Filtern
Dokumenttyp
- Zeitschriftenartikel (4)
- Beitrag zu einem Tagungsband (1)
- Vortrag (1)
- Posterpräsentation (1)
Sprache
- Englisch (7)
Schlagworte
- Silanes (7) (entfernen)
Organisationseinheit der BAM
Eingeladener Vortrag
- nein (1)
Industrial Applications of Low-Field NMR Spectroscopy for Process and Quality Control of Silanes
(2021)
The combination of different silanes as starting materials and as a product of hydrolysis by several alcohols or water creates a range of hundreds of technical products for a wide range of applications. In recent years, functional trialkoxysilanes have proven to be multi-purpose organosilanes. Applications range from weather protection of buildings to bonding-imparting properties in the glass fiber industry, for sealants and adhesives, for coatings and paints to the modification of polymer materials.
Commercial benchtop NMR spectrometers have the potential to be used in silane chemistry as an online method for reaction monitoring and quality control [1]. Interesting NMR nuclei for the above-mentioned products are 1H and 29Si. In a joint research cooperation between EVONIK and BAM, the applicability of low-field NMR spectroscopy for the chemical analysis of silanes was evaluated based on various case studies. In the course of the case studies it was shown how low-field NMR spectroscopy extends the application range of chemical analysis to new applications where existing technologies such as NIR, Raman, UV/VIS, etc. cannot be used quantitatively due to lack of reference data.
The combination of different silanes as starting materials and as a product of hydrolysis by several alcohols or water creates a range of hundreds of technical products for a wide range of applications. In recent years, functional trialkoxysilanes have proven to be multi-purpose organosilanes. Applications range from weather protection of buildings to additives for glass fiber industry, sealants, adhesives, coatings and paints to the modification of polymers.
Commercial benchtop NMR spectrometers have the potential to be used in silane chemistry as an online method for reaction monitoring and quality control. NMR nuclei of interest for silane products are 1H and 29Si. In a joint research cooperation between EVONIK and BAM, the applicability of low-field NMR spectroscopy for the chemical analysis of silanes was evaluated. It was shown how it can extend the application range where existing technologies like NIR, Raman, UV/VIS, etc. cannot be used quantitatively due to a lack of reference data.
In a first case study the process of hydrolysis and condensation was observed using online NMR analysis. For this purpose, the substituents of a trialkoxysilane are first hydrolyzed by adding water and corresponding silanols are formed, which can then bind to materials via SiOH functions and crosslink to form siloxane units. Another case study was dealing with the kinetics of the cleavage of a cyclic silane compound. Online NMR analysis was used both in the laboratory and in the manufacturing plant. For this purpose, a fully automated containment system was used, which enables the use of a commercial NMR spectrometer in ATEX-environments. In the third case study presented, quantitative 1H-NMR spectra were acquired on product mixtures of a trialkoxysilane and other components such as organic stabilizers, organotin compounds, an aromatic amine and organic peroxides. An automatic evaluation method based on Indirect Hard Modeling (IHM) was developed.
Ingress of moisture and harmful ions (e.g. Chloride, sulfate) into cementitious materials is one of the major factors in defining their durability. Modifications of building materials by targeted deposition of surface functional agents that make the surface hydro- and/or oleophobic aim to minimize moisture and ion ingress, and thus extend Service life of the cement based structures. Water repellent and easy-to-clean coatings for inorganic Substrates have gained strong attention during the last few years and various formulations based on silicones or alkylpolysiloxanes have been developed. Cementitious building materials are highly complex Systems with many components and changing properties in the course of a building’s Service life. The interactions between the Chemical agents and the cement based materials depend on many factors. The Chemical properties of the material Substrate appear to be the most important but in the context of their influence on the functionality of silanes and/or siloxanes these characteristics have not been well understood yet. The aim of this study was to evaluate the effect of different blended cements on water repellent agents’ performance. Two organosilicon compounds
were applied on fresh blended cements containing limestone (L), fly ash (F), slag (S) and trass (T), and investigated in terms of their functionality.
The surface properties of functionalized blended cements were studied based on wettability, i.e. contact angle measurements, before and after exposure to artificial and natural weathering. The first results indicate that slag and trass more distinctly affect the water repellent Surface performance after aging.
The paper presents the results of a study dealing with the performance of water repellents on hardened blended cement pastes. Since on the European market Portland cement does not play the dominant role anymore and due to the new national and European policies concerning Greenhouse Gases and sustainability, cement manufacturers produce more and more blended cements (CEM IICEM V). Nevertheless, the majority of experience concerning the efficacy of water repellents is gained from Portland cement; therefore knowledge in regard to the interactions of blended cement with water repellent agent is minimal. Two silane-based products were applied on 'fresh' and carbonated cement substrates containing limestone, fly ash, slag and trass, and were investigated in terms of their functionality. The evaluation of the treatments' performance and effectiveness were assessed using various laboratory measurements. Hydrophobicity, water absorption, colour changes and the penetration depth of silanes into the substrate were evaluated before and after artificial aging experiments. Moreover, the outdoor weathering test was performed to shed light on treated surface appearance in a 'real' outdoor environment. The results showed that surface wettability was independent on water ingress or colour variations, especially for cement specimens artificially aged by accelerated carbonation. Cement pastes containing slag and trass seemed to more distinctly affect the water repellents' surface performance.
This paper is a case study of complete substitution of sodium-metasilicate in zeolite Na-A synthesis by an electrostatic filterash (FA) arising in high amounts during silane waste incineration process.The silicate abundant FA is a suitable material for reinsertion in zeolite chemistry. This is shown in the presented investigation by the development of a model reaction process at low temperatures (50–60 °C) and short times (1.5–4 h). The experiments were performed under addition of NaAlO2 and variation of the alkalinity and the reaction period. Characterization and fine tuning of the process was mainly done by studying the kinetics of FA digestion and zeolite crystallization by XRD and chemical analyses (ICP-OES) of solutions and solids. It could be shown that pure FA was mostly dissolved (98%) in 8 m NaOH already after 1 h. Addition of NaAlO2 and crystallization for further 60 min under optimized conditions at 50 °C yielded to a suitable product. It consists of zeolite Na-A (92% by mass) beside some hydrosodalite (8% by mass). According to this low temperature short time process this study is a contribution for the development of energy efficient recycling solutions.
Synchrotron-radiation XPS analysis of ultra-thin silane films: Specifying the organic silicon
(2016)
The analysis of chemical and elemental in-depth variations in ultra-thin organic layers with thicknesses below 5 nm is very challenging. Energy- and angle-resolved XPS (ER/AR-XPS) opens up the possibility for non-destructive chemical ultra-shallow depth profiling of the outermost surface layer of ultra-thin organic films due to its exceptional surface sensitivity. For common organic materials a reliable chemical in-depth analysis with a lower limit of the XPS information depth z95 of about 1 nm can be performed. As a proof-of-principle example with relevance for industrial applications the ER/AR-XPS analysis of different organic monolayers made of amino- or benzamidosilane molecules on silicon oxide surfaces is presented. It is demonstrated how to use the Si 2p core-level region to non-destructively depth-profile the organic (silane monolayer) inorganic (SiO2/Si) interface and how to quantify Si species, ranging from elemental silicon over native silicon oxide to the silane itself. The main advantage of the applied ER/AR-XPS method is the improved specification of organic from inorganic silicon components in Si 2p core-level spectra with exceptional low uncertainties compared to conventional laboratory XPS.
Ananion-dopedaluminiumchlorofluoride AlCl0.1F2.8(OTeF5)0.1(ACF-teflate) was synthesized.The material contains pentafluor-oorthotellurate(teflate)groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by73 cm-1, which is larger than the shift for SbF5. Remarkably,ACF-teflate catalyzes dehydrofluorination reactions of mono-fluoroalkanes to yield olefins in C6D6. In these cases,no Friedel-Crafts products were formed.