scholarly journals Inorganic Polymers (Geopolymers) as Potential  Bioactive Materials

2021 ◽  
Author(s):  
◽  
Nils Rahner
Keyword(s):  
Calcium Phosphate ◽  
Calcium Hydroxide ◽  
Calcium Silicate ◽  
Mas Nmr ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
X Ray ◽  
Diametral Compression ◽  
Hydroxyl Apatite ◽  
Geopolymer Composites

<p>The primary aim of this project was to synthesise potassium activated geopolymer composites with bioactivity, and this was realised by adding 10wt% of calcium hydroxide, nano-structured calcium silicate or calcium phosphate to the geopolymer matrix. The synthesised samples were cured at 40'C then heated to 550'C and 600'C to reduce their alkalinity. Tensile strength was measured by diametral compression. The effect of exposure to simulated body fluid (SBF) was determined by x-ray diffractometry (XRD), 27Al, 29Si and 43Ca nuclear magnetic resonance spectroscopy with magic angle spinning (MAS NMR), pH measurements, inductively coupled plasma (ICP), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDS). XRD, 27Al and 29Si MAS NMR confirmed that all the samples retained their structural characteristics of a true aluminosilicate geopolymer, even after heating and exposure to SBF. EDS examination of the calcium-containing geopolymer composites showed that the calcium distribution was generally homogeneous. Exposure of the geopolymer composites to SBF at body temperature, was used to simulate the behaviour of the geopolymer composites in blood plasma. XRD and SEM/ EDS analysis showed that the geopolymers containing calcium hydroxide and calcium silicate formed hydroxyl apatite (HA) and carbonate hydroxyl apatite (HCA) after their exposure to SBF, indicating a degree of bioactivity. The absorption of calcium and phosphorus from the SBF and the observation of nano crystals rich in these elements provide some evidence of bioactive phases in the composite containing calcium phosphate and the reference geopolymer. The reference and the calcium phosphate geopolymer (both heated to 600XC) produced the lowest pH (ca.8) in the SBF. ICP analysis of the SBF after exposure shows that most of the aluminium remains in the geopolymer structure. The greatest release of aluminium (< 2.7 ppm after 168 hours) was found for the calcium hydroxide geopolymer (heated to 600'C). Diametral compression testing showed that the strength of the calcium phosphate-containing geopolymer heated to 550'C (4.17 MPa) is comparable with that of Bioglass(R)(5.56 MPa), currently used as a bio-material. Although none of the composites are ideal in all respects, they show sufficient promise to suggest that with further refinement, geopolymer materials may well be become candidates as bioactive ceramics.</p>

scholarly journals Inorganic Polymers (Geopolymers) as Potential  Bioactive Materials

2021 ◽  
Author(s):  
◽  
Nils Rahner
Keyword(s):  
Calcium Phosphate ◽  
Calcium Hydroxide ◽  
Calcium Silicate ◽  
Mas Nmr ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
X Ray ◽  
Diametral Compression ◽  
Hydroxyl Apatite ◽  
Geopolymer Composites

<p>The primary aim of this project was to synthesise potassium activated geopolymer composites with bioactivity, and this was realised by adding 10wt% of calcium hydroxide, nano-structured calcium silicate or calcium phosphate to the geopolymer matrix. The synthesised samples were cured at 40'C then heated to 550'C and 600'C to reduce their alkalinity. Tensile strength was measured by diametral compression. The effect of exposure to simulated body fluid (SBF) was determined by x-ray diffractometry (XRD), 27Al, 29Si and 43Ca nuclear magnetic resonance spectroscopy with magic angle spinning (MAS NMR), pH measurements, inductively coupled plasma (ICP), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDS). XRD, 27Al and 29Si MAS NMR confirmed that all the samples retained their structural characteristics of a true aluminosilicate geopolymer, even after heating and exposure to SBF. EDS examination of the calcium-containing geopolymer composites showed that the calcium distribution was generally homogeneous. Exposure of the geopolymer composites to SBF at body temperature, was used to simulate the behaviour of the geopolymer composites in blood plasma. XRD and SEM/ EDS analysis showed that the geopolymers containing calcium hydroxide and calcium silicate formed hydroxyl apatite (HA) and carbonate hydroxyl apatite (HCA) after their exposure to SBF, indicating a degree of bioactivity. The absorption of calcium and phosphorus from the SBF and the observation of nano crystals rich in these elements provide some evidence of bioactive phases in the composite containing calcium phosphate and the reference geopolymer. The reference and the calcium phosphate geopolymer (both heated to 600XC) produced the lowest pH (ca.8) in the SBF. ICP analysis of the SBF after exposure shows that most of the aluminium remains in the geopolymer structure. The greatest release of aluminium (< 2.7 ppm after 168 hours) was found for the calcium hydroxide geopolymer (heated to 600'C). Diametral compression testing showed that the strength of the calcium phosphate-containing geopolymer heated to 550'C (4.17 MPa) is comparable with that of Bioglass(R)(5.56 MPa), currently used as a bio-material. Although none of the composites are ideal in all respects, they show sufficient promise to suggest that with further refinement, geopolymer materials may well be become candidates as bioactive ceramics.</p>

scholarly journals The Application of 29Si NMR Spectroscopy to the Analysis of Calcium Silicate-Based Cement using Biodentine™ as an Example

2019 ◽  
Vol 10 (2) ◽  
pp. 25 ◽  
Author(s):  
Qiu Li ◽  
Andrew P. Hurt ◽  
Nichola J. Coleman
Keyword(s):  
Calcium Silicate ◽  
Zirconium Oxide ◽  
Tricalcium Silicate ◽  
Magic Angle Spinning ◽  
Mas Nmr ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
29Si Nmr ◽  
29Si Mas Nmr ◽  
Maximum Heat

Biodentine is one of the most successful and widely studied among the second generation of calcium silicate-based endodontic cements. Despite its popularity, the setting reactions of this cement system are not currently well understood. In particular, very little is known about the formation and structure of the major calcium silicate hydrate (C-S-H) gel phase, as it is difficult to obtain information on this poorly crystalline material by the traditional techniques of powder X-ray diffraction analysis (XRD) and Fourier transform infrared spectroscopy (FTIR). In this study, the hydration reactions of Biodentine are monitored by XRD, FTIR, isothermal conduction calorimetry and, for the first time, 29Si magic angle spinning nuclear magnetic resonance spectroscopy (29Si MAS NMR) is used to investigate the structures of the anhydrous calcium silicate phases and the early C-S-H gel product. XRD analysis indicated that the anhydrous powder comprises 73.8 wt% triclinic tricalcium silicate, 4.45 wt% monoclinic β-dicalcium silicate, 16.6 wt% calcite and 5.15 wt% zirconium oxide. Calorimetry confirmed that the induction period for hydration is short, and that the setting reactions are rapid with a maximum heat evolution of 28.4 mW g−1 at 42 min. A progressive shift in the FTIR peak maximum from 905 to 995 cm−1 for the O-Si-O stretching vibrations accompanies the formation of the C-S-H gel during 1 week. The extent of hydration was determined by 29Si MAS NMR to be 87.0%, 88.8% and 93.7% at 6 h, 1 day and 1 week, respectively, which is significantly higher than that of MTA. The mean silicate chain length (MCL) of the C-S-H gel was also estimated by this technique to be 3.7 at 6 h and 1 day, and to have increased to 4.1 after 1 week. The rapid hydration kinetics of Biodentine, arising from the predominance of the tricalcium silicate phase, small particle size, and ‘filler effect’ of calcite and zirconium oxide, is a favorable characteristic of an endodontic cement, and the high values of MCL are thought to promote the durability of the cement matrix.

X-ray diffraction and solid-state 119Sn CP-MAS NMR studies of some triaryltin(IV) chlorides

2003 ◽  
Vol 81 (11) ◽  
pp. 1187-1195 ◽  
Author(s):  
Jordan M Geller ◽  
Ian S Butler ◽  
Denis FR Gilson ◽  
Frederick G Morin ◽  
Ivor Wharf ◽  
...  
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Magic Angle Spinning ◽  
Mas Nmr ◽  
Spin Coupling ◽  
Magic Angle ◽  
X Ray ◽  
Tin Chloride ◽  
Angle Spinning ◽  
Spin Spin Coupling

The solid-state 119Sn cross-polarization (CP) magic angle spinning (MAS) NMR spectra of a series of triaryltin chlorides of the form Ar3SnCl have been acquired. The indirect spin-spin coupling constants (J(119Sn-35Cl)), quadrupolar-dipolar shifts (d(119Sn-35Cl)), and the 119Sn chemical shift tensors were extracted. For the spectrum of triphenyltin chloride (I) the validity of the first-order perturbation approximation was tested by comparing results of both the perturbation and cubic-equation approaches and a variable-temperature NMR study undertaken to investigate the influence of the previously reported molecular motion in the solid. The X-ray crystal structures of the tris(o-tolyl)tin chloride (II) and tris(p-tolyl)tin chloride (IV) complexes have been examined. They belong to the monoclinic and triclinic space groups P21/n and P[Formula: see text], respectively, which are different from the previously reported tris(m-tolyl)tin chloride (III) complex, which crystallizes in the space group R3 and has threefold molecular symmetry. The structures and NMR properties of the complexes with meta-substituents are quite different from those with ortho- or para-substituents having axially symmetric shift tensors with small spans and larger J values.Key words: aryltin chlorides, magic angle spinning NMR, tin-chlorine spin-spin coupling, 119Sn chemical shift tensor, crystal structure.

scholarly journals Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance

2016 ◽  
Vol 49 (3) ◽  
pp. 771-783 ◽  
Author(s):  
Sylvain Grangeon ◽  
Francis Claret ◽  
Cédric Roosz ◽  
Tsutomu Sato ◽  
Stéphane Gaboreau ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Calcium Silicate ◽  
Electron Probe ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
X Ray Diffraction ◽  
X Ray ◽  
Calcium Silicate Hydrates ◽  
Angle Spinning ◽  
X Ray Absorption

The structure of nanocrystalline calcium silicate hydrates (C–S–H) having Ca/Si ratios ranging between 0.57 ± 0.05 and 1.47 ± 0.04 was studied using an electron probe micro-analyser, powder X-ray diffraction,29Si magic angle spinning NMR, and Fourier-transform infrared and synchrotron X-ray absorption spectroscopies. All samples can be described as nanocrystalline and defective tobermorite. At low Ca/Si ratio, the Si chains are defect free and the SiQ3andQ2environments account, respectively, for up to 40.2 ± 1.5% and 55.6 ± 3.0% of the total Si, with part of theQ3Si being attributable to remnants of the synthesis reactant. As the Ca/Si ratio increases up to 0.87 ± 0.02, the SiQ3environment decreases down to 0 and is preferentially replaced by theQ2environment, which reaches 87.9 ± 2.0%. At higher ratios,Q2decreases down to 32.0 ± 7.6% for Ca/Si = 1.38 ± 0.03 and is replaced by theQ1environment, which peaks at 68.1 ± 3.8%. The combination of X-ray diffraction and NMR allowed capturing the depolymerization of Si chains as well as a two-step variation in the layer-to-layer distance. This latter first increases from ∼11.3 Å (for samples having a Ca/Si ratio <∼0.6) up to 12.25 Å at Ca/Si = 0.87 ± 0.02, probably as a result of a weaker layer-to-layer connectivity, and then decreases down to 11 Å when the Ca/Si ratio reaches 1.38 ± 0.03. The decrease in layer-to-layer distance results from the incorporation of interlayer Ca that may form a Ca(OH)2-like structure, nanocrystalline and intermixed with C–S–H layers, at high Ca/Si ratios.

13C NMR investigation of CVD diamond: Correlation of NMR and Raman spectral linewidths

1994 ◽  
Vol 9 (3) ◽  
pp. 631-635 ◽  
Author(s):  
Lawrence H. Merwin ◽  
Curtis E. Johnson ◽  
Wayne A. Weimer
Keyword(s):  
Cvd Diamond ◽  
Optical Quality ◽  
Magic Angle Spinning ◽  
Mas Nmr ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
Defect Sites ◽  
Spin Resonance ◽  
Angle Spinning ◽  
Good Signal

Six CVD diamond thin films were examined by magic angle spinning (MAS) 13C nuclear magnetic resonance (NMR), Raman, and electron spin resonance spectroscopy. The use of film samples cut to the diameter of the magic-angle spinning rotor provided ease of spinning and the opportunity to obtain good signal-to-noise spectra in 4 to 16 h. MAS NMR linewidths exhibit a linear correlation with Raman linewidths and reflect the optical quality of the material. Residual MAS NMR linewidths most likely arise from a combination of crystal defect sites and paramagnetic effects.

scholarly journals Use of Ecuadorian natural and acid-surfactant modified zeolites for remediation of oil- contaminated soils

2019 ◽  
Vol 9 (1) ◽  
pp. 93-104 ◽  
Author(s):  
Gladys Cristina Pinto-Santamaría ◽  
Carlos Alberto Ríos- Reyes ◽  
Luz Yolanda Vargas- Fiallo
Keyword(s):  
Contaminated Soil ◽  
Contaminated Soils ◽  
Oil Spills ◽  
Magic Angle Spinning ◽  
Absorption Capacity ◽  
Resonance Spectroscopy ◽  
Magic Angle ◽  
Experimental Conditions ◽  
X Ray ◽  
Modified Zeolites

Oil spills have been one of the greatest environmental problems worldwide. The contamination of soils due to oil spills generates an oil migration down the soil until reaching groundwater. The research focused on remediation of oil-contaminated soils by Ecuadorian natural and acid-surfactant modified zeolites of the Cayo Formation. The natural and modified zeolites were characterized by wavelength dispersive X-ray fluorescence, X-ray powder diffraction, environmental scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and solid-state magic-angle spinning nuclear magnetic resonance spectroscopy. The natural and modified zeolites were added to an artificially oil-contaminated soil to immobilize and limit the uptake of contaminants by rape through changing soil physical and chemical properties in the pot experiment under greenhouse conditions. Several oil contaminated soil-zeolite mixes were tested in replicated laboratory analyses in terms of their ability to absorb oil. Results indicated that the addition of natural and modified zeolites could increase or decrease soil pH and absorption capacity, with high potential in removing oil from soil. Statistical analysis of the experimental data was performed by the variance test analysis. The absorption process had an efficiency of 46% under well-optimized experimental conditions, with an absorbent dose of 30-M, pH = 3.8 and 15 days of contact time.

scholarly journals Synthetic Approaches to the Incorporation of Gallium and Germanium into Inorganic Polymer Structures

2021 ◽  
Author(s):  
◽  
Andrew Timothy Durant
Keyword(s):  
Solid State ◽  
Sol Gel ◽  
Mas Nmr ◽  
Inorganic Polymer ◽  
Magic Angle ◽  
29Si Nmr ◽  
Inorganic Polymers ◽  
X Ray ◽  
27Al Mas Nmr ◽  
Potassium Germanate

<p>New sol-gel and solid-state synthesis methods and combinations of these were developed for the preparation of several new inorganic polymers related to aluminosilicate inorganic polymers, attempting to substitute gallium and germanium for aluminium and silicon. Gallium could successfully substitute for aluminium, but germanium could not be substituted for silicon by these methods. Gallium silicate and gallium aluminosilicate inorganic polymers were synthesised from mixtures of KGaO2, KAlO2, KOH solutions with finely divided SiO2 (silica fume) using a combination of sol-gel and solid-state techniques. The products of these reactions were studied by X-ray powder diffraction (XRD), solid-state 27Al, 29Si, 71Ga and 39K nuclear magnetic resonance with magic-angle spinning (MAS NMR) and scanning electron microscopy (SEM). For the synthesis of these mixed gallium-aluminium silicate inorganic polymers, the optimal SiO2:(Ga2O3+Al2O3) ratio was found to be 7 and the Ga:Al ratio could range from 100% Ga to 100% Al, with all intermediate ratios yielding inorganic polymers. The products showed all the characteristics of a true inorganic polymer, being X-ray amorphous and containing gallium and/or aluminium in tetrahedral coordination states. 29Si MAS NMR showed the occurrence of Si(3Ga) and Si(2Ga) sites when gallium was present, and Si(3Al) and Si(2Al) sites when aluminium was present. Unreacted silica was also detected in these compounds by 29Si NMR and spherical silica particles were observed by SEM. Heat treatment of gallium silicate, gallium aluminosilicate and aluminosilicate inorganic polymers synthesised by variations of the sol-gel method was monitored by thermal analysis methods (DSC-TGA) which revealed a water loss at 75 [degrees]C and 160 [degrees]C followed by a phase transition at 950 [degrees]C. At this temperature the inorganic polymers crystallised to KGaSi2O6 and KAlSi2O6. The thermal behaviour of these samples was found to be different at 1200 [degrees]C; the high-temperature products derived from the gallium silicate inorganic polymers remained as crystalline KGaSi2O6 and retained their shape, while gallium aluminosilicate and aluminosilicate inorganic polymers melted and slumped, losing their shape and becoming X-ray amorphous. Attempts to substitute germanium for silicon in the inorganic polymer structure were unsuccessful. A sol-gel approach using GeO2 produced crystalline K6Ga6(GeO4)6(H2O)7. In an alternative solid-state approach, potassium germanate was synthesised and subsequently reacted with KGaO2 in a solidstate reaction to form partially amorphous hydraulic precursors; however, these did not set on the addition of water. A solid-state reaction of potassium germanate with KGa5O8 formed a partially amorphous precursor powder that set with the addition of water. However, the cured product was not amorphous, but proved to be crystalline K6Ga6(GeO4)6(H2O)7. In another approach, a sol-gel reaction of NaAlO2 solution and GeO2 with KOH solution set to an X-ray amorphous but brittle product. 27Al MAS NMR showed this to contain aluminium in both tetrahedral and octahedral coordination states. When KAlO2 was used instead of NaAlO2, the products were crystalline. The study of the structure of these germanium compounds is hindered by the inaccessibility of the germanium nuclide to MAS NMR. Nevertheless, the ability to synthesise a new category of materials by these new methods opens up the possibility of their potential applications as fluorescent materials and as components of optoelectronic devices.</p>

scholarly journals Comprehension of paraquat adsorption on faujasite zeolite X and Y in sodium form

2017 ◽  
Vol 36 (1-2) ◽  
pp. 684-693 ◽  
Author(s):  
Wina Rongchapo ◽  
Chalermpan Keawkumay ◽  
Nattawut Osakoo ◽  
Krittanun Deekamwong ◽  
Narong Chanlek ◽  
...  
Keyword(s):  
Fourier Transform ◽  
Infrared Spectroscopy ◽  
Fourier Transform Infrared Spectroscopy ◽  
Photoelectron Spectroscopy ◽  
Fourier Transform Infrared ◽  
Magic Angle Spinning ◽  
Mas Nmr ◽  
Magic Angle ◽  
Zeolite X ◽  
X Ray

The nature of paraquat adsorption is compared between zeolite NaX and NaY which have the same faujasite structure but different Si/Al ratio, namely 1.2 and 2.2, respectively. The adsorption was proposed to occur via ion exchange and expected to increase with Al content. However, NaX had a lower paraquat adsorption capacity than NaY. The bare and paraquat-containing zeolites (PQX and PQY) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, N2 adsorption–desorption analysis, magic-angle spinning nuclear magnetic resonance (MAS) NMR, and X-ray photoelectron spectroscopy. The presence of adsorbed paraquat was confirmed by Fourier transform infrared spectroscopy. Paraquat adsorbed in supercages of the zeolites resulting in a decrease of surface area and displacement of sodium cations. Results from 23Na MAS NMR and X-ray photoelectron spectroscopy indicated that interaction of sodium ions in the cavity of NaX was stronger than that in NaY, making it less exchangeable with paraquat.

scholarly journals Single-crystal X-ray diffraction and NMR crystallography of a 1:1 cocrystal of dithianon and pyrimethanil

2017 ◽  
Vol 73 (3) ◽  
pp. 149-156 ◽  
Author(s):  
Ann-Christin Pöppler ◽  
Emily K. Corlett ◽  
Harriet Pearce ◽  
Mark P. Seymour ◽  
Matthew Reid ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Chemical Shifts ◽  
Magic Angle Spinning ◽  
Mas Nmr ◽  
Double Quantum ◽  
Magic Angle ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nmr Crystallography

A single-crystal X-ray diffraction structure of a 1:1 cocrystal of two fungicides, namely dithianon (DI) and pyrimethanil (PM), is reported [systematic name: 5,10-dioxo-5H,10H-naphtho[2,3-b][1,4]dithiine-2,3-dicarbonitrile–4,6-dimethyl-N-phenylpyrimidin-2-amine (1/1), C14H4N2O2S2·C12H13N2]. Following an NMR crystallography approach, experimental solid-state magic angle spinning (MAS) NMR spectra are presented together with GIPAW (gauge-including projector augmented wave) calculations of NMR chemical shieldings. Specifically, experimental 1H and 13C chemical shifts are determined from two-dimensional 1H–13C MAS NMR correlation spectra recorded with short and longer contact times so as to probe one-bond C—H connectivities and longer-range C...H proximities, whereas H...H proximities are identified in a 1H double-quantum (DQ) MAS NMR spectrum. The performing of separate GIPAW calculations for the full periodic crystal structure and for isolated molecules allows the determination of the change in chemical shift upon going from an isolated molecule to the full crystal structure. For the 1H NMR chemical shifts, changes of 3.6 and 2.0 ppm correspond to intermolecular N—H...O and C—H...O hydrogen bonding, while changes of −2.7 and −1.5 ppm are due to ring current effects associated with C—H...π interactions. Even though there is a close intermolecular S...O distance of 3.10 Å, it is of note that the molecule-to-crystal chemical shifts for the involved sulfur or oxygen nuclei are small.

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