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Introduction
spinning. capillary line.
Introduction
1) Acquisition of spinnable liquid
Polymer melt or solution Under pressure through capillaries Dia: 0.002 to 0.04 cm 0 002 0 04 Length: Equal to or 3-4 times dia Pulled on winder Attenuated and solidified Uniform cross section
2) Jet formation:
Dry spinning
Cellulose diacetate Cellulose triacetate Acrylic Polyurethane Polyvinyl chloride Chlorinated PVC
Wet spinning
Acrylic Modacrylic Rayon Polyurethane Polyvinyl alcohol Aromatic polyamide
3) Jet hardening
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Melt Spinning
Simplest, youngest and most economical Melt stable material Solidification requires only heat transfer Fast production rates Smooth and circular fibres Polymers can be blended with plasticizers for stable melt
Solution Spinning
Dry Spinning
Solidification achieved by solvent evaporation Solidification requires one way mass transfer
Dry Spinning
Wet Spinning
Solidification by chemical coagulation Solidification requires two way mass transfer
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Wet Spinning
Special Techniques
Dry jet wet spinning: aromatic polyamides Gel spinning: Ultra high molecular weight PE Electrospinning: for producing nanofibres
Thermodynamics of Spinning
Low molecular weight compounds: continuous change of neighbours Polymeric compounds: Rotatory segmental jumps Quiescent state: Number of jumps in 1 direction = Number of jumps in other direction So, no net transport: self diffusion External stress: Preferential movement in direction of stress (flow) Ease of this depends on viscosity
For flow to become possible: activation energy needed With increase in C atoms, activation energy:
1. first increases 2. rate of increase becomes slower 3. becomes constant (25 carbon atoms)
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Thermodynamics of Spinning
Low molecular weight compounds: continuous change of neighbours Polymeric compounds: Rotatory segmental jumps Quiescent state: Number of jumps in 1 direction = Number of jumps in other direction So, no net transport: self diffusion External stress: Preferential movement in direction of stress (flow) Ease of this depends on viscosity
For flow to become possible: activation energy needed With increase in C atoms, activation energy:
1. first increases 2. rate of increase becomes slower 3. becomes constant (25 carbon atoms)
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Todays Lecture
What is rheology?
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Biofluids
Suspension (blood) Gel (mucin) Solutions (spittle)
Pharmaceuticals
Gels (creams, particle precursors) Emulsions (creams) Aerosols (nasal sprays)
Polymers
Rheologys Goals
1. Establishing the relationship between applied forces and geometrical effects induced by these forces at a point (in a fluid).
The mathematical form of this relationship is called the rheological equation of state, or the constitutive equation. The constitutive equations are used to solve macroscopic problems related to continuum mechanics of these materials. Any equation is just a model of physical reality.
Rheologys Goals
1. Establishing the relationship between rheological properties of material and its molecular structure (composition).
Related to:
Estimating E ti ti quality of materials lit f t i l Understanding laws of molecular movements Intermolecular interactions
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NEWTONIAN FLUIDS
Newtonian: Plot of rate of shear against shear stress is a straight line passing through the origin provided flow is laminar Examples: 1.Water 2.Simple Organic Liquids 3.True Solutions 4.Dilute suspensions 5.Emulsions 6.Gases
Laminar flow, sometimes known as streamline flow, occurs when a fluid flows in parallel layers, with no disruption between the layers. At low velocities the fluid tends to flow without lateral mixing, and adjacent layers slide past one another like playing cards. There are no cross currents perpendicular to the direction of flow, nor eddies or swirls of fluids. In laminar flow the motion of the particles of fluid is very orderly with all particles moving in straight lines parallel to the pipe walls
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Now,
i.e. rate of shear of liquid is equal to the velocity gradient normal to the direction of the flow
Newton observed: For laminar flow, shear stress acting over surfaces parallel to the direction of flow needed to maintain a given shear rate is proportional to the shear rate. Thus, , d/dt or = d/dt Where = coefficient of viscosity
is constant for Given liquid Given temperature Given pressure SI unit of = N s m or Pa s m CGS system: dyn s cm Note: If a force of 1 dyn acting on 1 cm area results in a shear rat of 1 s, then viscosity is 1 dyn s cm or 0.1 Pas or 1 poise.
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CAPILLARY FLOW
Flow through capillary derived by Poiseuille Flow is assumed to be 1. Streamline/Laminar 1 St li /L i 2. Pressure constant over any cross section 3. No radial flow Adjacent layers: different speeds
Incompressible, Newtonian liquid of Density , Viscosity Capillary of radius R and length L Capillary Let velocity of layer at distance r from the axis be V is the shear stress If P is applied pressure (pressure difference between inlet and outlet), accelerating force acting on liquid cylinder of radius r, Fpressure = Pr Viscous drag, Fviscosity = X 2rL
When the conditions are steady, these two forces must be equal and opposite, Pr = - X 2rL = - (dV/dr) X 2rL or dV/dr = -r(P/2L) r(P/2L) At the wall of tube, r = R and velocity = 0 Integrating, R - r = 4LV/P or V = P(R - r)/4L
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The volume of the liquid dQ flowing through the tube of thickness dr per second is dQ = 2 rVdr Hence, the total volume of the liquid flowing through the tube per second, is
This may be rearranged as = PR/8QL This is called Poiseuilles equation Two assumptions: Liquid is Newtonian All the energy supplied to push the liquid through the capillary is used to overcome the viscous drag or internal friction or rheological force.
CAPILLARY FLOW
Flow through capillary derived by Poiseuille Flow is assumed to be 1. Streamline/Laminar 1 St li /L i 2. Pressure constant over any cross section 3. No radial flow Adjacent layers: different speeds
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Incompressible, Newtonian liquid of Density , Viscosity Capillary of radius R and length L Capillary Let velocity of layer at distance r from the axis be V is the shear stress If P is applied pressure (pressure difference between inlet and outlet), accelerating force acting on liquid cylinder of radius r, Fpressure = Pr Viscous drag, Fviscosity = X 2rL
When the conditions are steady, these two forces must be equal and opposite, Pr = - X 2rL = - (dV/dr) X 2rL or dV/dr = -r(P/2L) r(P/2L) At the wall of tube, r = R and velocity = 0 Integrating, R - r = 4LV/P or V = P(R - r)/4L
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The volume of the liquid dQ flowing through the tube of thickness dr per second is dQ = 2 rVdr Hence, the total volume of the liquid flowing through the tube per second, is
This may be rearranged as = PR/8QL This is called Poiseuilles equation Two assumptions: Liquid is Newtonian All the energy supplied to push the liquid through the capillary is used to overcome the viscous drag or internal friction or rheological force.
NEWTONIAN FLUIDS
Newtonian: Plot of rate of shear against shear stress is a straight line passing through the origin provided flow is laminar Examples: 1.Water 2.Simple Organic Liquids 3.True Solutions 4.Dilute suspensions 5.Emulsions 6.Gases
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Bingham body: Connected internal structure that collapses above a yield stress Above yield stress (y ), shear rate increases linearly with shear stress i.e. = ( y ) where y Examples: Pottery clay, chocolate, toothpaste, butter
.
Examples: polymer melts and solutions, natural resins, rubbers, bitumens, heavy oils Advantage:
Reduction in viscosity with increasing rate of shear
Stresses required to produce high flow rates not as high as expected from viscosity measurements at low shear rates
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Shear rate increases, molecules become aligned so points of entanglements reduced Loss of existing entanglements higher than rate of generating new ones Number of entanglements in a given volume has lower equilibrium values at larger shear q g rates Frictional resistance between adjacent layer of the laminar fluid decreases Very high shear rates orientation of molecules complete, near Newtonian behaviour
Dilatant fluids: Increase in apparent viscosity with increase in shear rate Highly concentrated suspensions, particularly PVC pastes Irregularly shaped particles, closely packed with minimum voids in the stress free rate Low shear rate: Solid particles do not make much contact High shear rate: Particles do not pack easily, rubbing friction enhances resistance to flow Sand water suspensions, clay suspensions, printing inks Power law equation (n>1): . = k()n
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Thixotropic
Rheopectic
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