Rheological discrimination and characterization of carrageenans and starches by Fourier transform-rheology in the non-linear viscous regime

Classical rheological methods are often insufficient to characterize and to differentiate the non-linear rheological behavior of polysaccharide systems such as carrageenan or starch. In this article the non-linear rheological method of characteristic functions is used to discriminate between the different polysaccharides. This method is based on the Fourier transform-rheology (FT-rheology). The response of a sample is decomposed using simple characteristic functions. We show that there are differences in the response of a number of carrageenan and starch samples, which are not distinguishable with classical rheometry.     

The crossover between linear and non-linear mechanical behaviour in polymer solutions as detected by Fourier-transform rheology

 The application of oscillatory shear strain leads, in the non-linear regime, to the appearance of higher harmonic contributions in the shear stress response. These contributions can be analyzed as spectra in Fourier space, with respect to different frequencies, amplitudes and phase angles. In this article, we present an application of this new characterization method to a solution of the linear homopolymer polyisobutylene. The degree of non-linear response during oscillatory shear is quantified using the normalized intensity of the third harmonic contribution. We were able to show experimentally on polyisobutylene that there is an immediate onset of the non-linear response even for very small shear strain amplitudes. Received: 21 June 1999/Accepted: 21 August 1999     

Prediction of normal stresses under large amplitude oscillatory shear flow

The dynamic response of viscoelastic fluids under large amplitude oscillatory shear (LAOS) has been a subject of long history. In the LAOS flow, the analysis has been mostly focused on shear stress, possibly due to the lack of accurate measurement of normal stress. However, the normal stress may become larger than shear stress at high-strain amplitudes, and thus it is important that we have a good understanding of the normal stress behavior. Furthermore, with the advancement in the instrumentation, it has become possible to get more reliable data. The purpose of this paper is to develop a research platform to analyze and to understand the normal stress behavior of complex fluids under LAOS flow. In this study, we utilized the Giesekus model as a representative constitutive model, and investigated its diverse responses. We defined the dynamic properties corresponding to normal stress, in a similar way to define dynamic moduli from shear stress, and examine their behavior with various analyzing tools. Experimental data were also compared with model predictions. Despite the fact that it is not yet possible to compare all of the predictions because of instrumental limitation, the prediction has been found to fit well with the experimental data. This study is expected to provide a useful framework for further understanding the nonlinear behavior of complex fluids at large deformation.     

High sensitivity Fourier-transform rheology

The application of oscillatory shear strain leads, in the non-linear regime, to the appearance of higher harmonic contributions in the shear stress response. These contributions can be analyzed as spectra in Fourier space with respect to their frequencies, amplitudes and phase angles. In this article, we present several theoretical and practical aspects of measuring Fourier rheology spectra with high sensitivity. Using the hardware of a conventional rheometer, Fourier rheology spectra with a signal-to-noise ratio of about 18,000:1 for a single acquisition were obtained. This allowed the observation of harmonics up to the 21st harmonic. Signal averaging can further increase the sensitivity. Received: 4 November 1998 Accepted: 28 April 1999     

Non-linear rheology of a face-centred cubic phase in a diblock copolymer gel

The viscoelastic behaviour of a poly(oxyethylene)-poly(oxybutylene) diblock copolymer in aqueous solution forming a face-centred cubic (fcc) micellar phase has been investigated using oscillatory shear rheometry. With increasing strain amplitude, the micellar solution was observed to undergo a transition from linear to non-linear behaviour, characterized by strong shear thinning. The non-linear behaviour observed in the stress response was analyzed by Fourier transformation of the waveform. Fourier analysis revealed that the high harmonic contributions to the shear stress response increased with strain amplitude and up to the 81st harmonic was observed for very large amplitudes. The onset of non-linear response as defined from the dependence of isochronal dynamic shear moduli on strain amplitude was found to be in good agreement with that defined by the appearance of a higher harmonic in the stress waveform. The amplitudes of the harmonic coefficients are compared to the predictions of a model for the nonlinear rheological response of a lyotropic cubic mesophase based on the stress response to a periodic lattice potential (Jones and McLeish 1995). It is found that the model is able to account for qualitative trends in the data such as the development of finite higher harmonics with increasing strain, but it does not describe the full frequency and strain dependence of these coefficients. Received: 31 May 2000 Accepted: 21 August 2000     

Large amplitude oscillatory shear behavior of PEO-PPO-PEO triblock copolymer solutions

Rheological properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer solution in both linear and nonlinear regions have been investigated. PEO-PPO-PEO triblock copolymer solution shows a dramatic change in mechanical properties as temperature changes. PEO-PPO-PEO triblock copolymer undergoes a transition from sol to gel with increase of temperature. During this transition the copolymer solution passes through three different stages, namely sol, soft gel, and hard gel. In our previous research (Hyun et al. in J Non-Newtonian Fluid Mech 55:51–65, 2002), large amplitude oscillatory shear (LAOS) behavior was found to be very sensitive to the generated microstructures. In this study, we investigated the relationship between the LAOS type and the microdomain structure. Newtonian behavior is observed in sol region, while there appear two kinds of LAOS types in the soft gel region. One is type I (G′, G′′ decreasing) and the other is a combination of type I and type IV (G′, G′′ increasing followed by decreasing). Type III (G′ decreasing, G′′ increasing followed by decreasing) is observed in the hard gel region. We compared the shape of stress curves, Lissajous pattern, and Fourier transform (FT) rheology of hard gel and soft gel under LAOS, and tried to relate the complex LAOS behavior with the microstructural change. From these investigations, it was found that the LAOS behavior and the stress pattern at large strain are closely related to the microdomain structure of PEO-PPO-PEO triblock copolymer, and provide a lot of useful information on the microstructures induced by large deformation.     

Rheological properties of concentrated latex suspensions of poly(styrene-butadiene)

Concentrated suspensions of charged latex particles of poly(styrene-butadiene) have been used as model systems to investigate the influence of surface charges on the rheology of colloidal suspensions. The suspensions were found to behave as elastic solids at small strains and to require a finite stress to flow. This was related to an ordered structure of the suspensions at rest, resulting from electrostatic and van der Waals forces. Important shear-thinning effects were observed as a consequence of structure rearrangements under shear. At a fixed shear rate, the steady-shear viscosity as a function of the ionic strength exhibits a minimum. Under oscillatory shear flow, the behavior of the concentrated suspensions was found to be non-linear above a very small strain amplitude. The non-linear output signal from dynamic experiments was analyzed using a fast Fourier transform algorithm. A maximum in the third harmonic intensity as a function of the strain amplitude was observed and the intensity of higher harmonics decreased with increasing ionic strength. The behavior of the suspensions could be adequately described using the structural model of Yziquel et al. (Yziquel F, Carreau PJ, Moan M, Tanguy PA (1999) Rheological modeling of concentrated colloidal suspensions. J Non-Newtonian Fluid Mech 86:133–155).     

Detection and quantification of industrial polyethylene branching topologies via Fourier-transform rheology,NMR and simulation using the Pom-pom model

The significance of sparse long-chain branching in polyolefines towards mechanical properties is well-known. Topology is a very important structural property of polyethylene, as is molecular weight distribution. The method of Fourier-transform rheology (FTR) and melt state nuclear magnetic resonance (NMR) is applied for the detection and quantification of branching topology (number of branches per molecule), for industrial polyethylenes of various molecular weight and molecular weight distributions. FT rheology consists of studying the development of higher harmonics contribution of the stress response to a large amplitude oscillatory shear deformation. In particular, when applying large-amplitude oscillatory shear (LAOS), one observes the development of mechanical higher harmonic contributions at 3ω ₁, 5ω ₁,..., in the shear stress response. We correlate the relative intensity, I _3/1, and phase Φ ₃ of these harmonics with structural properties of industrial polyethylene, i.e. polymer topology and molecular weight distribution. Experiments are complemented by numerical simulations, using a multimode differential Pom-pom constitutive model (DCPP formulation), by fitting to the experimental linear and nonlinear viscoelastic behaviours. Simulation results in the nonlinear regime are correlated with molecular properties of the “pom-pom” macromolecular architecture. Qualitative agreement is found between predicted and experimental FT rheology results.     

Fourier transform mechanical spectroscopy of the sol-gel transition in zirconium alkoxide ceramic gels

The gelation of a ceramic precursor, zirconium alkoxide, has been studied using dynamic oscillatory measurements. The gelation time is controlled by varying the concentrations of zirconium propoxide, hydrolysis with water, and acetylacetone concentration which acts as a chelating ligand. Gelation times were varied from minutes to months. The gelation time varied with zirconium concentration to the –10 power, hydrolysis to the –7 power, and ligand concentration of the –17 power. The sol-gel transition was monitored using the criteria of Winter in which GG ⁿ and tan () = tan . It is shown that the use of multiple superimposed sinusoidal waves to simultaneously measure the moduli at several frequencies is faster than using individual frequency sweep experiments. The selection of rate and strain criteria for brittle network gels is discussed in detail.     

Vibration parameter measurement using the temporal digital hologram sequence and windowed Fourier transform

Real time digital recording and numerical reconstruction of a temporal digital hologram sequence have become feasible in recent years. They provide a new measurement method which enjoys the valuable advantages of being full-field, noncontact and high precision. In this paper, a combined method of temporal digital hologram sequence and windowed Fourier transform is proposed to measure the kinematic parameters of random vibration. A series of holograms are recorded by CCD camera and the original phase can be reconstructed by Fresnel reconstruction algorithm. The three-dimensional windowed Fourier transform is used to filter noise in phase and extract the instantaneous kinematic parameters of the specimen, such as the displacement, velocity and acceleration. An experiment is conducted on a chloroprene rubber latex membrane. Results demonstrate that the proposed method determines the vibration parameters precisely and enjoys many merits.     

Fourier and wavelet analyses for fatigue assessment of concrete beams

We investigate damage detection in a simply-supported pre-stressed beam. A crack was propagated by fatigue loads, which were applied up to two million cycles. Both fast Fourier transform (FFT) and continuous wavelet transform (CWT) are used in the analysis of the structural response to impulse loads. The acceleration response of the full-scale beam was measured each time a certain number of cycles of fatigue loads were applied. The results of this study show that both methods can clearly identify the crack growth induced by fatigue loads. The natural frequencies found by FFT are sensitive to the crack progression. The results from the CWT analysis show a clear difference in structural responses between the initial and damaged states of the structure. The response accelerations are de-noised by a soft-thresholding method before they are analyzed by CWT. In addition to the frequency components, the CWT shows the moment in time when particular frequencies occur. Therefore, wavelet analysis has the potential of becoming an effective tool for damage detection and health monitoring of structures for which the natural frequencies are irregularly changing. As the crack grows, the magnitude of ridges obtained by CWT analysis decreases significantly, which indicates the reduction in structural stiffness.     

Rheology of polymer blends: non-linear model for viscoelastic emulsions undergoing high deformation flows

Non-linear rheology of a mixture of two viscoelastic immiscible liquids undergoing high deformation flow was considered. Using Grmela's formalism (Grmela 1986, 1989, 1993a, b) and the coarse grained picture given by Onuki (1987) and Doi and Ohta (1991), we have derived a set of highly non-linear time-dependent transport equations that take into account a direct coupling between the rheology and morphology. Breakup, coalescence, and the high deformation of the interface were considered. Models of Doi and Ohta (1991), Lee and Park (1994), and Grmela et al. (1998) are recovered as special cases. The parameters of?the model were given a physical meaning in both shear and elongational flows and the predictions of the model were ¶compared to the predictions of the previous models on the basis of experimental results obtained on two model?blends PDM/PB polydimethylsiloxane/poly(1-butene) and PP/PS polypropylene/polystyrene blends.     

The extended Jordan's lemma and the relation between laplace transform and fourier transform

I.IntroductionItiswell4n0wnthatthecontourintergrationofcomp1exvariableftinctioncanmakealotintegrationveryconvenient.Jordan'slemmahasaveryimportantstatusintheonec0mplexvariableintegration,anditisveryusefulforavarityofintegration.Withthetheoryoffunctionsofo…     

Linear rheology of diluted linear, star and model long chain branched polymer melts

We present experiments and theory on the diluted melt dynamics of monodisperse entangled polymers of linear, star and H-shaped architecture. Frequency-dependent rheological data on a series of progressively diluted linear, star and H-polymers are in good agreement with a refined tube-model theory that, for H-polymers, combines star polymer melt behaviour at high frequency, with linear polymer reptation behaviour at low frequencies. Taking into account the effect of dilution via some simple scaling relations, mild polydispersity and by incorporating the high frequency Rouse modes, we are able to model quantitatively the entire frequency range. This work suggests a novel rheological route to analysing long chain branching in polymer melts. Received: 6 April 2000/Accepted: 21 December 2000     

Melt rheology of long-chain-branched polypropylenes

Rheological properties of long-chain-branched isotactic polypropylene (PP) via copolymerization with a very small amount of nonconjugated α,ω-diene monomer using metallocene catalyst system in both linear and nonlinear regions were investigated, comparing with conventional linear and long-chain-branched PP modified at postreactor. Although comonomer incorporation was equal to 0.05 mol% or less, it caused high molecular weight, broad molecular weight distribution, and long-chain branching. A detailed study on the effect of diene incorporation on the polymer properties was conducted, comparing with modified PP in postreactor. Polymer chain microstructures were characterized by gel permeation chromatography with multiangle laser light scattering (MALLS), differential scanning calorimetry, and rheological means: dynamic viscoelasticity, step-strain, uniaxial elongational flow measurements, and large amplitude oscillatory shear. The PP, which incorporated a small amount of diene monomer, showed significantly improved viscoelastic behaviors. The diene-propylene copolymer containing long-chain branches showed extremely long relaxation mode under shear and outstanding viscosity increase under elongational flow, so-called strain hardening. The difference in microstructure of diene-propylene copolymer with modified PP with long-chain branches is investigated by MALLS and rheological characterizations.     

Integral transform solution of multi-material structure with finite crack perpendicular to the interface

The plane elasticity problem for layered elastic systems containing a finite crack perpendicular to the interface is considered. To derive the singular integral equations. Fourier transform in conjunction with dislocation is used. The singular integral equation is solved with the Lobatto-Chebyshev method commonly applied to such problems. In order to have an idea about the usefulness of the method described, a two-layer structure which contains a cut parallel toh is considered.     

THE WAVELET TRANSFORM OF PERIODIC FUNCTION AND NONSTATIONARY PERIODIC FUNCTION

Some properties of the wavelet transform of trigonometric function, periodic function and nonstationary periodic function have been investigated. The results show that the peak height and width in wavelet energy spectrum of a periodic function are in proportion to its period. At the same time, a new equation, which can truly reconstruct a trigonometric function with only one scale wavelet coefficient, is presented. The reconstructed wave shape of a periodic function with the equation is better than any term of its Fourier series. And the reconstructed wave shape of a class of nonstationary periodic function with this equation agrees well with the function.     

Shear-induced aggregation and break up of fibril clusters close to the percolation concentration

To probe the behaviour of fibrillar assemblies of ovalbumin under oscillatory shear, close to the percolation concentration, c_p (7.5%), rheo-optical measurements and Fourier transform rheology were performed. Different results were found close to c_p (7.3%), compared to slightly further away from c_p (6.9 and 7.1%). For 6.9 and 7.1%, a decrease in complex viscosity, and a linear increase in birefringence, n, with increasing strain was observed, indicating deformation and orientation of the fibril clusters. For 7.3%, a decrease in complex viscosity was followed by an increase in complex viscosity with increasing strain, which coincided with a strong increase in n, dichroism, n, and the intensity of the normalized third harmonic (I₃/I₁). This regime was followed by a second decrease in complex viscosity, where n,n and I₃/I₁ decreased. In the first regime where the viscosity was decreasing with increasing strain, deformation and orientation of existing clusters takes place. At higher oscillatory shear, a larger deformation occurs and larger structures are formed, which is most likely aggregation of the clusters. Finally, at even higher strains, the clusters break up again. An increase in complex viscosity, n, n and I₃/I₁ was observed when a second strain sweep was performed 30 min after the first. This indicates that the shear-induced cluster formation and break up are not completely reversible, and the initial cluster size distribution is not recovered after cessation of flow.     

On the comparison of the solutions obtained by using two different transform methods for the second problem of Stokes for Newtonian fluids

The unsteady flow over a plane wall which is initially at rest and the plate begins suddenly to oscillate in own plane is considered. The solution subject to the boundary and initial conditions is obtained by applying to the governing equation the Laplace transform method or Fourier transform method. A comparison of the solutions obtained by two transform methods for flow considered is given. It is shown that the solution obtained by the Laplace transform method or Fourier transform method is the sum of the steady-state and the transient parts. The transient parts are found in terms of definite integrands whose integrals are oscillatory functions. Therefore, the transient parts are expressed in terms of the tabulated functions.     

用Fourier变换莫尔法测量流体自由表面微幅波的振幅

采用一种非接触的光学方法－傅立叶变换莫尔法（Fourier transformmethod），结合数字图像处理技术，对微幅振荡的水表面波的振幅进行测量。它是对全场中每一个像素点进行测量，比较触测量法具有更高的灵敏度。它为微幅水表面波振幅的测量提供了一种手段。通过将计算机生成的周期性光栅图像经投影机直接投影到被测物体的参考平面，经CCD摄像头、图像板捕捉存储形成数字化的光栅图像，利用傅立叶变换莫尔法处理光栅图像，从而获得包含有水表面波的振幅的相位信息，再经适当的几何变换获得振幅信息。我们在垂直振荡装置上进行了不同激励频率和不同振幅的表面波的振幅测量。