4 Material und Umwelt
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- Affinity chromatography (3)
- Antibodies (3)
- Polyglycerol (3)
- Bassanite (2)
- Calcium sulfate (2)
- Glutaraldehyde (2)
- Gypsum (2)
- Iron oxide nanoparticles (2)
- MOF (2)
- Particle size (2)
Organisationseinheit der BAM
- 6.3 Strukturanalytik (21) (entfernen)
Eingeladener Vortrag
- nein (4)
Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). The optimum conditions for the efficient production of bassanite in a short time (<5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the better-known behaviour of the bassanite phase in low-salt environments. In low-salinity aqueous solutions, bassanite is considered to be metastable with respect to gypsum and anhydrite, and therefore gypsum-to-bassanite conversion does not occur in pure water. Interestingly, the high-salinity transformation of gypsum-to-bassanite has been reported by many authors and used in practice for several decades, although its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures was inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline phase for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios.
Calcium sulfate hemihydrate (CaSO4ᐧ0.5H2O), also known as bassanite, has been used as a precursor to produce gypsum (dihydrate, CaSO4ᐧ2H2O) for various construction and decorative purposes since prehistoric times. The main route to obtain hemihydrate is a thermal treatment of gypsum at temperatures typically between 150 °C and 200 °C to remove some of the structural water.
In this contribution, we introduce (Fig. 1) a more efficient and sustainable method (T < 100 °C) that enables the direct, rapid, and reversibly conversion of gypsum to bassanite using reusable high salinity aqueous solutions (brines with c[NaCl] > 4 M). The optimum conditions for the efficientproduction of bassanite in a short time (< 5 min) involve the use of brines with c(NaCl) > 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the typical behaviour of the bassanite phase in low salt environments.
Traditionally, hemihydrate is obtained through a solid state thermal treatment because bassanite is considered to be metastable with respect to gypsum and anhydrite in aqueous solutions, and therefore gypsum-to-bassanite conversion should not occur in water. Its very occurrence actually contradicts numerical thermodynamic predictions regarding solubility of calcium sulfate phases. By following the evolution of crystalline phases with in situ and time-resolved X-ray diffraction/scattering and Raman spectroscopy, we demonstrated that the phase stability in brines at elevated temperatures is inaccurately represented in the thermodynamic databases. Most notably for c(NaCl) > 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline structure for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios.
We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.
Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.
Industrial and agricultural waste streams (waste water, sludges, tailings, etc.) which contain high concentrations of NH4+, PO43–, and transition metals are environmentally harmful and toxic pollutants. At the same time, phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate independently from each other. Investigations on the simultaneous removal of multiple components have been carried out only to a limited extent. Here, we report the synthesis routes for Ni- and Co-struvites (NH4MPO4·6H2O, M = Ni2+ and Co2+), which allow for P, ammonia, and metal co-precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites as well as their crystal morphologies and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal amorphous nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the involved metal cation in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size makes precipitation of transition metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially up-cycled as precursor powders for electrochemical or (electro)catalytic applications, which require transition metal phosphates.
Herein we report the synthesis of a zeolitic imidazolate framework (ZIF-8) by an easy “mix and wait” procedure. In a closed vial, without any interference, the mixture of 2-methylimidazole and basic zinc carbonate assembles into the crystalline product with approx. 90% conversion after 70 h. The reaction exhibits sigmoidal kinetics due to the self-generated water which accelerates the reaction.
Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids are used to introduce functional groups for further conjugations. The common cross-linker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter is oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower nonspecific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by SDS-PAGE. A binding capacity of 1.8 mg IgG per g of corundum powder was achieved. The advantages of corundum are the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, and flexible application.
Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, EDS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids were used to introduce functional groups for further conjugations. The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower non-specific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). A binding capacity of 1.8 mg IgG per gram of corundum powder was achieved. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application.
Nonporous corundum powder was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices.The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). As a proof of concept, IgG was extracted with protein A from crude human plasma. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application.
Sehr geehrte Damen und Herren,
liebe Leserinnen und Leser,
bereits im ersten Band der N.i.Ke. Schriftenreihe des Netzwerks zur interdisziplinären Kulturerhaltung hatte ich angeführt, dass bei der Untersuchung von kulturellen Artefakten naturwissenschaftliche Untersuchungsmethoden zunehmend an Bedeutung gewinnen, sie eigentlich unverzichtbar geworden sind.
Ein besonders einprägsames Beispiel dieser fächerübergreifenden Zusammenarbeit zwischen Geisteswissenschaften, Naturwissenschaften und Restaurierungswissenschaften war die Ausstellung Johannes Vermeer. Vom Innehalten, die in diesem Jahr in der Gemäldegalerie Alter Meister in den staatlichen Kunstsammlungen Dresden gezeigt wurde. Eigens für diese Ausstellung wurde das Gemälde Brieflesendes Mädchen am offenen Fenster einer grundlegenden Restaurierung unterzogen. Diese Restaurierung diente jedoch nicht nur der Reparatur des Bildes. Um sich dem ursprünglichen Zustand des Gemäldes zwischen 1657 und 1659 anzunähern, wurden später hinzugefügte Malschichten großflächig abgenommen. Möglich wurde dies durch unterschiedliche, bildgebende materialwissenschaftliche Untersuchungen im Vorfeld, welche die wissenschaftlichen Grundlagen für die Diskussion über den weiteren Umgang mit der Lesenden schufen.
Materialanalytische Verfahren wurden und werden ständig weiterentwickelt und optimiert. Sei es, um aus einer Vielzahl von Einzelmessungen ein Gesamtbild zu erstellen, oder die Größe einer Probenentnahme so zu reduzieren, dass von einer „minimal-invasiven“ oder „quasi nicht-invasiven“ Untersuchung ausgegangen werden kann. Nun feiert die Bundesanstalt für Materialforschung und -prüfung, zusammen mit ihren Vorgängerinstitutionen, den königlichen Versuchsanstalten, in diesem Jahr ihren einhundertfünfzigsten Geburtstag. Sie blickt damit auf eine lange Tradition materialwissenschaftlicher Analysen zurück, an deren Beginn beispielsweise die metallographischen Untersuchungen von Adolf Martens stehen. Derartige Untersuchungen bilden auch heute noch einen wesentlichen Bestandteil archäometallurgischer Forschung. Die Historie bzw. die Weiterentwicklung der Methodik lässt sich hier besonders gut nachzeichnen. Jedoch blicken auch Verfahren zur Charakterisierung weiterer Werkstoffe, wie Glas, Keramik, oder organischer Materialien auf eine lange Geschichte zurück.
Die in diesem Band der N.i.Ke.-Schriftenreihe präsentierten Beiträge dokumentieren einerseits aktuelle Forschungsarbeiten, die erst in diesem Jahr in entsprechenden Fachjournalen publiziert wurden, andererseits liegen einige der Arbeiten bereits 50 Jahre zurück. Sie bekunden damit nicht nur die materialtechnologische und historische Bandbreite der Projekte, sondern offenbaren die Vielfältigkeit kulturhistorischer oder restauratorischer Fragestellungen, zu deren Beantwortung natur- und materialwissenschaftliche Forschung wesentliche Beiträge liefern können.
Ich bedanke mich bei allen Kolleginnen und Kollegen, die zur Erstellung dieser dritten Ausgabe der N.i.Ke. Schriftenreihe des Netzwerks zur interdisziplinären Kulturerhaltung beigetragen haben. Ihre Aufsätze ermöglichen den Blick in die Vielfältigkeit materialwissenschaftlicher Untersuchungen im Bereich Kunst- und Kulturgut. Ich wünsche Ihnen viel Spaß auf dieser kleinen Zeitreise.