crystals in BTS (2BaO-TiO2-xSiO2, x=0-3) can occur in a distinct [101]-orientation perpendicular to the surface and claimed that this orientation is not a result of growth selection. During these previous studies, however, the effect of surface preparation and surrounding atmosphere during the crystallization experiments were not considered. As these parameters may influence crystal orientation, we studied the surface crystallization of a BTS glass (2BaO-TiO2–2.75SiO2) under controlled conditions with the help of light, electron and polarisation microscopy as well as EBSD. Heat treatments for one hour at 840°C of fractured BTS glass surfaces in air resulted in a large number of not-separable surface crystals. This large number of crystals can be caused by dust particles, which act as nucleation agents. As crystal growth velocity could further be influenced by humidity, our experiments are performed in a filtered and dried air atmosphere. The crystal morphology and orientation will be analysed in dependence of the sample preparation and a differing surrounding atmosphere.
The process of viscous flow sintering is a phenomenon that is closely linked to the surface properties of the glass particles. In this work, we studied the extreme case of acid-leaching of soda-lime-silicate glass beads of two different particle size distributions and its effects on non-isothermal viscous sintering of powder compacts. Depth profiling of the chemical composition after leaching revealed a near-surface layer depleted in alkali and alkaline earth ions, associated with concurrent hydration as mass loss was detected by thermogravimetry. Heating microscopy showed that acid treatment of glasses shifted the sinter curves to higher temperatures with increasing leaching time. Modelling of the shrinkage with the cluster model predicted a higher viscosity of the altered surface layer, while analysis of the time scales of mass transport of mobile species (Na+, Ca2+ and H2O) during isochronous sintering revealed that diffusion of Na+ can compensate for concentration gradients before sintering begins. Also, exchanged water species can diffuse out of the altered layer, but the depletion of Ca2+ in the altered surface layer persists during the sinter interval, resulting in a glass with higher viscosity, which causes sintering to slow down.
Since decades electric contacts based on silver metallization pastes are key components of photovoltaics and advanced microelectronics. For the metallization of commercial Si solar cells, high conductive silver glass pastes are cost effectively applicated by screen printing. Nevertheless, silver pastes are still one of the most crucial and expensive none Si materials in solar cells. Ever shorter time to market as well as increasing demands on reduced Ag consumption and line width require the targeted development of silver-glass-pastes with increased sinter ability and electrical conductivity. As a main difficulty, however, the liquid phase sintering of silver glass pastes is poorly understood so far.
In the present study, the influence of different network modifier in alkali-zinc-borate paste glasses on liquid phase sintering of silver-glass-pastes was investigated. Low melting X2O-ZnO-B2O3 glasses with X = Na, Li and Rb (abbr. LZB, NZB, and RZB) were utilized to prepare silver-glass-composites containing 30 %Vol glass. Shrinkage behavior of the silver-glass-composites compared with that of pure silver and pure glass powder compacts was studied with heating microscopy. The powder compacts were uniaxially pressed and heated at 5 K/min to the glass softening temperature. Glass transformation temperature and viscosity of the glasses were respectively measured with dilatometry and rotational viscometry. The thermal behavior of the pure glasses was analyzed with thermal analysis. Additionally, the contact angle of glass on pure silver foil was determined by means of heating microscopy between room temperature and 830 °C.
Thermal analysis of the alkali-zinc-borate-glasses under study has shown transformation temperatures between 450 °C (RZB), 460 °C (LZB) and 465 °C (NZB). For all glasses crystallization was found to start approximately at about 550 °C. However, different peak areas hint on a different degree of crystallization. Conformingly, the sintering behavior, measured in terms of area shrinkage, significantly differed for the silver-pastes under study. For silver-pastes with NZB or LZB-glass, sintering starts at 464 °C for NZB Ag pastes and at 451 °C for LZB Ag pastes and ends at 597 °C for NZB Ag paste and at 594 °C for LZB Ag paste. The sintering of the RZB Ag paste proceeds between 426 °C and 703 °C. The final densification was retarded possibly due to crystallization or swelling. The low sinter onset at 426 °C seems to correlate with the good wetting behavior of the RZB glass. Thus, the lowest apparent contact angle between the just densified powder compact sintered at a silver substrate was found for this glass. Moreover, microstructure analyses of the various composites indicate differences in silver dissolution and reprecipitation.
Low melting zinc borate glasses awake interest to replace lead borate glasses in the silver metallization pastes for solar cells or microelectronics. In the current study, characteristic properties of alkali zinc borate glasses (X2O-ZnO-B2O3, X = Li, Na, K, Rb) were compared to an earth alkali zinc borate glass (CaO-ZnO-B2O3). Additionally, zinc oxide is partially substituted by lead oxide or cooper oxide in the borate glasses (Li2O-PbO-B2O3, Na2O ZnO CuO-B2O3). The alkali zinc borate glasses indicate less differences in Raman spectra, and thus in structural properties, in comparison to the Ca and Pb ions influence. LPbB (Tg = 401 °C) has a lower viscosity than LZB (Tg = 468 °C) and CaZB has the highest glass transition temperature (Tg = 580 °C). The Angell plot for the alkali zinc borate glasses shows a high fragility m = 80. Besides Tg, the density measured by means of the Archimedean principle, molar volume, and coefficient of thermal expansion (CTE) of the glasses were investigated. Trends could be found according to alkali ions or intermediate oxides. The density increases with decreasing alkali ion size from KZB (2.632 g/cm3) to LZB (2.829 g/cm3) and increases from LZB to LPbB (3.764 g/cm3). CTE ranges between 7.09 10-6 K-1 for CaZB and 11.5 10 6 K 1 for KZB and RZB. The differential thermal analysis (DTA) and X ray diffraction (XRD) indicate crystallization of various crystalline phases during heating with 5 K/min in most cases.
Network modifier ions can decisively influence properties and structure of low melting alkali-zinc-borate glasses and thus cause complex effects on the liquid phase sintering of silver-glass metallization pastes. This effect was studied for X2O-ZnO-B2O3 (X = Li, Na, Rb) glasses for silver-glass metallization pastes. Viscosity and the glass transition temperature, Tg, were measured with rotational viscometry and dilatometry. Dried model pastes with 30 vol% LZB, NZB or RZB glass were prepared for sintering studies by means of heating microscopy measuring the silhouette area shrinkage of uniaxially pressed powder compacts during heating at 5 K/min. For comparison, the silhouette area shrinkage of pure glass and silver powder compacts were determined. Glass-silver wetting was investigated during heating of bulk glass cylinders placed on silver substrates. Glass RZB turned out to have the lowest viscosity among the glasses under study. Its glass transformation temperature, Tg, was found at 444 °C and it caused the lowest sintering onset for its glass and paste powder compacts. Slightly increased values of Tg were found for NZB and LZB (468 °C and 466 °C, respectively) and a slightly retarded sintering was found for both paste powder compacts. These results indicate that liquid phase sintering of silver-glass pastes under air atmosphere is mainly influenced by glass viscosity.
Liquid phase sintering of glass bearing silver pastes used in photovoltaics and microelectronics is poorly understood. In particular, the role of different network modifiers acting in the glass component and the question of the most suitable atmospheric oxygen level during sintering are still under considerable debate. To tackle these issues, low-melting and lead-free X2O-ZnO-B2O3 glasses with X = Li, Na, K and Rb (LZB, NZB, KZB and RZB) were prepared. Infrared spectroscopy showed that the glass structure was similar to each other, while an increase of tetrahedrally coordinated boron with increasing field strength of the alkali was evident. In turn, the glass transition temperature (from differential thermal analysis) increased in the order: RZB (449 °C) < KZB (460 °C) < NZB (465 °C) < LZB (472 °C). Powders of each glass were mixed with organics to receive silver-glass-pastes containing 30 vol% glass and these were subjected to heating microscopy in air. Although similar onset temperatures of sintering were recorded for Ag-NZB and Ag-LZB glass pastes, and for Ag-RZB paste and KZB-Ag-paste, respectively, differences in the crystallization behavior and final densification were observed between the former and the latter group. These were translated in terms of differences in silver dissolution and reprecipitation among the two groups. Further, running the experiments in nitrogen gas showed that sintering of all pastes was considerably hampered. The slow-down of the sinter kinetics was found to be in line with the assumed lower oxidation and dissolution of silver ions into the glass-forming liquid.
Melting of Na2CO3-ZnO-B2O3 batches containing up to 16.8 wt% AgNO3 (5 mol% Ag2O in the target glass composition) was observed in situ by means of hot stage microscopy. In all batches metallic silver precipitation took place as most of the silver nitrate was reduced to metallic silver before Ag+ ions could be dissolved in the evolving borate melts. In turn, only traces of Ag+ (<300 ppmw) were dissolved in the sodium zinc borate glass melts under study. It is assumed that the oxidation to Ag+ was limited due to poor availability of reducible oxygen in the glass melts and presence of Na2O being a stronger base than Ag2O. Thus, the precipitated metallic silver formed droplets of different sizes. The larger droplets (d > 20 µm) were already settled at the bottom of the container and remained constant in size upon dwelling for 1 h at 1050 °C of about one hour and the subsequent cooling (45 K/min) to room temperature, whereas the smaller droplets (d < 20 µm) were mobile in the borate melt due to Marangoni and Stokes motion. For the latter droplets, coalescence was observed in situ. A growth of larger droplets at the expense of smaller ones, i.e., Ostwald ripening was also expected but could not be studied with the used experimental equipment.
Silber-Glas Wechselwirkungen spielen eine wichtige Rolle zum Beispiel in Glas-haltigen Silberpasten, die in der Photovoltaik oder Mikroelektronik verwendet werden. Um ein besseres Verständnis der Vorgänge zu erhalten, werden niedrig-schmelzende, bleifreie X2O ZnO B2O3 Gläser (X = Li, Na, K und Rb, Abk.: LZB, NZB, KZB and RZB) zur Untersuchung der Pasten verwendet.
Raman und Infrarot Spektroskopie zeigen, dass die Glasstruktur weitgehend vergleichbar ist, aber Unterschiede in der Bildung von Pentaboratgruppen in LZB und NZB oder Diboratgruppen in KZB und RZB auftreten. Die Anzahl an vierfach koordinierten Bor-Ionen (N4) sinkt mit zunehmendem Alkaliionenradius. Die Verringerung von N4 führt zu einer niedrigeren Glasübergangstemperatur in der Reihe LZB (472 °C) < NZB (465 °C) < KZB (460 °C) < RZB (449 °C).
Zur Herstellung der Pasten wurde kommerzielles Silber-Pulver mit 30 Vol.-% Glas und Organik gemischt. Das Sinterverhalten der gepressten Pulver wurde mittels Erhitzungsmikrospie untersucht. Der Sinterbeginn der Pasten ist vergleichbar und korrespondiert mit den geringen Unterschieden der Viskosität bei vergleichbarer Partikelgröße der Gläser. In den Ag-KZB- und Ag-RZB-Pasten ist die Schwindung durch die stärker einsetzende Kristallisation im Vergleich zu LZB und NZB verzögert.
High conductive silver metallization pastes are key components in advanced electronics and photovoltaics. Increasing demands on efficiency, miniaturization and ever shorter time-to-market require tailored glass-silver-pastes. In these pastes, low-melting glasses act as a sintering aid achieving better sintering, adhesion and contact formation for solar cells. Yet, the related liquid phase sintering of silver-glass-composites and the underlying mechanism of silver dissolution, transport and reprecipitation are rarely investigated. In this study, systematically varied low melting alkaline zinc borate, alkaline earth borate, and Pb- and Bi-glasses are investigated. Glass transition and crystallization are studied with dilatometry, DTA and XRD. Sintering of the pure glasses, pure silver and silver-glass-composites is analyzed with Hot Stage Microscopy, optical and electron microscopy. Since oxygen dissolved in silver powders can affect the silver dissolution as silver oxide in the matrix oxide glasses, the O2-content of silver powders is determined by Vacuum Hot Extraction. The glass transition temperature of the glasses under study varies between 370 °C and 590 °C whereas the sinter onset largely ranges between 400 °C and 600 °C. On the other hand, it scattered between 200 °C and 450 °C for selected commercial Ag-powders of different particle size and morphology.
Substitution of lead oxide in low-melting glasses, e.g., for application in silver metallization pastes, is a current research goal. This work is focused on the investigation of silver diffusion in alkali zinc borate glasses (X2O-ZnO-B2O3, X = Li, Na, K, Rb). In addition, the redox state of silver (Ag) and thus the type of diffusing silver species were studied. For this purpose, a metallic silver coating was applied on glass cubes by means of sputtering. Heat treatment of the samples was performed close to the glass transition temperatures at 470 °C for 2 h under air and nitrogen atmosphere. Coating thickness was 1.8 µm after heat treatment, measured by a white light interferometer.
Silver diffusion profiles were measured by means of secondary neutral mass spectrometry. The silver diffusion coefficients are in the range of ~10-14 cm2/s and indicate no significant differences depending on the type of alkali ions in the glass. Dissolved Ag+-ions and [Agm]n+-clusters in the glasses were differentiated using fluorescence spectroscopy.
Precipitated metallic silver particles in the sodium containing glass were observed by means of transmission electron microcopy. Their mean particle diameter was ~6 nm.
In many late-breaking research fields as in photovoltaics, microelectronics, nuclear waste glasses or at least mirror glasses silver diffusion in glasses is relevant to the issues of high-level functionality and recycling. The present study is focused on silver diffusion in innovative, low-melting alkali zinc borate glasses (X2O-ZnO-B2O3, X = Li, Na, K, Rb) potentially usable for silver metallization-pastes in solar cells. The glasses were coated with a thin metallic silver layer and heat treatments in air and nitrogen close to Tg at 470 °C for 2 h were performed. After heat treatment under air and nitrogen atmospheres the coating thickness, measured by a white light interferometer, was about 1.8 µm thick. Silver depth profiles determined by means of secondary neutral mass spectrometry (SNMS) indicate the fastest silver diffusion to a depth of 3.5 µm for Li2O-ZnO-B2O3 (LZB) glass. Nevertheless, the influence of the different alkali ions on the silver diffusion is small. The oxygen availability determines the silver diffusion into the glasses. The oxygen promotes the oxidation of the silver layer enabling Ag+ to diffuse into the glass and to precipitate as Ag0. Both species were detected by x-ray absorption spectroscopy (XAS). The precipitated metallic silver particles in Na2O-ZnO-B2O3 (NZB) glass have a mean size of 5.9 nm ± 1.2 nm diameter, which was determined using transmission electron microscopy (TEM). Phase separation in zinc-rich and zinc-poor phases with a mean diameter of 75 nm ± 20 nm occurred in NZB glass after heat treatment. Ion diffusion of the glasses into the silver layer was suggested by EDX-line scans.
Low melting Li2O-PbO-B2O3, Me2O-ZnO-B2O3, Me = Li, Na, K, Rb and CaO-ZnO-B2O3 glasses were studied with Raman and infrared spectroscopies to advance the structural understanding of zinc borate glasses as potential candidates for substitution of lead containing glasses. Although the effect of type of alkali ions on the number (N4) of fourfold coordinated boron (B4) in the glasses is small, the alkali ions direct the type of borate groups, i.e., pentaborate in lithium, sodium, and calcium zinc borate glasses, as well as diborate in potassium and rubidium containing ones. Both groups were simultaneously found in Li2O-PbO-B2O3. Alkali ions are mainly responsible for the formation of B4-units and metaborate. Zinc ions favorably compensate non-bridging oxygen and partially form ZnO4. With decreasing N4 and field strength of the alkali ions the atomic packing density, glass transition temper ature and Young’s Modulus also decrease. The coefficient of thermal expansion increases with decreasing N4.
Glasses in the systems Me2O-ZnO-B2O3 with Me = Li, Na, K, Rb (MeZB), Na2O-ZnO-CuO-B2O3 (NZCuB), CaO-ZnO-B2O3 (CaZB), and Li2O-PbO-B2O3 (LPbB) as a reference, were studied by differential thermal analysis, dilatometry, rotational viscometry, and heating microscopy. A decrease of viscosity and sintering range was found with decreasing number of fourfold coordinated boron. The viscosity of the alkali zinc borate glasses varies only slightly. LPbB and CaZB stand out by their reduced and increased viscosities, respectively. Sodium, potassium, and calcium zinc borate glasses possess a fragility above 76. All glasses were sintered to full density before crystallization. Mostly binary zinc borate phases govern crystallization. A ternary crystalline phase was detected only in the potassium containing sample. The Weinberg glass stability parameter ranges between 0.07 and 0.12. This is caused by the presence of several crystalline phases and varying melting points of even the same crystalline phase in different glass matrices.
Thermally stimulated interactions between silver and glass, that is, silver dissolution as Ag+ and precipitation as Ag0 were studied in two glass series of molar target composition xAg2O–(19 − x)Na2O–28ZnO–53B2O3 with x = 0, 0.1, 0.5, 5 and (19Na2O–28ZnO–53B2O3)+yAg2O with y = 0.01, 0.05. These act as model for low-melting borate glasses being part of metallization pastes. The occurrence of metallic silver precipitates in melt-quenched glass ingots demonstrated that silver dissolved only in traces (< 0.01 mol%) in the glasses. The dissolved silver was detected by means of Raman spectroscopy and energy-dispersive X-ray spectroscopy. Increasing x in the batch could not lead to a significant increase of the silver ion fraction in the glass as possible in binary silver borate glasses. In situ observation of heated AgNO3 mixed with the base glass frit in a hot stage microscope showed that Ag0 precipitation occurs already at the solid state. At higher temperatures, small droplets of liquid silver were found to move freely within the melt, whereas coalescence caused a stepwise increase of their size.
These results contribute to the understanding of formation of silver precipitates in metallization pastes described in the literature.
High conductive silver-glass-metallization-pastes are key components in photovoltaics and advanced microelectronics. However, the underlying mechanisms of liquid phase sintering as silver dissolution, diffusion and reprecipitation are poorly understood so far.
In the current work, the influence of different network modifier in alkali-zinc-borate paste-glasses on liquid phase sintering of silver-glass-composites was studied. Therefore, silver-glass-composites containing 30 vol% glass were prepared, using low melting X2O-ZnO-B2O3 glasses with X = Na, Li, and Rb (NZB, LZB, and RZB). Glass transition temperature, viscosity, glass-silver wetting, crystallization and sintering behavior was studied by means of thermal analysis, dilatometry, heating microscopy and microscopy.
Similar glass transition temperatures of 450 °C (RZB), 460 °C (LZB) and 465 °C (NZB) were found by means of thermal analysis for glasses under study. Also, all glasses have a similar crystallization onset at about 550 °C, even though exhibiting with a different degree of crystallization.
Despite these similarities, however, the sintering behavior, measured in terms of area shrinkage, significantly differs for the composites. This finding indicates a different degree of silver dissolution. Assuming that dissolved silver reduces the viscosity, this effect could explain why glass crystallization starts at lower temperature in the composites. For example, the crystallization peak of LZB at 629 °C measured for pure glass powder compacts was decreased to 586 °C for the composite. Confirmatively, microstructure analyses indicate different degrees of silver dissolution, as e.g. revealed by different amount of silver precipitates within the residual glass phase, and reprecipitation. Best silver dissolution appeared for the RZB glass. Nevertheless, the final densification of RZB was retarded probably due to swelling and crystallization.
The search for strong and tough oxide glasses is important for making safer, more environmentally friendly, thinner glass products. However, this task remains generally difficult due to the material’s inherent brittleness. In search for tougher glasses, fracture toughness (KIC) prediction models are helpful tools to screen for promising candidates.
In this work, a novel model to predict KIC via the fracture surface energy, γ, is presented. Our approach uses readily available crystallographic structure data of the glass’s isochemical crystal and tabled diatomic chemical bond energies, D0. The method assumes that γ of a glass equals the fracture surface energy of the most likely cleavage plane of the crystal. Calculated values were not only in excellent agreement with those calculated with a former well-working model, but also demonstrates a remarkable equivalence between crystal cleavage planes and glass fracture surfaces.
Finally, the effectiveness of fracture toughness enhancement by chemical substitution is discussed based on our results and alternative toughening strategies will be suggested.
Enhancing the fracture toughness is still one of the major challenges in the field of oxide glasses. To screen different glass systems for promising candidates, a theoretical expression for the fracture surface energy, G, linked to the fracture toughness, KIc, is thus of interest. Extending our earlier work on nucleation and surface energies [1], we present a simple approach for predicting the fracture surface energy of oxide glasses, G using readily available crystallographic structure data and diatomic bond energies. The proposed method assumes that G of glass equals the surface fracture energy of the weakest fracture (cleavage) plane of the isochemical crystal. For non-isochemically crystallizing glasses, an average G is calculated from the weighed fracture energy data of the constitutional crystal phases according to Conradt [2]. Our predictions yield good agreement with the glass density- and chemical bond energy-based prediction model of Rouxel [3] and with experimentally obtained G values known at present.
[1] C. Tielemann, S. Reinsch, R. Maass, J. Deubener, R. Müller, J. Non-Cryst. Solids 2022, 14, 100093
[2] R. Conradt, J. Non-Cryst. Solids 2004, 345-346, 16
[3] R., Tanguy, Scripta Materialia 2017, 109-13, 137
The search for strong and tough oxide glasses is important for making safer, environment-friendlier, thinner glasses. As fracture toughness experiments in brittle materials are complicated and time-consuming , modelling glass fracture surface energy, G, and fracture toughness, KIc, is of interest for screening promising candidates. Inspired by Rouxel´s idea of preferred crack growth along cutting weakest bonds within a glass structure and a study by Tielemann et al. , which indicates a correlation between crystal fracture surface and glass-crys¬tal interfacial energies, we present a new approach for predicting G. Combining both ideas, we used diatomic bond energies and readily available crystallographic structure data for estimating G. The proposed method assumes that G of the glass equals the surface fracture energy of the cleavage plane in its respective isochemical crystal. We calculated G- values for more than 25 iso-chemical silicate systems and compared them to calculated values from Rouxel’s widely used procedure, which is well working and based on glass densities and chemical bond energies. Not only does our model yields good agreement with [3], but it also enables an estimation for glasses with unknown density and can therefore contribute to broaden the data basis for glass property modelling tools. Most interestingly, however, this agreement indicates an interesting similarity between cleavage planes in a crystal and its corresponding glass state in terms of fracture processes.
Silicate glass fracture surface energy calculated from crystal structure and bond-energy data
(2023)
We present a novel method to predict the fracture surface energy, γ, of isochemically crystallizing silicate glasses using readily available crystallographic structure data of their crystalline counterpart and tabled diatomic chemical bond energies, D0. The method assumes that γ equals the fracture surface energy of the most likely cleavage plane of the crystal. Calculated values were in excellent agreement with those calculated from glass density, network connectivity and D0 data in earlier work. This finding demonstrates a remarkable equivalence between crystal cleavage planes and glass fracture surfaces.
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.