Determination of Yield Stress of Complex Fluids by Model Fitting Using a Rotational Rheometer – Gel

Introduction

Many complex fluids, such as network forming polymers, surfactant mesophases and concentrated emulsions do not flow until the applied StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress exceeds a certain critical value, known as the yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress. Materials exhibiting this behavior are said to be exhibiting yield flow behavior. The yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress is therefore defined as the StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress that must be applied to the sample before it starts to flow. Below the yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress, the sample will deform elastically (like stretching a spring), above the yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress the sample will flow like a liquid.

Most fluids with yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress can be considered as a structural skeleton that extends over the entire volume of the system. The strength of the skeleton is governed by the structure of the dispersed phase and its interactions. Normally, the continuous phase is low in viscosity, however, high volume fractions of a dispersed phase can increase the viscosity by a thousand times and induce solid-like behavior at rest. These materials are often called viscoplastic materials.

where σ0 is the yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress and ηB is the Bingham viscosity or plastic viscosity. It should be noted that the Bingham viscosity is not a real viscosity, it is used to describe the slope of the Newtonian portion of the curve.

An alternative model to the Bingham model is the Casson model. This model has all components in the Bingham equation raised to the power of 0.5, and consequently has a more gradual transition between the yield and Newtonian regions. It tends to fit many materials better than the Bingham model and is widely used to characterize inks and chocolate in particular. The Casson equation can be written as:

Equation 2

where K is the consistency and n is the Shear ThinningThe most common type of non-Newtonian behavior is shear thinning or pseudoplastic flow, where the fluid vis­cosity decreases with increasing shear.shear thinning index. This describes the degree to which a material is Shear ThinningThe most common type of non-Newtonian behavior is shear thinning or pseudoplastic flow, where the fluid vis­cosity decreases with increasing shear.shear thinning (n<1) or Shear ThickeningWhile most suspensions and polymer structured mate­rials are shear thinning, some materials can also show shear thickening behavior where viscosity increases with increasing shear rate or shear stress.shear thickening (n>1).

Yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress is defined as the StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress that must be applied to the sample before it starts to flow.

Schematic shear StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress versus shear rate curves for a Herschel-Bulkley and Bingham type fluid are illustrated in Figure 1. Note, these are presented using linear scaling but will show different profiles when displayed on a logarithmic scale as which is how such curves are usually represented.

1) Illustration of Bingham and Herschel-Bulkley model fits using linear scaling

To determine which model is most appropriate, it is necessary to measure the steady shear StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress over a range of shear rates and fit each model to the data. The correlation coefficient is then a good indicator of the goodness of fit. The range of data used in the analysis can, however, have a bearing on the results obtained since one model might better fit the low shear data and another the high shear data.

It should be noted that Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress values determined by model fitting are often termed dynamic yield stresses as opposed to the static Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress attributed to other methods such as StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress ramps and StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress growth1. The dynamic yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress is defined as the minimum StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress required to maintain flow, while the static yield StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress is defined as the StressStress is defined as a level of force applied on a sample with a well-defined cross section. (Stress = force/area). Samples having a circular or rectangular cross section can be compressed or stretched. Elastic materials like rubber can be stretched up to 5 to 10 times their original length.stress required to initiate flow and is usually higher in value. It is usually better to measure the static Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress when looking at initiating flow in a material, i.e., pumping, while dynamic Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress may be more applicable in applications for maintaining or stopping flow after initiation.

This application note shows test data and model fitting methodology for a gel sample.

Experimental

  • A carbopol-based hair gel was chosen for analysis.
  • Rotational rheometer measurements were made using a Kinexus rheometer with a Peltier plate cartridge and 40 mm roughened parallel plates measuring system (to avoid sample slip at the geometry surfaces)1, and utilizing standard pre-configured sequences in rSpace software.
  • A standard loading sequence was used to ensure that the sample was subject to a consistent and controllable loading protocols.
  • A table of shear rates was run over the range from 0.1 s-1 to 100 s-1.
  • The measured data was fitted using three Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress model fits – Bingham, Casson and Herschel Bulkley.
  • All rheology measurements were performed at 25°C.

Results and Discussion

Figure 2 shows the shear stress-shear rate plot (rheogram) for the hair gel, and with the data fitted with a Herschel-Bulkley model. Figure 3 shows the same data, but fitted with a Bingham model.

2) Shear stress-shear rate data for the Carbopol-based hair gel with Hershel-Bulkley model fit
3) Shear stress-shear rate data for the Carbopol-based hair gel with Bingham model fit

Table 1: Yield stress values and coefficients for the three model fits

Action NameBingham ModelHerschel-Bulkley ModelCasson Model
Yield stress (Pa)89.959.373.3
k11.5925.79 
n 0.395 
k2  0.474
Correlation coefficient0.93700.99980.9877

Clearly, the Herschel-Bulkley model fits the data better than the Bingham model, as confirmed by the correlation coefficients given in Table 1. It also gives a slightly better fit than the Casson model over the shear rate range measured.

The Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress values also vary considerably between the three models with Herschel-Bulkley values much lower than the other two models. Being more specific about the data being selected in the model can however, be important. Excluding some of the higher shear data for the Casson model, for instance, will give a Yield StressYield stress is defined as the stress below which no flow occurs; literally behaves like a weak solid at rest and a liquid when yielded.yield stress value closer to that of Herschel-Bulkley, so sometimes it can be beneficial to fit curves outside of the sequence using a smaller range of data.

The coefficients k1, k2 and n represent different values based on the model used. For example k1 is Bingham viscosity in the Bingham model and consistency in the Herschel-Bulkley model. k2 is the Casson viscosity in the Casson model, and n is the Shear ThinningThe most common type of non-Newtonian behavior is shear thinning or pseudoplastic flow, where the fluid vis­cosity decreases with increasing shear.shear thinning index in the Herschel-Bulkley model.

Conclusion

Model fitting can be used to determine the yield stress of a viscoplastic fluid by analysis of a shear stress-shear rate curve. Various models are available including Bingham, Casson and Herschel-Bulkley.

Herschel-Bulkley was found to best describe the properties of a Carbopol-based hair gel measured between 0.1 and 100 s-1, which gave a yield stress of 59.3 Pa.

1Please note testing can be undertaken with cone and plate or parallel plate geometry – with the latter being preferred for dispersions and emulsions with large particle sizes. Such material types may also require the use of serrated or roughened geometries to avoid artefacts relating to slippage at the geometry surface.

Literature

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