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Chemische Technologie, 76327 Pnztal, Germany; and 2 Bruker BioSpin GmbH, Am Silberstreifen, 76287 Rheinstetten, Germany
Introduction
In food process engineering, the handling, pumping, extrusion, or mixing of highly concentrated disperse systems is of importance for initial, intermediate, or nal products. Examples are suspensions (beer mashes, chocolate, dough), foams (protein-, carbohydrate-based), emulsions, porous solids (baked products), and dry/wet bulk solids (malt, sugar). Although plenty of information concerning the rheology of multiphase system is available, the modeling of the ow behavior, structure of the produced system, and its stability cannot be considered as totally completed. In spite of its great importance, the determination of viscosities of disperse systems is difcult in principle [1,2]. Dened velocity proles in rheometers (so-called viscometric ows), the homogeneity of the sample during the experiment, and applicability of continuous mechanics are usually prerequisites for rheometric studies. In disperse multiphase systems, demixing (phase separation: sedimentation, creaming, wall layers), scale effects [3], preparation, time effects (crushing, de-/agglomeration), tearing apart (fat, ointments), and wall slip cause problems when studying the ow behavior and determining ow functions of disperse systems with conventional rheometric methods. Materials with volume fractions of the disperse phase higher than 5 vol.% are usually opaque [4]. NMR offers the possibility to perform measurements non-invasively, non-destructively, and highly selective (in situ, online) in order to study the structure, structural changes, or inner transport processes (without preparations) in owing materials. The objective of this contribution is to demonstrate the potential of various NMR techniques in monitoring ow processes and the structure of disperse systems. The relevance of NMR for engineering is based on the following possibilities and applications of noninvasive and non-destructive spectroscopic/tomographic sequences with possible temporal, spatial, and chemical resolution: r The composition and inner structure of static and dynamic systems and processes are accessible for quantitative characterization.
r Process and quality control can be realized without preparing or disturbing the corresponding product or process. r Micromodels and physically established, phenomenological constitutive laws may be derived from the microscopic data. These models are required for the professional design of industrial processing units and products. The corresponding material functions can be derived by tting the experimental data. r By means of the microscopic non-destructive and noninvasive access, the development and validation of models concerning the ow behavior, boundary/initial conditions, and the critical verication of predictions for technical solutions is possible by comparison with NMR results. The ow behavior is specially important in process engineering: (i) it can be used for process and quality control, (ii) it is required for the design of production plants, and (iii) it has an obvious impact on the structure of materials (sensory behavior). According to the denition used for the scope of this contribution, Rheo-NMR encloses all NMR applications dealing with the combination of ow behavior, ow induced structural changes, and NMR data. Thus, it is possible: (a) to realize ow experiments [5,6] (viscometric ows: tube ow, Couette ow, plane shear ow, plate/plate, cone/plate) in NMR devices in order to determine the corresponding velocity proles. By means of additional information (tube ow: pressure drop, Couette: tormentum) assuming constitutive laws it is possible to derive the corresponding viscosity- and wall slip functions. (b) to study and quantify ow induced structural changes by means of appropriate NMR experiments [79]. (c) to derive correlations between microscopic NMR data and macroscopic rheological material parameters. These correlations could be very helpful for an effective process and quality control by an online determination of practice relevant quantities (viscosity, molar mass) [1,10] in order to control the assumed
2008 Springer.
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or required process conditions and increase the efciency of production units. (d) to realize experimental conditions (concentration/velocity elds) which simulate the practice relevant test conditions in apparatus or processes in food technology. The corresponding materials or phenomena evolve differently without mixing. Therefore, it is impossible to perform these experiments using conventional NMR techniques. NMR applications analyzing the impact of structure of solid systems on the convective/diffusive ow processes [1] are not taken into consideration.
and hydrocolloids [2228], tomato juice [29], butter and margarine [30], egg-white and polymer solutions [31 33], suspensions [26,3437], brous suspensions [38,39], blood [40], and wet bulk solids [41,42]. Tube Flow Assuming appropriate material laws the corresponding material functions can be derived from the velocity proles in a tube ow determined with MRI. The ow of polymer solutions, particle dispersions, and aqueous polysaccharide solutions was already analyzed with MRI velocimetry [13,14,26,36,4347] in order to characterize the ow behavior and detect apparent wall slip for these materials in Poiseuille ow. MRI was used to study the ow of PSPB-water pastes (polystyrenepolybutadiene copolymer) in steady state ows [17]. The velocity proles and volume concentrations of free water and the solid matrix of owing pastes could be mutually independently determined via MRI ow experiments. This supplies direct proof of the relative displacement of free water in owing pastes. It was possible to measure the wall slip of the two phases and, therefore, to differentiate between the shear and slip shares of the total volumetric ow. The ow in tubes with various geometric structures, e.g. a tube with constant circular cross-section [48], tubes with contraction and expansion [48], a tube with one or more cylinders [11], or with a U-bend [14] were studied. The measurement of the time-averaged velocity offers, in a technological view, the possibility to study the inuence of material characteristics (ratio of the uid and solid, type and concentration of additives, general formulation) and process parameter (pretreatment of the sample, process and store temperature, convey distance) on the ow behavior and structure of dispersions. Couette Ultrafast MRI techniques were presented to visualize steady and unsteady Couette ows of water [4951]. In several papers [29,5255], the velocity proles of the Couette ow for homogeneous Newtonian and NonNewtonian uids were visualized by MRI and, thus, shear rate distributions could be derived. The aim was to evaluate standard rheometric methods for one-phase uids by means of MRI. Like in the case of the tube ow, viscosity functions can be derived from the velocity proles determined with MRI [21]. The shear induced diffusion and structure in concentrated density matched suspensions undergoing Couette ow was monitored [41,42]. MRI reveals that PMMA suspensions demix during the shear experiment. The uid fraction increases at the rotating inner cylinder and decreases monotonously from the inner shaft to the outer cylinder. The ow behavior of PTFE pastes and other highly viscous uids was analyzed in a new Couette shear device, developed especially for pastes [21]. The results prove that Couette shear
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experiments are generally not suitable for all pastes or concentrated suspensions. It cannot be guaranteed, without additional experiments, that the assumed constitutive law and corresponding viscosity functions can be transferred to model the velocity prole in any 3D problem. Flow experiments in extruders or other test devices are described in [1,56,57].
relaxation times. The correlation between characteristic viscosities such as the zero-shear rate viscosity 0 or the viscosity at high shear rates can, nevertheless, be used to determine viscosities by means of the corresponding T1 or T2 . In other words, the viscosities are a function of the relaxation times T1 and T2 : = (T1 , T2 ). For the modied four-parameter Carreau model holds [72] () = 0 + [1 + (/1 )a ]0.5 (1)
:shear rate, 0 : zero-shear rate viscosity, : viscosity at high shear rates, a, 1 : parameters. Only nely ground malt can be tested in conventional rheometers, as due to scale effects [3] with respect to the maximum particle size suspensions containing particles with diameters in the order of the characteristic dimensions of the rheometer do not fulll the prerequisites of continuum mechanics. Continuum mechanics is, however, one of the main prerequisites of conventional rheometry. For silicone oils with different molecular weights, it is possible to determine the viscosity and molecular mass by using a correlation with the corresponding T2 [10]. Similar correlations between T1 or T2 and have been found for cis-polyisoprene solutions [73], solutions and suspensions of carbohydrates and sugars of corn [74], milk during acidication with yoghurt culture with and without stabilizers (storage and loss moduli G and G [75]), paper pulps [76], industrial sauces containing starch with different cooking time (G , G [77]), model cheese samples (compression and stress relaxation measurements [78]), emulsions (phase diagrams, shear ow [79]), and chocolate masses (microscopy, shear ow [80]). Besides scale effects, homogeneity is another prerequisite for simple rheological constitutive laws. This is a crucial aspect in process engineering, as many products are multiphase systems. Phenomena causing heterogeneity (phase separation: sedimentation, creaming) and tearing apart (fats, ointments) are usually difcult to detect and quantify in conventional rheometry. Flow experiments combined with spatially resolved spectroscopy or possibly MRI will allow to observe heterogeneity causing ow induced effects and wall slip. Appropriate spectroscopic methods enable to characterize ow induced time effects caused by the energy input or due to special preparation techniques like de-/agglomeration or crushing [66]. Due to the great importance of the viscosity, especially for process and quality control, viscometric methods were developed which allow an online determination of the viscosity [81]. Besides the possibility of combining velocity or, furthermore, concentration proles with the corresponding stress distribution (assuming constitutive laws) [see (a)] ow- and wall slip-functions can be derived by tting the velocity frequency distributions [35,82]: (i) direct 2D imaging of the tube cross-section and subsequent
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determination of the velocity frequency distribution, (ii) radial velocity proles from 1D projections and subsequent determination of the velocity frequency distribution, and (iii) velocity spectra [38]. Principally, it is possible to derive the ow functions (assuming constitutive laws) and information concerning the pore radius distribution from the velocity frequency distribution and an additional single-point measurement of the shear stress [38].
tions, and water as reference. Thus, using triggered NMR sequences it is possible to detect sediments (possibly causing fouling, spoilage, undesired reactions due to overheating at the vessel walls) and, at the same time, evaluate the mixing potential of stirring vessel and stirrers in combination with the applied process conditions for a given material [84].
Relevance of NMR for Process Engineering Realization of Practice Simulating Test Conditions
Rheo-NMR probes enable one, as shown above, to monitor ow induced structural changes in complex uids undergoing well-dened ow types and mechanical treatments (stress, deformation, deformation velocity tensor and derivatives). They could, furthermore, be used to guarantee homogeneity as mixing devices with known shear rate distributions during arbitrary NMR experiments. Mixtures of substances are (i) miscible on molecular level or (ii) only miscible on a non-molecular level [83]. In many industrial disperse mixtures, constituents are present which dissolve partially during the processing. Furthermore, the system may tend to phase separation. Thus, the mixture is not stabile and separates, if the mixing process has been stopped. Examples for this combination of mixture (i) and (ii) behavior (dissolving and sedimentation/ascending) are beer mashes or starch/water mixtures. In order to develop reliable online process and quality controls and analyze efciently the evolution of possible concentration dependent reactions in food systems [protein denaturation, starch plasticization or gelling, degradation of polysaccharides (beer: -glucan)] at practice similar conditions, homogenize composition patterns have to be realized during processing and simultaneous NMR experiments. The corresponding materials or phenomena evolve differently without mixing. As a consequence the corresponding processes achieve a minor efciency and quality. The same holds for ceramic masses which require sufcient mechanical energy input by shearing or kneading [66] or ultra-sonication [67] in order to obtain and maintain structural homogeneity for time periods sufcient for a reliable handling during processing. Comparable materials are problematic to study by non-localized NMR spectroscopy without continuous mixing. Thus Rheo-NMR probes enable one to characterize online reacting, eventually phase separating disperse systems, to identify occurring processes, and to derive relevant kinetic parameters. NMR studies of reacting or non-reacting disperse food systems can be performed in adapted Rheo-NMR devices. Besides the thermally or enzymically induced reactions/structural changes the corresponding velocity proles have been derived in beer mashes, starch soluIf a material in a specic production process (extrusion, pumping, or mixing) has certain advantages and disadavantages, it naturally to enhance the advantages and simultaneously reduce the disadvantages by a simple treatment. Therefore, measuring techniques (empirical plus advanced, if necessary) are required to identify the relevant microprocesses and microstructures in the owing material. If the microprocesses are known, the material can be modied by an appropriate adaption process (additives, coating, ultrasonication [67], kneading [66]), to meet the requirements of the customers. To summarize the ndings, NMR enables one to study many food products and processes in food processing which are often inaccessible by other measuring techniques. The ow behavior is especially important in process engineering: (i) it can be used for process and quality control, (ii) it is required for the design of production plants, and (iii) it has an obvious impact on the structure of foods (sensory behavior). Reviews on spectroscopic/tomographic methods applied in process engineering are given in Refs. [1,8587]. The advantages of NMR applications in engineering in order to study combined ow- and NMR-phenomena are r None or only minor preparation (dilution for optical techniques) is necessary. r Tracers do not have to be added in general. Detectable spins themselves can act as tracers. r NMR measurements are non-destructive and noninvasive. r Processes can be studied completely by means of NMR using one single sample, thus reducing systematic measuring errors resulting from compositional/experimental variations. r Using other techniques without spatial resolution, effects are averaged, e.g. in systems tending to phase separating, and might be misinterpreted or added possibly to measuring errors. r An online determination of practice relevant quantities (viscosity, water-holding capacity, denaturation fraction) is possible in order to control the assumed or required process conditions (temperature, concentration, velocity distributions). r Demixing can be prevented (ultra-sonication or RheoNMR probe).
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References 1823
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