Quantitative Si MAS NMR spectroscopy of cement and silica fume containing paramagnetic impurities

The low natural abundance and the long spin lattice relaxation time of ²⁹Si lead to long measurement times and/or low signal-to-noise ratios using ²⁹Si magic angle spinning NMR spectroscopy. By contrast, samples containing paramagnetic iron ions have much shorter relaxation times, making measurements up to seven times more efficient, but at the same time making quantitative analysis unreliable. To solve the problem, the spin-lattice relaxation times of ordinary Portland cement (opc) and silica fume with and without iron content has been determined with inversion recovery experiments. The effect of varying the spectrum repetition time on the quantitative analysis is demonstrated for mixtures of opc with silica fume. For opc and silica fume with iron impurities repetition times as short as 5 s has permitted accurate quantitative analysis of the silicates present in these materials.     

Zr K-Edge XAS and 29Si MAS NMR Studies on Hexagonal Mesoporous Zirconium Silicate

Hexagonal mesoporous silicate (HMS) molecular sieve containing zirconium species (Zr-HMS) has been synthesized using a neutral template of hexadecylamine with ethanol and water. A disordered channel structure with a uniform diameter of 44.1 Å was confirmed by powder X-ray diffraction after calcination. From N₂ adsorption/desorption measurement, it is found that Zr-HMS has a very high surface area of about 910 m²/g (BET) and a mesopore with a size of 21 Å (BJH). According to the X-ray absorption spectroscopy at the Zr K-edge, it is confirmed that Zr atoms are coordinated by six oxygen neighbors with a distance of 2.13 Å, which is shorter than the (Zr—O) bond distance found in ZrO₂ or ZrOCl₂·8H₂O. The ²⁹Si MAS-NMR spectrum for Zr-HMS shows two additional peaks around –94.6 and –107.2 ppm due to the Q³Zr and Q⁴Zr components, respectively, besides three peaks at –91.1, –101.5, and –111.3 ppm due to the silicate network. The relation between the pore and crystal structures and the local environment around Zr is discussed in detail.     

Semiquantitative analysis of thiophenic compounds in light cycle oil (LCO) using C NMR spectroscopy

S-methyltetrafluoroborate salts of the thiophenic compounds (CH₃-S⁺:BF₄⁻) present in LCO petroleum fractions were obtained and analyzed by ¹H and ¹³C NMR spectroscopy. The methylation of the samples was carried out using 99.5% ¹³C enriched methyl iodine, to improve the sensitivity of the technique. The amount of the methylated derivatives was determined by the internal standard method; using dioxane as a reference, 37 sulphur compounds were detected. Among them, benzo[b]thiophene, dibenzo[b,d]thiophene, and several isomers of methyl, dimethyl and trimethyl[b]benzothiophenes were the most abundant. With this research, it was demonstrated that NMR spectroscopy can be used to analyze thiophenic compounds from petroleum medium fractions.     

C NMR study on structure, composition and curing behavior of phenol-urea-formaldehyde resole resins

Phenol-urea-formaldehyde (PUF) resole resins were synthesized and analyzed by both liquid and solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The liquid ¹³C NMR analysis indicated that the co-condensation reactions between the phenolic ring and the urea unit occurred during the synthesis of the resins. The addition of the urea component effectively reduced the free formaldehyde content in the resin systems. Methylene ether bridges in the resins were found to be mainly associated with the urea units. pH had significant influences on the structure and composition of the resins. Solid-state ¹³C NMR measurements of the cured resins suggested that the pH probably affected the curing mechanism. A longer time and a higher temperature can generally accelerate the curing process and increase the rigidity of the cured network.     

On the Quantification of Lignin Hydroxyl Groups With 31P and 13C NMR Spectroscopy

Factors affecting the accuracy of the analysis of lignin hydroxyl and carboxyl groups with ³¹P NMR have been further elucidated. Two modifications of ³¹P NMR analysis of lignin, namely the protocols using 1,3,2-dioxaphospholane (PR-I) and 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (PR-II) as phosphorylation reagents with different internal standards, were studied. The previous ³¹P NMR standard protocol with PR-II underestimated OH groups by about 30%, whereas the ³¹P NMR standard protocol with PR-I tended to produce overestimated data. It has been shown that cholesterol is not an appropriate internal standard, resulting in underestimated values for OH groups due to incomplete baseline resolution. The best internal standard has been found to be endo-N-hydroxy-5-norbornene-2,3-dicarboximide. Strong care should be taken related to the stability of the internal standards to avoid inflated results due to IS degradation. Under modified optimized conditions, both methods show a good correlation with the ¹³C NMR protocol in the quantification of hydroxyl groups as average, with the variability between the methods in the range of 5–15%. However, the ³¹P NMR protocols report COOH content that is twice as low as that of ¹³C NMR data. Finally, the best approach for the use of the ³¹P and ¹³C NMR methods in lignin analysis is discussed.     

NMR Studies of Sol-Gel Derived Hybrid Materials Based on Triethoxysilylated Diethylenetriamine and Tetramethoxysilane

Inorganic-organic hybrid materials were prepared by hydrolysis and condensation of triethoxysilylated diethylenetriamine (f-DETA) and tetramethoxysilane (TMOS). The prehydrolysis stage of this f-DETA/TMOS system was monitored by ²⁹Si NMR spectroscopy. The NMR experiments indicated that f-DETA hydrolyzes and condenses nearly as fast as TMOS at pH 0–1, but lags far behind the latter at pH~4.2. Gels derived from f-DETA and TMOS were studied using ¹³C or ²⁹Si solid state NMR spectroscopy. The concentration of the alkoxy groups and the extent of condensation of the T & Q species in the cured gels were estimated. The contents of the Si–OMe group and Si–OEt group were barely detectable in most water-abundant systems (equivalent ratio of water to alkoxysilane ~4.0). However, a significant amount of Si–OⁱPr groups was found if the reactant f-DETA was stored at room temperature in solvent 2-propanol for three weeks or longer. The relative composition of each T^z or Q^z species was estimated for gels prepared in media of different acidity levels and water concentrations and then cured at 125–130°C for 4 h. As the acidity of the medium increased from pH 0–2 to pH 4–5, the extent of condensation of the T species decreased but that of the Q species increased. The hydrolysis of urea groups in f-DETA during the sol-gel process was also evaluated by ¹³C solid state NMR spectroscopy. The results indicated that only a very small fraction of urea groups was hydrolyzed during the sol-gel process.     

NMR study of the gamma radiolysis of poly(dimethyl siloxane) under vacuum at 303 K

The structural changes which occur on the γ-radiolysis of poly(dimethyl siloxane) (PDMS) under vacuum at 303 K have been investigated using ²⁹Si and ¹³C NMR. New structural units consistent with main chain scission and crosslinking through both H-linking and Y-linking reactions have been identified. The results obtained at various absorbed doses have been used to calculate the G-values for scission and crosslinking. G-values for scission of G(S)=1.3±0.2, for H-linking of G(D^CH₂-R)=0.34±0.02 and for Y-linking of G(Y)=1.70±0.09 were obtained for radiolysis under vacuum at 303 K. Thus crosslinking predominates over scission for radiolysis of PDMS under these conditions, and, by contrast with previous studies, Y-links have been shown to be the predominant form of crosslinks.     

Analysis of sequence distribution in methyl methacrylate-methyl acrylate copolymers by C NMR spectroscopy

Methyl methacrylate (MMA)-methyl acrylate (MA) copolymers, prepared in bulk at 50 °C using AIBN as initiator, were characterized by 150 MHz ¹³C NMR spectroscopy, including use of the Distortionless Enhancement by Polarization Transfer (DEPT) experiment to obtain methylene and methine carbon resonances as subspectra. Dyad, triad, tetrad and partial pentad distributions were measured from the α-methyl, methine and methylene carbon resonances. These were in good agreement with distributions calculated for the copolymers based on monomer feed compositions, conversions and reactivity ratios of 2.60 and 0.27 for methyl methacrylate and methyl acrylate, respectively.     

C NMR Molecular dynamic investigation of tropical wood Angelin Pedra (Hymenolobium paetrum)

Time has shown wood as a very important material in several areas related to civil construction. Because of its organic origin, wood presents different physical and mechanical properties for different species. In consequence of these variations, there is the necessity to study chemical composition and molecular dynamic to better understand its property that will promote the use in civil construction. The focus of this work is to evaluate the Angelin Pedra wood in relation to the main chemical components, the domain type and the chemical components that constitute these domains. Solid state nuclear magnetic resonance (NMR) will be used for that, since the main advantage of NMR comparing to other techniques specially for the sample in question, is the potential of this spectroscopy to provide analysis of all functional group without pre-treatment of the sample. Some solid state NMR techniques were used and it was observed that the wood in investigation presents different packing, cells arrangements and chains ordination along the fibers in the different parts of the wood, because of the different distribution of the main wood components along the fibers.     

Molecular model of Estonian kukersite kerogen evaluated by C MAS NMR spectra

The chemical structure of Estonian kukersite kerogen is evaluated using a simulation of ¹³C MAS NMR spectrum. A reasonable fit to the experimental NMR spectrum is obtained by assuming a model of the geomacromolecule with empirical formula C₄₂₁H₆₃₈O₄₄S₄NCl and a set of structural elements comprising mainly alkylated phenolic structures particularly alkyl-1,3-benzenediols and condensed alicyclic rings. From the presented model new views are coming up on the carbon skeleton of kerogen and constraints on the phenol formation pathways in the retorting process, i.e. up to 80% of methylene groups in kerogen are located in aliphatic chains and the complicated mixture of phenols in the retort oil seems to result mainly from the thermal conversion of alkyl-1,3-benzenediol units originally present in kerogen.     

THE STRENGTH OF MUTAGENICITY, 13C NMR CHEMICAL SHIFTS,AND ELECTRONIC STATES OF NITROBENZANTHRONES

Mutagenic activities of nitrated benzanthrones (NBAs) vary largely with the position and the number of the nitro group. To investigate the structure-activity correlations for NBAs, we have performed nuclear magnetic resonance (NMR) measurements and molecular orbital calculations for the three nitrobenzanthrones, 2-NBA, 3-NBA, 11-NBA; the three dinitrobenzanthrones, 1,9-DNBA, 3,11-DNBA, 3,9-DNBA; and the trinitrobenzanthrone, 3,9,11-TNBA. It was confirmed that the ¹³ C chemical shifts (δ) of the ortho carbon atoms with respect to the nitro group of the compounds tend to be more upfield with decreasing mutagenic activities. The molecular orbital calculations revealed that the LUMO energies of the compounds decrease with mutagenic activities, and that the HOMO and LUMO densities tend to decrease and increase, respectively, with decreasing mutagenic activities. These results indicate that reduction is very important in the metabolism of nitrobenzanthrones.     

Sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer using H and C NMR

The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz ¹H NMR. The well-resolved alcoholic CH₂ proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics.     

Effects of Solvation and Ionization on 13C NMR Spectra of Lignin Model Compounds,Spruce Milled Wood Lignin and Kraft Lignin

The effects of alkali and polar aprotic solvent on the aromatic carbons signals in ¹³C NMR (Carbon-13 nuclear magnetic resonance) spectra of lignin model compounds and spruce milled wood lignin (MWL) were studied. It was found that in 1 M aqueous NaOH signal shifts of C-1 and C-4 carbon atoms in the aromatic ring were the most noticeable in lignin models with free phenolic hydroxyl groups, which are ionized under the conditions. A similar effect in the spectra of the studied model compounds was observed in 0.5 M aqueous NaOD-deuterated dimethyl sulfoxide (DMSO) mixture (DMSO: water ratio 3:7 v/v). The model data help explaining changes in the ¹³C NMR spectra of MWL and lignin in situ dissolved in spruce kraft black liquor caused by ionization. In the ¹³C NMR spectra of spruce black liquor the signals of phenolic and non-phenolic lignin units are clearly separated and do not overlap with the signals of the carbon atoms of carbohydrates and other aliphatic products of wood degradation. The data obtained are useful in understanding the important role of solvation and ionization processes leading to lignin solubilization.     

13C NMR analysis and gas uptake measurements of pure and mixed gas hydrates: Development of natural gas transport and storage method using gas hydrate

¹³C NMR spectra were obtained for pure CH₄, mixed CH₄+THF, and mixed CH₄+Neohexane hydrates in order to identify hydrate structure and cage occupancy of guest molecules. In contrast to the pure CH₄ hydrates, the NMR spectra of the mixed CH₄+THF hydrate verified that methane molecules could occupy only the small portion of 5¹² cages because the addition of THF, water-soluble guest component, to aqueous solution prevents the complete filling of methane molecules into small cages. Furthermore, from these NMR results one important conclusion can be made that methane molecules can’t be enclathrated at all in the large 5¹²6⁴ cages of structure II. In addition, gas uptake measurements were carried out to determine methane amount consumed during pure and mixed hydrate formation process. The moles of methane captured into pure CH₄ hydrate per mole of water were found to be similar to the full occupancy value, while the moles of methane captured into the mixed CH₄+THF hydrate per moles of water were much lower than the ideal value. The overall results drawn from this study can be usefully applied to storage and transportation of natural gas.     

Strain-induced crystallization of natural rubber as studied by high-resolution solid-state C NMR spectroscopy

A series of high-resolution solid-state ¹³C NMR experiments were performed on both unstretched and in situ stretched natural rubber samples. From the ¹³C CP/MAS spectra, it was found that natural rubber does form small crystals at room temperature though the degree of crystallinity is very small. Furthermore, from the ¹³C DD/MAS spectra, the crystalline signals were found to increase with the increase of draw ratio. ¹³C spin-lattice relaxation time (T₁) and ¹H spin-spin relaxation time (T₂) of in situ stretched natural rubber were measured for the first time, which provided further evidences for the conclusion that there exist crystals in both stretched and unstretched natural rubber samples. Quantitative ¹³C NMR measurements indicated that strain-induced crystallization occurs when the draw ratio reaches about 2.0 and the maximum crystallinity of our natural rubber samples can be as high as 19.3% upon stretching.     

Changes upon heating of the distribution of Al,P and Si atoms in the SAPO-37 molecular sieve

A drastic change in the environment of Si atoms in SAPO-37 after heating at 1173 K is seen in the²⁹Si MAS NMR spectrum. This suggests a modification of the location of Si, Al and P atoms. Three main phases would coexist in large amounts in the faujasite structure, the SAPO-37 originating phase, pure SiO₄ islands and an aluminosilicate phase comparable to Si-Al faujasite.     

Structural characterization of maleic anhydride grafted polyethylene by C NMR spectroscopy

Maleic anhydride grafted polyethylene, [2,3-¹³C₂] MA-g-PE, which was synthesized with ¹³C labeled maleic anhydride [2,3-¹³C₂] MA in solution, was characterized by ¹³C NMR spectroscopy in order to make clear the structure of graft groups. The results reveal that [2,3-¹³C₂] MA-g-PE has succinic anhydride oligomeric grafts with a terminal unsaturated MA ring in addition to well-known saturated succinic anhydride oligomeric grafts and that the former grafts are longer but fewer than the latter.     

Solid-state C NMR investigation of the structure and dynamics of highly drawn polyethylene—detection of the oriented non-crystalline component

The structure and dynamics of highly drawn polyethylene samples were studied by solid-state ¹³C NMR spectroscopy. The analyses of the ¹³C spin-lattice relaxation time (T_1C) and the ¹³C spin-spin relaxation time (T_2C) have revealed that at least three components with different T_1C and T_2C values, which correspond to the crystalline, less mobile non-crystalline, and rubbery amorphous components, exist for these materials, as in the case of isothermally crystallized samples. However, another component with a mass fraction of 0.13-0.18 exists which has a ¹³C chemical shift very close to that of the orthorhombic crystalline phase but has an extremely small T_1C. Since this component is believed to have the all-trans conformation, it is termed fast all-trans. The chemical shift anisotropy (CSA) spectra for various samples that have small T_1C values have been recorded and resolved into those of the non-crystalline and fast all-trans components. As expected, the CSA spectra of the less mobile non-crystalline and rubbery amorphous components that have the smallest T_1C values display only a slight asymmetry. In contrast, the CSA spectrum of the fast all-trans component displays higher asymmetry. However, the spectrum is still much narrower than that of the normal orthorhombic crystalline phase, indicating a high degree of motional averaging. It is proposed that this component should be a highly oriented non-crystalline component, which may exist as taut tie-molecules traversing the non-crystalline region. To account for the narrow CSA, this component must undergo rapid fluctuation with large amplitudes at the torsional potential minimum in each C-C bond and possibly an additional random jump or diffusional rotation around the chain axis. Additional measurements obtained by aligning the draw axis of the sample parallel or perpendicular to the static magnetic field indicate that the fast all-trans component is oriented along the drawing direction and subjected to rapid motion around the chain axis.     

13C NMR spectroscopic characterization of trimethylol propane ester lubricants

The ability to identify the different acyl groups present in lubricants composed of mixed acid esters of trimethylol propane by¹³C nuclear magnetic resonance spectroscopy is demonstrated. The technique discriminates between esters with acyl groups containing between 5 and 10 carbon atoms and can be used similarly to identify acyl groups in pentaerythritol or neopentyl glycol ester lubricants.     

Separation of isotope C using high-performance structured packing

A special high-performance structured packing, PACK-¹³C, with the surface area high as 1135 m² m⁻³ was developed, and the first stable isotope ¹³C pilot-scale plant using structured packing was designed and constructed by carbon monoxide cryogenic distillation, which has run smoothly over 6 months. The height and inner diameter of the distillation column were respectively, 20 m and 45 mm and the height of packing bed was 18 m. The column was well insulated by vacuum multilayer insulation and the total heat leakage of the column was less than 30 W. When the F-factor changes from 0.18 to 0.90 ms⁻¹ (kg m⁻³)^1/2, the numbers of theoretical plates per meter decreases from 30 to 20, the pressure drop is less than 25 Pa for each theoretical plate, the dynamic liquid holdup is between 11% and 21%, and the pilot-scale plant produces 2.1 g 15% isotope ¹³C each day. The fluid mechanical and mass transfer empirical equations were developed according to the experimental data of PACK-¹³C. The PACK-¹³C structured packing exhibits very high performances in isotope separation efficiency and operational flexibility, which is far superior to the traditional random packing. PACK-¹³C is a perfect packing to serve in ¹³C separation to increase productivity and reduce consumption.