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4.2 Shear-thinning and shear-thickening fluids

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Non-Newtonian fluids are fascinating materials that change their viscosity when stressed. Shear-thinning fluids become less viscous under stress, while shear-thickening fluids do the opposite. These behaviors impact how we use and process many everyday products.

Understanding non-Newtonian fluids is key for industries like food, cosmetics, and pharmaceuticals. Their unique properties allow for innovative applications, from better-flowing ketchup to impact-resistant materials. Studying these fluids helps us create smarter, more efficient products.

Non-Newtonian fluid behavior

  • Non-Newtonian fluids exhibit complex rheological behavior where viscosity changes with applied shear stress or shear rate
  • Understanding the behavior of non-Newtonian fluids is crucial for various applications in colloid science, such as formulation development, processing, and quality control
  • Non-Newtonian fluids can be classified into shear-thinning (pseudoplastic) and shear-thickening (dilatant) fluids based on their response to shear stress

Shear-thinning fluids

Characteristics of shear-thinning fluids

  • Shear-thinning fluids experience a decrease in viscosity with increasing shear rate or shear stress
  • The apparent viscosity of shear-thinning fluids is higher at low shear rates and lower at high shear rates
  • Shear-thinning behavior is often observed in complex fluids containing long-chain molecules or particles that align or disentangle under shear

Examples of shear-thinning fluids

  • Polymer solutions (polyethylene oxide, xanthan gum)
  • Concentrated suspensions (ketchup, toothpaste)
  • Emulsions (mayonnaise, salad dressings)
  • Blood and other biological fluids

Mechanisms of shear-thinning behavior

  • Alignment of elongated particles or molecules in the direction of flow reduces viscosity at higher shear rates
  • Disentanglement of polymer chains under shear allows for easier flow and lower viscosity
  • Breakdown of flocculated or aggregated structures in suspensions leads to reduced viscosity

Applications of shear-thinning fluids

  • Improved pumpability and reduced energy consumption in pipeline transportation
  • Enhanced spreading and leveling of paints and coatings
  • Controlled release and targeted delivery of drugs in pharmaceutical formulations
  • Efficient mixing and processing of food products

Shear-thickening fluids

Characteristics of shear-thickening fluids

  • Shear-thickening fluids exhibit an increase in viscosity with increasing shear rate or shear stress
  • The apparent viscosity of shear-thickening fluids is lower at low shear rates and higher at high shear rates
  • Shear-thickening behavior is less common than shear-thinning and is often observed in concentrated suspensions of rigid particles

Examples of shear-thickening fluids

  • Cornstarch suspensions
  • Silica nanoparticle suspensions
  • Certain polymer solutions (polyvinyl alcohol)
  • Electrorheological and magnetorheological fluids

Mechanisms of shear-thickening behavior

  • Formation of hydroclusters or particle aggregates under high shear rates increases viscosity
  • Transition from a lubricated to a frictional regime between particles at critical shear rates
  • Entanglement of polymer chains or alignment of particles in a way that resists flow

Applications of shear-thickening fluids

  • Development of body armor and impact-resistant materials
  • Vibration damping and shock absorption in mechanical systems
  • Controllable hydraulic fluids for advanced machinery
  • Rheological additives for enhanced oil recovery

Rheological models

Power-law model

  • The power-law model describes the relationship between shear stress ($\tau$) and shear rate ($\dot{\gamma}$) as: $\tau = K \dot{\gamma}^n$
  • $K$ is the consistency index, and $n$ is the flow behavior index
  • For shear-thinning fluids, $n < 1$, while for shear-thickening fluids, $n > 1$
  • The power-law model is simple but limited in describing the behavior at very low or high shear rates

Carreau model

  • The Carreau model captures the plateau viscosities at low and high shear rates and the transition between them
  • The model is given by: $\eta = \eta_\infty + (\eta_0 - \eta_\infty)[1 + (\lambda \dot{\gamma})^2]^{(n-1)/2}$
  • $\eta_0$ and $\eta_\infty$ are the zero-shear and infinite-shear viscosities, $\lambda$ is the relaxation time, and $n$ is the power-law index
  • The Carreau model is more accurate than the power-law model but requires more parameters

Cross model

  • The Cross model is another four-parameter model similar to the Carreau model
  • The Cross model is given by: $\eta = \eta_\infty + \frac{\eta_0 - \eta_\infty}{1 + (K \dot{\gamma})^m}$
  • $K$ is a time constant, and $m$ is a dimensionless exponent related to the power-law index
  • The Cross model is particularly useful for describing the behavior of polymer solutions and melts

Comparison of rheological models

  • The choice of rheological model depends on the specific fluid and the range of shear rates of interest
  • The power-law model is simple and often sufficient for engineering calculations but may not capture the full behavior
  • The Carreau and Cross models provide more accurate descriptions but require more parameters and experimental data
  • Other models, such as the Herschel-Bulkley model for yield stress fluids, may be appropriate for specific cases

Measurement techniques

Rotational rheometry

  • Rotational rheometers measure the viscosity and viscoelastic properties of fluids using a rotating geometry (cone-and-plate, parallel plates, or concentric cylinders)
  • The sample is placed between the rotating and stationary parts, and the torque and angular velocity are measured
  • Rotational rheometers can perform steady-shear, oscillatory, and creep tests to characterize the rheological behavior

Capillary rheometry

  • Capillary rheometers measure the viscosity of fluids by forcing them through a narrow capillary at controlled flow rates or pressures
  • The pressure drop across the capillary and the volumetric flow rate are used to calculate the shear stress and shear rate
  • Capillary rheometers are suitable for high-viscosity fluids and can achieve high shear rates

Oscillatory rheometry

  • Oscillatory rheometers apply a sinusoidal deformation to the sample and measure the resulting stress response
  • The complex modulus (G*) is determined from the amplitude ratio and phase shift between the stress and strain
  • Oscillatory tests can probe the viscoelastic properties of fluids, such as the storage modulus (G') and loss modulus (G")

Challenges in measuring non-Newtonian fluids

  • Non-Newtonian fluids can exhibit time-dependent behavior (thixotropy or rheopexy), making measurements sensitive to shear history
  • Wall slip and shear banding can occur in some fluids, leading to inaccurate measurements
  • Sample preparation and loading can affect the rheological properties, especially for sensitive structures like gels and emulsions
  • Selecting appropriate measurement geometries and protocols is crucial for obtaining reliable data

Factors affecting non-Newtonian behavior

Influence of particle size and shape

  • Particle size and shape significantly influence the rheological behavior of suspensions and emulsions
  • Smaller particles generally lead to higher viscosities due to increased surface area and particle-particle interactions
  • Anisotropic particles (rods, plates) can align under shear, resulting in shear-thinning behavior

Effect of particle concentration

  • Increasing particle concentration typically increases the viscosity of suspensions and emulsions
  • At high concentrations, particle-particle interactions become dominant, leading to non-Newtonian behavior
  • The maximum packing fraction and the percolation threshold are important parameters affecting rheology

Role of particle-particle interactions

  • Attractive interactions (van der Waals, depletion) can lead to flocculation and increased viscosity
  • Repulsive interactions (electrostatic, steric) can stabilize suspensions and reduce viscosity
  • The balance between attractive and repulsive forces determines the rheological behavior

Impact of temperature on rheology

  • Temperature affects the viscosity and rheological behavior of non-Newtonian fluids
  • Increasing temperature generally decreases viscosity due to increased molecular motion and reduced intermolecular interactions
  • Temperature-sensitive fluids, such as thermoresponsive polymers, can exhibit significant changes in rheology with temperature

Industrial applications

Food and beverage processing

  • Control of texture, mouthfeel, and stability of food products (sauces, dressings, yogurts)
  • Optimization of pumping, mixing, and filling operations in food processing plants
  • Development of novel food formulations with desired rheological properties

Pharmaceuticals and cosmetics

  • Formulation of stable and effective drug delivery systems (suspensions, emulsions, gels)
  • Control of spreading, absorption, and retention of topical products (creams, lotions)
  • Design of injectable formulations with appropriate syringeability and injectability

Paints and coatings

  • Optimization of flow and leveling properties for uniform coating application
  • Control of sagging, dripping, and brushing characteristics
  • Formulation of high-solids and water-based coatings with desired rheological behavior

Enhanced oil recovery

  • Injection of non-Newtonian fluids (polymers, surfactants) to improve oil displacement efficiency
  • Control of mobility ratio and sweep efficiency in porous media
  • Design of viscoelastic surfactant solutions for improved oil recovery

Future research directions

Development of novel non-Newtonian fluids

  • Design of smart fluids with stimuli-responsive rheological properties (pH, temperature, electric or magnetic fields)
  • Synthesis of bio-based and sustainable non-Newtonian fluids from renewable resources
  • Exploration of nanoparticle-based fluids with unique rheological behavior

Optimization of rheological properties

  • Tailoring of particle size, shape, and surface properties to achieve desired rheological behavior
  • Formulation of multi-component systems with synergistic effects on rheology
  • Use of machine learning and artificial intelligence for guided optimization of rheological properties

Modeling and simulation of non-Newtonian flow

  • Development of advanced constitutive models for capturing complex rheological behavior
  • Multiscale modeling approaches linking molecular dynamics, mesoscale simulations, and continuum mechanics
  • Computational fluid dynamics simulations of non-Newtonian flow in complex geometries and industrial processes

Emerging applications of non-Newtonian fluids

  • 3D printing and additive manufacturing with non-Newtonian inks and materials
  • Biomedical applications, such as injectable hydrogels for tissue engineering and regenerative medicine
  • Functional coatings and adhesives with tunable rheological properties
  • Energy storage and conversion devices utilizing non-Newtonian electrolytes and redox-active fluids