Oil and water determination in emulsions by pulsed low-resolution NMR

A pulsed, low-resolution nuclear magnetic resonance (NMR) technique has been used for the oil and water determination in O/W emulsions. The method is based on the analysis of the longitudinal magnetization decay curve, that, due to the different relaxation times of oil and water, consists of 2 recognizable components. Correlation of NMR results with fat content is described. A good correlation between the NMR response and fat content by weight has been found. The rapidity and accuracy of the measurements are comparable to those of other techniques.     

Applications of pulsed NMR to fatty emulsions

Pulsed NMR was used to measure solid fat content in oil-in-water type emulsions. The data obtained were useful in selection of optimum types and levels of emulsifiers for each system. By using a flow-through cell in the NMR magnet, the rate and extent of phase separation could be measured accurately. This approach provides a new, quantitative method to measure emulsion stability. Presented at the AOCS Fall Meeting in Cincinnati, September 1975.     

Fully automated determination of solid fat content by pulsed NMR

Pulsed NMR has been developed into a quick, accurate fully automated method for the determination of the solid fat content in partially crystallized fats. Accepting a standard deviation of 0.3% solids, the percentage of solids is displayed on a digital voltmeter or printed out 6 sec after placing the sample into the sample holder. To allow for the dead time of the receiver, a correction factor has been introduced giving rise to only small errors (<1%) in the solid fat content. Due to the short measuring time, no temperature control of the sample holder is needed between 10–45 C. Pulsed NMR values can be converted into dilatations and vice versa.     

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.     

Surface crystallization of poly(ethylene terephtalate) studied by atomic force microscopy

Poly(ethylene terephtalate) (PET) crystallization was shown by atomic force microscopy (AFM) to occur at 85 °C in the first few nanometers near the polymer-air interface. The surface was fully transformed into spherulites after 30 min, while no signs of bulk crystallization were observed by FTIR. All the observed spherulites presented a nucleation centre, indicating that the crystallization process started at the surface of the film. Tapping mode AFM confirmed that the spherulites were not covered by an amorphous layer. The most probable explanation is a decrease of T_g near the surface. Due to the poor crystallization conditions, the constitutive units of the spherulites were small crystalline blocks. By changing the annealing time, it was possible to produce PET surfaces with different surface fractions consisting of semi-crystalline material (spherulites) and amorphous matrix. This provided a controlled surface heterogeneity on the submicrometer scale, with a contrast in terms of stiffness, roughness and swelling by organic solvents.     

Measurement of emulsion stability by pulsed nuclear magnetic resonance (NMR)

The stability of emulsions can be measured rapidly and accurately using pulsed nuclear magnetic resonance (NMR).     

A pulsed low resolution NMR study on crystallization and melting processes of cocoa butter

Pulsed low resolution nuclear magnetic resonance (NMR) was employed to measure the «melting» curves of different series of cocoa butter samples. The samples were prepared from completely liquid phase by cooling and tempering them at different temperatures T_c for varying time Δt. The «melting» curves were measured while keeping the sample at a fixed temperature T_m. The complex shape of each curve was interpreted in terms of cocoa butter polymorphism, and the results were compared with data obtained by other techniques available in the literature. Using just two tempering temperatures (+7 C and −18C), we were able to distinguish four solid phases and identify them with the phases II, III, IV, and V described in literature. Our data are in full agreement with literature. Several novel results have been also found. These include the kinetic constants of the melting processes of phases II and III, the rate constants of solidification of phase V, the conversion of phase III into phase IV before melting at temperatures ≥30 C, and the growth of phase V out of phase II at −18 C (including the rate constant of this process). We are convinced that NMR may serve as a principal tool in fat polymorphism investigations, especially if it is combined with other techniques such as differential scanning calorimetry. Its advantage, apart from rapidity of measurement, is the fact that the measurement itself does not interfere with the melting or solidification process studied. On the other hand, it does not distinguish in a direct way between different solid phases present in the sample; this can be done only in inference from the behavior upon melting.     

Comparison of ultrasonic and pulsed NMR techniques for determination of solid fat content

In this work an ultrasonic velocity technique was compared to direct pulsed NMR (pNMR) spectroscopy for the determination of the solid fat content (SFC) of anhydrous milk fat (AMF), cocoa butter (CB), and blends of AMF and CB with canola oil (CO) in the range 100 to 70% (w/w). In situ measurements of ultrasonic velocity were carried out during cooling (50–5°C) and heating (5–50°C) of the fat samples, and SFC values were calculated. The SFC were also determined simultaneously by pNMR. Peak melting temperatures determined by DSC were used as an indicator of the polymorphic state of the different fats and fat blends. Estimates of SFC obtained using pNMR and ultrasonic velocimetry did not agree. Our results suggested that ultrasonic velocity was highly dependent on the polymorphic state of the solid fat. Ultrasonic velocity in fat that contained crystals in a more stable polymorphic form was consistently higher than in fat that contained crystals in a less stable polymorphic modification. A high attenuation of the signal was observed in milkfat and CB at lower temperatures, particularly after sitting for 24 h. This high attenuation could be a product of scattering by crystallites or by microscopic air pockets formed upon solidification of the material, or it could be due to high ultrasonic absorption associated with phase transitions. This research highlights some of the problems associated with applying ultrasonics to the determination of SFC.     

Segmental mobility in poly(isoprene) rubber studied by deuterium-carbon NMR correlation spectroscopy

Summary A HMQC based deuterium-carbon correlation method is used for the first time to study the segmental mobility in a fully deuterated poly(isoprene) (PI) rubber network. The isotropic J _CD couplings can be utilized for polarization transfer between ²H and ¹³C spins in a mobile solid polymer. This makes it possible to correlate the ²H resonances with the ¹³C chemical shifts of the attached carbon in a two-dimensional (2D) experiment, and thus allow the extraction of the individual ²H signals. The experimental data obtained from the 2D correlation spectrum indicates differences in the segmental mobility of the C-D vectors in perdeuterated PI. The conclusions are fully consistent with ²H and ¹³C T ₁ relaxation data. The results shown in this paper demonstrate the potential of ²H-¹³C NMR correlation spectroscopy in solid systems which produce overlapped 1D ²H spectra. Received: 11 December 2000/Revised version: 1 March 2001/Accepted: 1 March 2001     

Milk fat fractionation by solid-layer melt crystallization

The layer crystallization process has the potential to produce the same milk fat fractions as can be obtained by the suspension crystallization process. That is, milk fat fractions with solid fat content melting profiles similar to those obtained by suspension fractionation can be produced with this technique. The fatty acid profiles as well as the melting enthalpies of the different fractions confirm the separation of milk fat by the layer technique. Furthermore, there is potential to improve the results of separation presented in the first part of this paper. The two sources of improvement, temperature control of the process and controlled nucleation, lead to (i) a smooth crystalline layer with a low amount of entrapped mother liquor, contrary to the layers composed of agglomerated needles, and (ii) a good quality of attachment of the crystalline layer to the cooled surface. Moreover, the product quality can be increased using sweating as a postcrystallization step. “Sweating by warm gas” seems to have a better outlook concerning handling and controlling the process than “sweating by warm tube” because sloughing of the crystal layers can be avoided. Further investigations of the mass ratio of sweating fraction and amount of product as well as the aspect of energy consumption will determine the technical feasibility of solid-layer crystallization for fractionation of milk fat.     

Quiescent crystallization of poly(lactic acid) studied by optical microscopy and light‐scattering techniques

The crystallization behavior of poly(lactic acid) (PLA) has been studied extensively, and this has resulted in different reported values for the nucleation densities (Ns) and crystal growth rates (Gs) for similar grades. These inconsistencies may be magnified when they are used in subsequent modeling studies. Therefore, the quiescent crystallization behaviors of three PLA grades were studied with polarized optical microscopy and small‐angle light‐scattering experiments. The Gs and Ns were determined at several isothermal crystallization temperatures with a device that provided near‐instantaneous cooling to the isothermal crystallization temperature. Two growth rate regimes, which were attributed to α and α′ crystallization with a transition around 120 °C, were observed. Avrami analysis revealed that the poly(l ‐lactic acid) homopolymer crystal growth was three‐dimensional and was unaffected by the presence of stereocomplex PLA. The PLA copolymer crystals had a transition from an initial sheaflike conformation to three‐dimensional growth. Furthermore, the lamellar twisting of the homopolymer was observed at the isothermal crystallization temperature around 144 °C. These findings can be used for future modeling studies to predict material behavior in various industrial processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44566.     

Dynamics of novel hydrogen-bonded acidic fluorinated poly(amide-imide-silica) hybrids studied by solid-state NMR

Novel hydrogen-bonded acidic fluorinated poly(amide-imide-silica) hybrid materials, FPAI-SiO₂ (6E and 6F) series, were synthesized by a sol-gel process. The structures and spin relaxation of the hybrids were characterized by infrared (IR), and ²⁹Si and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The abundant Q⁴ structures implied that in free catalyst the degree of condensation of tetramethoxysilane was enhanced by hydrogen-bonded acidic fluorinated poly(amide-imide). The dynamics on the local mobility of the hybrids was investigated by the time constant for energy exchange between ¹H and ²⁹Si spin system (T_SiH) and spin-diffusion path length (L) measurements. It was found that the faster T_SiH of 6E and 6F hybrids compared with the previous study of similar 6C and 6D hybrids implied that 6E and 6F hybrids had more aggregated structures even though the organic terminal segment changed from rigid imide to more flexible amide. The interactions of the charge transfer between donor and acceptor molecules or π-π aromatic stacking may be the dominant factors to affect the structures of 6E and 6F hybrids. Moreover, M¹ and D² segments of 6F hybrids had the same level mobility and the mobility of the 6F hybrids was little improved as the soft and flexible 1,3-bis(3-aminopropyl)-tetramethyl-disiloxane segment was incorporated in the dense structures of 6F hybrids. All of the L values of 6E and 6F hybrids were on the scale of 3.5-4.0 nm. The result also suggested that 6E and 6F hybrids had similar denser structures as 6D hybrids.     

Determination of oil in aqueous emulsions by wide-line NMR

The radio frequency (r-f) saturation method was shown valid for determination of four edible oils in aqueous emulsions but not in commercial margarine. The interference in case of margarine was shown to be due to nonfat solids. The signal from water at low RF level was eliminated by converting to water of crystallization. Of three anhydrous salts studied for this purpose, only magnesium perchlorate was satisfactory. The method could be made quantitative for oil in margarine only by addition of carbon tetrachloride to the margarine before addition of magnesium perchlorate. One of 10 papers to be published from the Symposium “Wide Line Nuclear Magnetic Resonance,” presented at the AOCS Meeting, Minneapolis, October 1969.     

Local order and strain-induced orientation in poly(butadiene) networks studied by 2H NMR

Summary Deuterium nmr has been employed to determine the average orientation of chain segment in poly(butadiene) networks. The nmr spectrum lineshape reveals the orientation distribution of network vectors due to the crosslinks, whereas the observed splitting gives information about the orientation due to segmental interactions. Both the lineshape and the splitting have been fitted simultaneously for a range of deformed poly(butadiene) networks varied in crosslink density and precursor chain length. From the fitting parameters the separate contribution to the average orientation arising from network constraints and interaction are calculated. These are used to estimate the effective molecular weight between topological constraints and the size of the segmental interaction. It could be shown that the latter remains constant as the crosslink density is varied. This is a strong evidence of the recently published theoretical framework. Received: 28 August 1999/Revised version: 6 October 1999/Accepted: 6 October 1999     

Ion solvation studied by NMR and electrochemical methods

Electrochemical and NMR experiments with solutions of silver salts in mixtures of water—acetonitrile, water—dimethylsulphoxide, and methanol—dimethylsulphoxide have been compared and discussed in terms of ion solvation and solvent-solvent interactions. The solvation of aluminum(III) in mixtures of N,N-dimethylformamide, dimethylsulphoxide, and nitromethane depends also on solvent-solvent interactions, as ¹H- and ²⁷Al-NMR measurements show.     

Buildup of thermoset and crystallization of thermoplastics studied by electrical techniques

Up to now, few techniques were available that allowed nondestructive in situ characterization of polymerization during the curing of a thermoset resin. Dynamic dielectric measurements made over a wide range of frequencies provide a sensitive and convenient control to follow up the epoxy-amine cure or to follow the formation of the thermoplastic materials. The direct current measurements and the time of flight measurements were developed to confirm interpretation of the electrical techniques in terms of correlations of the evolution of the conductivity and the network formation and also to evaluate the real value of the ion mobility and its evolution in a course of reaction. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2529–2543, 1997     

Stereoregularity of PVC studied by 13C NMR

The proton decoupled ¹³C NMR spectra of PVC polymerized at various temperatures were obtained using a 150-MHz NMR spectrometer. Chemical shift changes induced by a solvent effect were utilized to allow the detection of the six possible tetrads. Eight of ten possible pentads were also observed. The relative areas of tetrads and triads indicate that the polymerization of PVC above ?20°C is Bernoullian.     

Measurement of crystallization in stretched rubber by rapid-passage NMR

Continuous-wave rapid-passage proton NMR (30 MHz) was performed on lightly crosslinked natural cis-polyisoprene at elongations up to 720%, at temperatures between ?100° and 100°C, and after delays of up to several weeks after stretch. A method of separating the spectra into a narrow and a wide component was developed and applied. The results are interpreted in terms of the effects of a glass transition and strain-induced crystallinity and are in general agreement with results by other methods. The degree of crystallinity is found to increase strongly with strain (from zero for unstretched samples to 31% at elongations of 720% at room temperature), to increase with time, reaching equilibirium most rapidly in the most highly strained samples, and to decrease approximately linearly with temperature above about 20°C.