Study on the rheological properties of Portland cement pastes with polycarboxylate superplasticizers

The coupling effects of temperature and time on the fluidity of fresh cement mixtures were investigated. Mini-cone tests on cement mortars and rheological tests on cement pastes under different temperatures (0 to 60 °C) were conducted to characterize the development of the fluidity of fresh cement mixtures over time. In addition, total organic carbon tests were performed to quantify the adsorption amount of superplasticizers on the cement surface. The amount of free water in cement pastes was determined via centrifugation. Isothermal calorimetry was employed to characterize the hydration kinetics of cement under different temperatures. Results show that the spread diameter of mortars decreases in a roughly linear fashion over elapsed time. Higher temperature facilitates a sharper decrease in fluidity with time, although the initial fluidity of fresh mortars is not significantly affected by temperature. Higher temperature results in a greater amount of adsorbed polycarboxylate ester/ether on the cement surface and a lower amount of free water in fresh cement pastes, which is believed to result from the higher hydration rate of cement. The evolution of rheological properties over time can be attributed to the development of hydration degree. Relative hydration degree is introduced to indicate the development of rheological properties with time. Two models to describe the evolution of yield stress and plastic viscosity for fresh cement pastes were developed.     

Beneficial use of a cell coupling rheometry, conductimetry, and calorimetry to investigate the early age hydration of calcium sulfoaluminate cement

A specific cell was designed to monitor simultaneously the evolution of the viscoelastic properties, electrical conductivity, and temperature of a cement paste with ongoing hydration. Hydration of calcium sulfoaluminate cement by demineralised water or by a borated solution was then investigated as an example. Borate anions acted as set retarders but to a smaller extent than with ordinary Portland cement. The delay in cement hydration resulted from the precipitation of an amorphous or poorly crystallized calcium borate, which also caused a rapid stiffening (and thus a loss of workability) of the paste after mixing. The gypsum content of the CSA cement was shown to play a key role in the control of the cement reactivity.     

Rheological models for gypsum plaster pastes

Shear stress and shear rate data obtained for gypsum plaster pastes were correlated by means of different rheological models. The pastes were prepared from a commercial calcium sulfate hemihydrate at various water/plaster ratios ranging from 100/150 to 100/190. The tests were performed at 25°C using a rotating coaxial cylinder viscosimeter. The measurements were accomplished by applying a step-wise decreasing shear rate sequence. Discrimination among the models was made: (1) on the basis of the fitting goodness; (2) by checking the physical meaning of the calculated parameters; (3) on the basis of the stability of the parameters and of their prediction capacity beyond the limits of the experimental data. In the light of above, the Casson model seemed to be most effective for application to gypsum plaster pastes. K Consistency - n Power-law index - N Number of experimental data - P Number of parameters - Shear rate (s^–1) - ₀ Viscosity (Pa · s) - _d Dispersing medium viscosity (Pa · s) - _p Plastic viscosity (Pa · s) - Viscosity at zero shear rate (Pa · s) - Viscosity at infinite shear rate (Pa · s) - [] Intrinsic viscosity - ² Variance - Shear stress (Pa) - ₀ Yield stress (Pa) - Solid volume fraction - _m Maximum solid volume fraction     

水泥水化的微结构与性能演化研究进展

水泥是一类重要的工程结构材料,其力学性能依赖于水泥的水化过程．综述了水泥水化的微结构和性能演化的研究进展;评述了研究水泥水化过程的实验方法和理论方法;详细介绍和评述了水泥水化的微结构仿真模型、力学分析模型以及建立微结构．性能关系的基本方法．分析和展望了未来水泥水化的主要问题和研究方向．     

Lubricated and nonlubricated squeezing flow of a double layered array of two power law liquids

Force-time relationships of a double-layered array of two power law liquids in squeezing flow at a constant displacement rate were generated with a computer. As in the case of a single layer, lubrication, or lack of it, has the strongest influence on the magnitude of the forces and the flow pattern. Transient flow regimes that were prominent in the behavior of Newtonian liquid arrays in lubricated squeezing flow were also found in the behavior of the power law liquids. Their prominence was influenced by the liquid's flow index and it was drastically magnified as the differences in the liquid's consistency increased.     

Consistency tests for start-up and cessation deformations of viscoelastic fluids

The time-dependent shear stress and first normal stress difference were measured for a polystyrene solution for start-up and cessation-flow experiments over a relatively wide range of shear rate. Consistency tests for the K-BKZ model were applied to the data, and it was concluded that the K-BKZ equation generally does not satisfactorily describe the start-up and cessation data. Modified consistency tests were developed using a strain-coupling constitutive equation, and the evidence suggests that most of the differences between the predictions of the K-BKZ theory and experiment can be explained by including a strain-coupling effect in the rheological constitutive equation.     

Evolution of properties in hydration of cements—A numerical study

The present work develops a numerical method for analysis of the microstructure and property evolution in the hydration of the cement. A time-dependent micro-mechanical model is established to investigate the microstructure development and the effective property evolution of the cement paste, while the input parameters of the model are based on experimental data. It is assumed that the cement paste composite consists of the anhydrous cement particles, cement gel and pores. The cement particles have a periodically spatial array and are wrapped by the cement gel. The Young’s modulus and Poisson’s ratio of the cement paste are calculated by direct average method and two-scale expansion method. The comparisons between the numerical results and experimental data show that this model can simulate the evolution of the microstructure and properties during the hydration of the cements quite satisfactorily.     

Phenomenological description of the thixotropic behaviour of gypsum plaster pastes

Gypsum plaster pastes are concentrated suspensions of calcium sulfate hemihydrate in water. The knowledge of their rheological behaviour plays an important role in the manufacture of gypsum products. In the present work, the approach suggested by Cheng and Evans has been taken into consideration in order to derive a constitutive equation suitable for characterizing completely the flow behaviour of these materials in the first stages after preparation. To this end, gypsum plaster pastes were produced with solid volume fractions in a range of practical interest. The rheological tests were performed using a coaxial-cylinder viscometer.     

A boundary element simulation of the unsteady motion of a sphere in a cylindrical tube containing a viscoelastic fluid

A boundary element method is used to simulate the unsteady motion of a sphere falling under gravity along the centreline of a cylindrical tube containing a viscoelastic fluid. The fluid is modelled by the upper-convected Maxwell constitutive equation. Results show that the viscoelasticity of the liquid leads to a damped oscillation in sphere velocity about its terminal value. The maximum sphere velocity, which occurs in the first overshoot, is approximately proportional to the square root of the Weissenberg number when the ratio of the sphere radius to the tube radius is sufficiently small. Particular attention is also paid to the wall effects. It is shown that a closer wall reduces the oscillatory amplitude of the sphere velocity but increases its frequency. The results suggest that the falling-ball technique, which is now widely used for viscosity measurement, might also be used for the determination of a relaxation time for a viscoelastic fluid.     

INFLUENCE OF GLASS CULLET IN CEMENT PASTES

1. Introduction The necessity for glass cullet recycling is becoming more and more imperative not only due to the general need of solid waste volume reduction, but also due to the strict European legislation, which defines the levels of re- cycling packaging materials including glass cullet. Accord- ing to valid estimates, the total consumption of packaging materials was 58 million tones for 1997 in Europe, 25% of which comprised glass. The present target for recycling is a minimum of 25% for…     

Evolution of viscoelastic properties of polyurethane in the course of curing

Simultaneous measurements of the components of dynamic modulus at the set of frequencies were made by Fourier-Transform Mechanical Spectroscopy (FTMS) to investigate the curing process of a segmented polyurethane.The whole process of curing is treated as consisting of three stages. In the first stage, the material can flow and this stage is complete at the gel-point. In the second stage, the curing proceeds in the network and ends with phase separation of aggregating segments (blocks) of polymeric chains. In the third stage, the curing continues in the two-phase system. The object of investigation was the transition from the second to the third stage. It was shown that the position of the maximum of loss tangent depends on frequency and does not coincide with different characteristic points marking the time dependencies of G and G. This is due to the formation of micro-particles of the newly formed phase. The FTMS method is used for separation of the modulus changes into parts related to formation of chemical and physical networks.Special means of treating calorimetric measurements identified a weak maximum heat output at the moment corresponding to the transition point.     

Viscosity of some clay-based coating colors at high shear rates

The shear viscosity of clay-based coating colors containing latex and carboxymethyl cellulose (CMC) has been measured over a relatively large shearrate region. In the shear-rate range of 50–1500 s^–1 the measurements were performed using a rotational viscometer and, at higher shear rates extending into the region 10⁵ – 10⁶ s^–1, a high pressure capillary viscometer was employed. The viscosity of the clay colors increased with increasing CMC-concentration, but the influence of the CMC-content was less pronounced at higher shear rates. The apparent shear-thinning behavior of the investigated colors could, in part, be attributed to the shear-thinning of the corresponding polymer (CMC) solution constituting the liquid phase of the color, but the influence of another factor was also indicated. At low shear rates, the interaction between the color components can produce relatively high viscosity levels, but in the high shear rate region these interactions appear to be less important for the viscosity level. It is also of interest to note that the viscosity dependence on the solids content in the high shear-rate region could be described with reasonable accuracy using an empirical equation neglecting interactions between the color components.     

Flow mechanisms in dense silica-metal oxide-water suspensions

The rheological properties of dense silica in water suspensions (approx. 50% solids by volume) containing additions of metal oxides were examined. Metal oxides used were ferric, zinc and stannic. To prevent settling, testing was performed in a rheometer which was modified to provide for continual stirring of the materials. Relatively small oxide additions had the effect of thickening the mixtures and making them non-Newtonian. Different rate-limiting steps for flow were identified depending on the particular mixture, testing temperature and shear strain rate. Flow could be described using empirical equations which are identical to those often used to describe plastic flow in solid crystalline materials.     

Measurement of rheological and ultrasonic properties of food and synthetic polymer melts

A slit die viscometer has been used in conjunction with a co-rotating twin screw extruder to study the rheological behaviour of maize grits, potato powder and low density polyethylene, as a function of feed rate, screw speed and temperature. The shear viscosity of both maize and potato decreased with increasing feed rate. Increasing the temperature or screw speed at any given feed rate also reduced the viscosity. The ultrasonic velocity through the material has also been shown to be sensitive to the extruder operating conditions. Overall, the ultrasonic velocity decreased as screw speed and temperature increased and feed rate decreased.     

Instabilities in multi-hole converging flow of viscoelastic fluids

Studies of the onset of instabilities were conducted on single hole and multi-hole contractions using laser speckle visualization. A well characterized elastic fluid was used with constant viscosity of 13.1 Pa · s and elasticity characterized by a longest relaxation time constant of 2.233 s. The onset of instabilities was characterized in terms of the Deborah number and the contraction ratio. Three types of instabilities were observed: pulsing vortices, azimuthally rotating vortices, and swirling vortices. For the single hole contractions the critical Deborah number for instability increased from 4.4 to 5.07 to 5.25 as the contraction ratio increased from 4: 1 to 8: 1 to 12: 1. The magnitude of the instabilities was much greater for the 4: 1 contraction than for the other two contraction ratios. For the multi-hole contraction a square array of nine holes was used and the ratio of the hole diameter to hole spacing was varied. The height of the vortices is very similar for the single hole and multi-hole contractions at low Deborah numbers. At high Deborah numbers the effect of adjacent holes is to reduce the height of the vortices by a factor of three. For the 4: 1 spacing no secondary vortex was observed below a Deborah number of De = 3.7. Secondary vortices occurred for the 8:1 and 10:1 spacing at all Deborah numbers. Unstable pulsing vortices appeared for all spacings at a critical Deborah number around 5.5. Adjacent holes decreased the strength of the unsteady vortex motions. The centerline velocities were measured for the multi-hole contraction at shear rates of 5, 30, and 300 s^–1. The elongational strain rates are similar at a low shear rate of 5 s^–1. As shear rate is increased the onset of stretching occurs closer to the plane of the contraction for the smaller contraction ratios.     

A slit viscometer for the measurement of the viscosity of aqueous systems at high temperatures

A slit viscometer has been constructed to measure the viscosity of aqueous systems at temperatures up to 140 °C. Liquid is forced backwards and forwards through the slit by the use of varying air pressure. The flow rate is obtained from the time for the liquid to pass conductivity probes located in liquid reservoirs either side of the slit. The pressure difference between two points on the slit wall is determined using a differential pressure transducer. By varying the slit height measurements can be made on liquids with viscosities in the range 10 to 10^–3 Pa s. Shear rates from 10 to 10⁴ s^–1 can be achieved. A simple microcomputer control system enables the shear stress to be automatically increased and decreased stepwise. Representative data on polysaccharide solutions and strach suspensions are presented. The viscometer is particularly well-suited for following temperature-dependent biopolymer transitions and the thermal depolymerisation of water soluble polymers.     

Evaluating Herschel-Bulkley fluids with the back extrusion (annular pumping) technique

A mathematical model was developed to describe the behavior of Herschel-Bulkley fluids in a back extrusion (annular pumping) device. A technique was also developed to determine the rheological properties (yield stress, flow behavior index, and consistency coefficient) of these fluids. Mathematical terms were expressed in four dimensionless terms, and graphical aids and tables were prepared to facilitate the handling of the expressions.Nomenclature a radius of the plunger, m - dv/dr shear rate, s^–1 - F force applied to the plunger, N - F _b buoyancy force, N - F _cb force corrected for buoyancy, N - F _T recorded force just before the plunger is stopped, N - F _Te recorded force after the plunger is stopped, N - g acceleration due to gravity, m/s² - H(t) momentary height between plunger and container bottom, m - K a/R, dimensionless - L length of annular region, m - L(t) depth of plunger penetration, m - n flow behavior index, dimensionless - p static pressure, Pa - P _L pressure in excess of hydrostatic pressure at the plunger base, Pa - p ₀ pressure at entrance to annulus, Pa - P pressure drop per unit of length, Pa/m - Q total volumetric flow rate through the annulus, m³/s - r radial coordinate, measured from common axis of cylinder forming annulus, m - R radius of outer cylinder of annulus, m - s reciprocal of n, dimensionless - t time, s - T dimensionless shear stress, defined in Eq. (3) - T ₀ dimensionless yield stress, defined in Eq. (4) - T _w dimensionless shear stress at the plunger wall - _p velocity of plunger, m/s - velocity, m/s - mass density of fluid, kg/m³ - Newtonian viscosity, Pa s - P p ₀ –p _L , Pa - consistency coefficient, Pa sⁿ - value of where shear stress is zero - _–, ₊ limits of the plug flow region (Fig. 1) - r/R - shear stress, Pa - _y yield stress, Pa - _w shear stress at the plunger wall, Pa - dimensionless flow rate defined in Eq. (24) - dimensionless velocity defined by Eq. (5) - _–, ₊ dimensionless velocity outside the plug flow region - _max dimensionless maximum velocity in the plug flow region - _p dimensionless velocity at the plunger wall     

Boundary element simulations of spheres settling in circular,square and triangular conduits

Numerical simulations of a spherical particle sedimenting in circular, triangular and square conduits containing a viscous, inertialess, Newtonian fluid were investigated using the Boundary Element Method (BEM). Settling velocities and pressure drops for spheres falling along the centre-lines of the conduits were computed for a definitive range of sphere sizes. The numerical simulations for the settling velocities showed good agreement with existing experimental data. The most accurate analytic solution for a sphere settling along the axis of a circular conduit produced results which were almost indistinguishable from the present BEM calculations. For a sphere falling along the centre-line of a square conduit, the BEM calculations for small spheres agreed well with analytic results. No analytic results for a sphere falling along the axis of a triangular conduit were available for comparison. Extrapolation of the BEM predictions for the pressure drops, to infinitely small spheres, showed remarkable agreement with analytic results. For the circular conduit, the sphere's settling velocity and angular velocity were computed as a function of drop position for small, medium and large spheres. Excellent agreement with a reflection solution was achieved for the small sphere. In addition, end effects were investigated for centre-line drops and compared where possible with available experimental data and analytic results.Los Alamos National Laboratory, Los Alamos, New Mexico, USA.     

The time-dependent stress-optical behavior of polycarbonate in the glass transition region

The mechanical and stress-optical behavior of Bisphenol-A polycarbonate was investigated in the glass-transition region. For this purpose, optical creep experiments were carried out in shear and elongation on a tensile tester specially designed for use on a microscope state. A Kohlrausch Williams Watts equation (KWW) with a temperature-independent parameter could successfully be applied to the curves describing the time-dependent values of the stress-optical coefficient for several temperatures. The temperature dependence of the corresponding retardation time could be established and described by the WLF equation. For variable stresses the time-dependent birefringence is obtained from a generalized linear stress-optical rule as modeled according to linear superposition. The time-temperature superposition principle was applied to all measurements. With the dynamic moduli some deviations were observed at the transition from the rubbery plateau to the relaxation. The strain-optical coefficient was found to decrease with increasing time and strain. The strain dependence was found to be independent of temperature at constant stress.     

Shear and extensional flow of polyacrylamide solutions

As part of an EEC Science Stimulation programme on extensional viscosity two major conferences were organised on the subject. The second of these was devoted to the results obtained on a standard fluid, M 1. The data obtained in shear flow was remarkably consistent from laboratory to laboratory. Extensional flow results presented quite a different picture. Using a series of nonequilibrium techniques such as the spinline rheometer, opposing jet, falling drop and converging flow, extensional viscosity results were obtained which differed by as much as two to three orders of magnitude. Nevertheless, it was apparent that consistancy did exist between similar techniques. It is in the context of this information that the measurements described below have been made.The shear and extensional flow properties of partially ionised polyacrylamide in solution at concentrations ranging from 5 ppm were measured. The method of solution preparation was found to have a profound effect on the behaviour of the solutions in shear flow. The influence of salt concentration and pH was investigated and is discussed in the context of molecular shape in solution.Extensional flow measurements, using the spinline rheometer, show that the solutions are strongly strain thickening even at concentrations as low as 5 ppm. These results are considered in the light of polymer entanglement and association in the strong flow field.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.