TY - JOUR A1 - Wettmarshausen, Sascha A1 - Min, Hyegeun A1 - Unger, Wolfgang A1 - Jäger, Christian A1 - Hidde, Gundula A1 - Friedrich, Jörg Florian T1 - Significance of hydrogen-deuterium exchange at polyolefin surfaces on exposure to ammonia low-pressure plasma N2 - Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to Polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. H–D exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant H–D exchange within the sampling depth of ATR (2.5 µm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers). KW - Deuterated ammonia KW - Ammonia plasma KW - Deuterated polyolefins KW - Hexatriacontane KW - H-D exchange PY - 2011 DO - https://doi.org/10.1007/s11090-011-9304-5 SN - 0272-4324 VL - 31 IS - 4 SP - 551 EP - 572 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-24178 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Jäger, Christian T1 - Towards nature and quantification of acid sites of amorphous silicia alumina using NMR T2 - Kooperationstreffen, Sasol GmbH CY - Brunsbüttel, Germany DA - 2011-09-27 PY - 2011 AN - OPUS4-24385 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kosslick, H. A1 - Pitsch, I. A1 - Deutsch, J. A1 - Pohl, M.-M. A1 - Schulz, A. A1 - Vu, A.T. A1 - Nguyen, D.T. A1 - Frunza, L. A1 - Jäger, Christian T1 - Improved large mesoporous ordered molecular sieves - Stabilization and acid/base functionalization N2 - The preparation of nanoporous materials with enhanced stability using an improved synthesis route using reactive inorganic silica and alumina species is reported. This way improved mesoporous molecular sieves were obtained. The synthesized aluminum substituted mesoporous molecular materials (Al-MMS) contain very large pores of 50–200 Å size combined with an improved pore wall thickness. Increased wall thickness and Al substitution lead to an improved chemical stability against alkaline solution. The textural, structural and acid properties are investigated by physico-chemical methods. The catalytic performance acidic materials was tested in the benzoylation reaction; amino functionalized materials were studied in the base catalyzed Michael addition. KW - Nanoporous molecular sieve KW - Al substitution KW - Stability KW - Synthesis KW - Acidity KW - Catalysis PY - 2010 DO - https://doi.org/10.1016/j.cattod.2010.03.005 SN - 0920-5861 VL - 152 IS - 1-4 SP - 54 EP - 60 PB - Elsevier CY - Amsterdam AN - OPUS4-23960 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Barheine, Sabrina A1 - Hayakawa, S. A1 - Jäger, Christian A1 - Shirosaki, Y. A1 - Osaka, A. T1 - Effect of disordered structure of boron-containing calcium phosphates on their in vitro biodegradability N2 - This study proposes a new guideline for designing biodegradable apatite ceramics. Boron-containing hydroxyapatite (BHAp) particles were prepared by a high-temperature solid-state reaction processing method and were characterized in terms of their chemical composition, apatite lattice defects and in vitro biodegradability. Solid-state nuclear magnetic resonance analysis showed that boron-incorporation into hydroxyapatite (HAp) derived by thermo-chemical reactions between borate and calcium phosphate phases led to disordered phases (BCaP) of a CaO–P2O5–B2O3–OH system covering the crystalline HAp core. X-ray diffraction analysis indicated that the BCaP phase must consist mainly of a crystalline oxyboroapatite (OBAp) phase. An in vitro biodegradability test showed that BHAp degraded quicker than HAp or ß-tricalcium phosphate. The biodegradability of BHAp particles can be controlled by boron incorporation into a HAp lattice leading to the formation of a disordered OBAp phase. KW - Boron KW - Hydroxyapatite KW - Calcium phosphate KW - NMR KW - Biodegradability KW - Disorder KW - Oxyboboapatite PY - 2011 DO - https://doi.org/10.1111/j.1551-2916.2011.04400.x SN - 0002-7820 SN - 1551-2916 VL - 94 IS - 8 SP - 2656 EP - 2662 PB - Blackwell Publishing CY - Malden AN - OPUS4-26244 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - König, R. A1 - Scholz, G. A1 - Veiczi, M. A1 - Jäger, Christian A1 - Troyanov, S.I. A1 - Kemnitz, E. T1 - New crystalline aluminium alkoxide oxide fluorides: evidence of the mechanism of the fluorolytic sol-gel reaction N2 - This study reports three new crystalline aluminum isopropoxide oxide fluorides with molar ratios of Al:F equal to 1:1 and 1:1.25. These are the first three representatives isolated without the incorporation of external donor molecules. Compound 1 Al4F4(µ4-O)(µ-O'Pr)5[H(O'Pr)2] contains a tetranuclear unit consisting of two different five fold coordinated AlFO4-units, with F exclusively in the terminal position. Compound 2, Al4F4(µ4-O)(µ-O'Pr)5[H(O'Pr)2]·Al5F5(µ5-O)(µ-O'Pr)8, contains both a tetranuclear unit (as in 1) and a pentanuclear Al-unit. Al-atoms in the latter are five- and six fold coordinated. Compound 3, Al16F20(µ4-O)4(µ-O'Pr)20·2('PrOH), exhibits a slightly higher fluorination degree and contains an oligomeric chain of four F-linked tetranuclear Al-units. In addition to X-ray structure analysis, compound 1 was characterized by different solid state MAS NMR techniques, including 27Al triple quantum MAS NMR and 1H, 1H→13C CP, 19F and 27Al MAS NMR. On the basis of the collected data, a reliable decomposition of 27Al single pulse MAS NMR spectra and an unambiguous assignment of the resonances to the respective structural AlFO4-units are given. The new crystalline aluminum isopropoxide oxide fluorides are direct evidence of the fluorolytic sol–gel mechanism previously discussed. KW - Aluminium fluorine KW - MAS NMR KW - Qudrupolar nuclei KW - Crystalline aluminium isopropoxide fluoride PY - 2011 DO - https://doi.org/10.1039/c1dt10514k SN - 1477-9226 SN - 1477-9234 SN - 1364-5447 VL - 40 IS - 34 SP - 8701 EP - 8710 PB - RSC CY - Cambridge AN - OPUS4-26245 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hemmann, F. A1 - Scholz, G. A1 - Scheurell, K. A1 - Kemnitz, E. A1 - Jäger, Christian T1 - Time-optimized 15N qNMR determination of Lewis and Brønsted site concentrations and chemical bonding of pyridine at Brønsted sites in amorphous aluminium hydroxide fluoride N2 - Time-optimized 15N quantitative NMR (qNMR) is described for the precise determination of Lewis and Brønsted site concentrations per gram catalyst, enabling a measurement time reduction of more than a factor of 10. The proof-of-principle is demonstrated for amorphous aluminum hydroxide fluorides with their tunable Lewis to Brønsted functionalities and relevance to highly active and selective heterogeneous catalysis using pyridine as a widely accepted probe molecule for Lewis and Brønsted sites. Two different Lewis centers were found, and reliable site concentrations down to the micromole per gram region can be determined. Furthermore, 1H{15N} REDOR NMR for the acid proton at the Brønsted site yields a distance of the 15N atom of bonded pyridine to this acid proton of (0.112 ± 0.002) nm, such that fast motion/diffusion of the Brønsted site-bonded pyridine at the surface can be excluded. KW - Catalysis KW - Lewis/Brønsted acid sites KW - Acid site concentration KW - Pyridine KW - Quantitative NMR KW - 15N KW - REDOR PY - 2012 DO - https://doi.org/10.1021/jp212045w SN - 1932-7447 SN - 1089-5639 VL - 116 IS - 19 SP - 10580 EP - 10585 PB - Soc. CY - Washington, DC AN - OPUS4-27724 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Debatin, F. A1 - Behrens, K. A1 - Weber, J. A1 - Baburin, I. A. A1 - Thomas, A. A1 - Schmidt, J. A1 - Senkovska, I. A1 - Kaskel, S. A1 - Kelling, A. A1 - Hedin, N. A1 - Bacsik, Z. A1 - Leoni, S. A1 - Seifert, G. A1 - Jäger, Christian A1 - Günter, C. A1 - Schilde, U. A1 - Friedrich, A. A1 - Holdt, H.-J. T1 - An isoreticular family of microporous metal-organic frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate: syntheses, structures and properties N2 - We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1–4, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0–1.7 Å), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345–400°C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-1–4 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions. KW - Adsorption KW - Metal-organic frameworks KW - Microporous materials KW - N,O ligands KW - Zinc PY - 2012 DO - https://doi.org/10.1002/chem.201200889 SN - 0947-6539 SN - 1521-3765 VL - 18 IS - 37 SP - 11630 EP - 11640 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hayakawa, S. A1 - Kanaya, T. A1 - Tsuru, K. A1 - Shirosaki, Y. A1 - Osaka, A. A1 - Fujii, E. A1 - Kawabata, K. A1 - Gasqueres, G. A1 - Bonhomme, C. A1 - Babonneau, F. A1 - Jäger, Christian A1 - Kleebe, H.-J. T1 - Heterogeneous structure and in vitro degradation behavior of wet-chemically derived nanocrystalline silicon-containing hydroxyapatite particles N2 - Nanocrystalline hydroxyapatite (HAp) and silicon-containing hydroxyapatite (SiHAp) particles were synthesized by a wet-chemical procedure and their heterogeneous structures involving a disordered phase were analyzed in detail by X-ray diffractometry (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The effects of heterogeneous structure on in vitro biodegradability and the biologically active Ca(II)- and Si(IV)-releasing property of SiHAp particles were discussed. The 29Si NMR analysis revealed that the Si(IV) was incorporated in the HAp lattice in the form of Q0 (SiO4-4 or HSiO3-4) species, accompanied by the formation of condensed silicate units outside the HAp lattice structure, where the fraction and amount of Q0 species in the HAp lattice depends on the Si content. The 31P and 1H NMR results agreed well with the XRD, TEM and FTIR results. NMR quantitative analysis results were explained by using a core–shell model assuming a simplified hexagonal shape of HAp covered with a disordered layer, where Si(IV) in Q0 was incorporated in the HAp lattice and a disordered phase consisted of hydrated calcium phosphates involving polymeric silicate species and carbonate anions. With the increase in the Si content in the HAp lattice, the in vitro degradation rate of the SiHAps increased, while their crystallite size stayed nearly unchanged. The biologically active Ca(II)- and Si(IV)-releasing ability of the SiHAps was remarkably enhanced at the initial stage of reactions by an increase in the amount of Si(IV) incorporated in the HAp lattice but also by an increase of the amount of polymeric silicate species incorporated in the disordered phase. KW - Silicate KW - Calcium phosphate KW - Hydroxyapatite KW - Degradation KW - Apatite formation PY - 2013 DO - https://doi.org/10.1016/j.actbio.2012.08.024 SN - 1742-7061 VL - 9 IS - 1 SP - 4856 EP - 4867 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-27319 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mohamed, Zeinab A1 - Krüger, Simone A1 - Hidde, Gundula A1 - Schimanski, A. A1 - Jäger, Christian A1 - Friedrich, Jörg Florian T1 - Deposition of thick polymer or inorganic layers with flame-retardant properties by combination of plasma and spray processes N2 - Mixtures of hexamethyldisiloxane (HMDSO) and oxygen have been used for deposition of SiO2-like layers by plasma polymerization under low-pressure conditions onto polyethylene and polystyrene used as basecoat. Water glass was cast onto these 0.5 µm plasma thick siloxane-like layers with a thickness of 5 to 40 µm. The adhesion of these bilayer systems and their flame resistance were tested. The effect of different plasma parameters such as monomer/gas ratio, pressure and power input into the discharge on the deposition rate and the composition of the formed layers was studied. Characterization and chemical composition of the formed films were performed using infrared, X-ray photoelectron and solid state nuclear magnetic resonance spectroscopy. Peel strengths of composites were measured and the locus of peel front propagation was detected. Thermal properties of composites were analyzed by thermo-gravimetric analysis. Finally, the fire-retardant properties of thick coated polymers were determined by exposure to flames and the behavior of coatings on the polymers during flaming was observed visually. KW - Plasma polymerization KW - Hexamethyldisiloxane plasma polymer KW - Polystyrene KW - Polyethylene KW - Flame retardancy PY - 2013 DO - https://doi.org/10.1016/j.surfcoat.2013.04.039 SN - 0257-8972 VL - 228 SP - 266 EP - 274 PB - Elsevier B.V. CY - Lausanne AN - OPUS4-28735 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Diakité, M. A1 - Paul, Andrea A1 - Jäger, Christian A1 - Pielert, J. A1 - Mumme, J. T1 - Chemical and morphological changes in hydrochars derived from microcrystalline cellulose and investigated by chromatographic, spectroscopic and adsorption techniques N2 - Hydrothermal carbonization (HTC) can be used for converting the biomass into a carbon-rich material, whose application as a fuel requires higher heating value, whereas soil amendment needs stable carbon. This work was focused on the characterization of hydrochars derived from microcrystalline cellulose. The chars were investigated using elemental analysis, Brunauer–Emmett–Teller technique, nuclear magnetic resonance spectroscopy, Raman, Fourier transform infrared, and electron spin resonance spectroscopy. Severity in temperature between 230 and 270 °C with reaction times between 2 and 10 h only affect the carbon content moderately. The results show that aromatization of HTC chars correlates well with temperature, which was further supported by the increase of organic radicals with decreasing g values at higher temperatures. Based on these results, the energetic use of chars favors mild HTC (T < 230 °C and t ≤ 6 h), while the soil amendement favors serve conditions (T ≥ 230 °C, and t > 6 h). KW - Hydrothermal carbonization KW - Hydrochar KW - Microcrystalline cellulose KW - NMR-spectroscopy KW - ATR-FTIR-spectroscopy PY - 2013 DO - https://doi.org/10.1016/j.biortech.2013.09.129 SN - 0960-8524 SN - 1873-2976 VL - 150 SP - 98 EP - 105 PB - Elsevier Ltd. CY - Barking, Essex AN - OPUS4-29824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Jäger, Christian A1 - Pauli, Jutta A1 - Berger, Georg A1 - Spitzer, Andrea T1 - Entwicklung neuartiger Knochenersatzwerkstoffe und strukturelle Charakterisierung mittels der 31P-NMR-Spektroskopie T2 - Tagung "Tag der Chemie" CY - Berlin, Deutschland DA - 2002-12-04 PY - 2002 AN - OPUS4-1900 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -