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TTL212: Manufactured Fibre Technology

Outline of Next Few Lectures

Fundamental of Spinning

Recap of the last 12 lectures

Polymers and Polymerization Techniques Batch and Continuous Processes Synthesis and Production of: y
Nylon 6 Nylon 66 PET PAN

Introduction
spinning. capillary line.

to spinning and thermodynamics of

Polymer rheology including shear flow through a

and elongational flow in a Spinning

Melt instabilities. Momentum and heat transport in spinning.

Modification of PET and Nylons

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

Fibre Spinning Methods

Melt spinning Dry spinning Wet spinning
Melt spinning
Nylon 6,6 Nylon 6 PET PE PP

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

Melt Spinning Set-Up

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)

States of Polymer Liquid

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Todays Lecture

What is rheology?? The study of deformation and flow.

Polymer Rheology - N t i Fluids Newtonian Fl id

What is rheology?

What is Rheology? An answer for your baffled family and friends. *

Rheology is the study of the flow of materials that behave in an interesting or unusual manner. Oil and water flow in familiar, normal ways, whereas mayonnaise, peanut butter, chocolate, bread dough, and silly putty flow in complex and unusual ways. In rheology, we study the flows of unusual materials. all normal or Newtonian fluids (air, water, oil, honey) follow the same scientific laws. On the other hand, there are also fluids that do not follow the Newtonian flow laws. These non-Newtonian fluids, for example mayo, paint, molten plastics, foams, clays, and many other fluids, behave in a wide variety of ways. The science of studying these types of unusual materials is called rheology
*Faith Morrison, The News and Information Publication of The Society of Rheology, Vol 73(1) Jan 2004, pp 8-10

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Rheology Core: Viscosity and Elasticity

Examples of Complex Fluids

Foods
Emulsions (mayonaisse, ice cream) Foams (ice cream, whipped cream) Suspensions (mustard, chocolate) Gels (cheese)

Biofluids
Suspension (blood) Gel (mucin) Solutions (spittle)

Personal Care Products

Suspensions (nail polish, face scrubs) Solutions/Gels (shampoos, conditioners) Foams (shaving cream)

Electronic and Optical Materials

Liquid Crystals (Monitor displays) Melts (soldering paste)

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

Interested in what happens inside a point during deformation of the medium.

What happens inside a point?

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Rheological Behaviour of Fluids: Newtonian

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

Viscous Flow and Newtonian Fluids

Force F (dyn) applied on upper plane Shear stress (F/A dyn cm) Moves with velocity relative to lower plane Streamline or laminar flow: material planes sliding over another Angle measure of shear strain

Incompressible fluid is a fluid which is not reduced in volume by an increase in pressure.

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Now,

So, in the limit, d/dt d /d d /dt = du/dy

Rate of shear = /dt Velocity along C = u Velocity along D = u + (du/dy) Then, in time t, Distance moved by P = u t Distance moved by Q = [u + (du/dy) ] t

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

The profile of the advancing liquid is therefore a parabola.

Fluid flow through a capillary (a) laminar flow (b) parabolic velocity profile

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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

The profile of the advancing liquid is therefore a parabola.

Fluid flow through a capillary (a) laminar flow (b) parabolic velocity profile

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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

NON NEWTONIAN FLUIDS

Do not exhibit the characteristics of Newtonian Polymer melts and solutions Fluids in general can be divided into 2 categories: a) Time independent : rate of shear is a function of shearing stress b) Time dependent: Shear stress-shear rate relationships depend on how fluid has been sheared and its history

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TIME INDEPENDENT FLUIDS

Line A: Newtonian fluid Line B: Bingham body Line C: Shear thinning/pseudoplastic Line D: Shear thickening/dilatant

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
.

Pseudoplastic flow: Apparent viscosity decreases as the rate of shear is increased

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

Slope of OP > OP => <

This reduces power requirements for processing to a considerable extent

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Cause of shear thinning

Extensively entangled and randomly oriented nature of long chain molecules

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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TIME DEPENDENT FLUIDS

Thixotropic: At a constant shear stress or shear rate, the viscosity falls as time increases Time dependent collapse of ordered structure which breaks down to a lower apparent viscosity when sheared. Reversible effects. Paints, shaving cream, margarine, printing ink. Rheopectic: Apparent viscosity increases with time.

Thixotropic

Rheopectic

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