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PST 522E
SYNTHESIS & CHARACTERIZATION OF
MACROMOLECULES
17.05.2017
1. THEORETICAL PART
Rheology is a branch of physics that deals with the deformation and flow of matter under
stress rooted in the laws of elasticity and viscosity proposed by Hooke and Newton in the late
17th Century. It is particularly concerned with the properties of matter that determine its
behavior when a mechanical force is exerted on it. Rheology is distinguished from fluid
dynamics because it is concerned with the three traditional states of matters rather than only
liquid and gases. For many years, rheology has been used as semi quantitative tools in
polymer science and engineering. The relationship between the structure and rheology of a
polymer is of practical interest for two reasons: firstly, rheological properties are very
sensitive to certain aspect of structure and they are simpler to use than analytical methods,
such as nuclear magnetic resonance. Secondly, it is the rheological properties that govern the
flow behavior of polymers when they are processed in the molten state.
In the last three decades, considerable progress has been made in the rheology of polymer
solutions and polymer melts. The measurement of rheological properties of any polymeric
material in the molten state is crucial in order to gain fundamental understanding of the
processability of that material. This is because rheological behaviors are strongly influenced
by the material structure and the interfacial characteristics. The rheology of polymer melt is
crucially essential for two reasons. Firstly, it has helped to resolve many polymer problems,
such as wide gauge variations in films, poor optical quality of sheet and films, slow
production rates, dimensional instability and poor mechanical properties. Secondly, it has
been employed for the analysis of parameters, such as: molecular structures, branching type
and extent of branching, content, entanglements and crosslink density.
Newtonian Fluids: Fluids which obey the Newtons law of viscosity are called as Newtonian
fluids. Newtons law of viscosity is given by;
= - (dv/dy) where is shear stress, = viscosity of the fluid and dv/dy is the shear rate,
rate or strain or velocity gradient.
All gases and most liquids which have simpler molecular fomula and low molecular weight
such as water, benzene, ethyl alcohol, CCl4, hexane etc. and most solutions of simple
molecules are Newtonian fluids.
Non-Newtonian Fluids: Fluids which do not obey the Newtons law of viscosity are called as
non-Newtonian fluids and viscosity of these fluids calculated by;
= (dv/dy) where is the apparent viscosity and is not constant for non-Newtonian
fluids.Shearing stress is not linearly related to the shear rate. ( not constant depends also
on shear rate)
If the viscosity is influence by the shear rate, it is important to specify that the values are
different from the constant ones of an ideally viscous fluid. The values obtained called as
apparent viscosity or apparent shear viscosity values. Generally non-Newtonian fluids are
complex mixtures such as slurries, pastes, gels, polymer solutions, blood, ketchup etc. Non-
Newtonian behaviors classified as time-independent, time-dependent and viscoelastic.
Flow of pseudoplastics is
consistent with the random coil model of polymer solutions and melts. At low stress,
flow occurs by random coils moving past each other without coil deformation. At
moderate stresses, the coils are deformed and slip past each other more easily. At high
stress, the coils are distorted as much as possible and offer low resistance to flow.
Entanglement Disentanglement
Shear thinning behavior is often a result of;
The Power-Law or Ostwald-De Waale Model: The relationship between shear stress and
shear rate for fluids can often be approximated by a straight line over a limited range of shear
rate, and hence this part of the flow curve can be described by the power law expression;
Where n and m, known as the power-law index and the fluid consistency coefficient, or the
flow index for a Newtonian fluid n=1, for a pseudoplastic substance n<1 and for a dilatant
fluid n>1.
Viscoplastic Fluid Behavior: A visco-elastic fluid displays both elastic and viscous
properties.Viscoplastic fluids behave as if they have a yield stress (0). Until the yield
stress is exceeded they do not appear to flow. A Bingham plastic fluid has a constant
plastic viscosity.
Often the two model parameters 0 and are treated as curve fitting constants, even
when there is no true yield stress.
Time-Dependent Fluid Behavior: The apparent viscosity of a fluid changes with
time as the fluid is continuously sheared.
Thixotropic Behavior: If the apparent viscosity decreases with time (e.g. paints,
cream, aqueous iron oxide gels, some drilling muds etc.) the fluid is called thixotropic.
This behavior is result of a break down in the microstructure of the material as
shearing continues. This behavior happens when the shear is exceeded of a limit. It
leads to non-linear stress-strain behavior.
Brookfield DV-III type low shear of DV-II + type low shear rheometer is used in
experiment. Small Sample Adapter (SSA), accesory with SC4-18 Spindle and
SC4-13RPY Sample Chamber with embedded PTD Temperature Probe and
Circulating Bath with Programmable Controller is used also. The spindle can be
changed according to the material to be measured.
Chitosan Experiment:
162
157
y1 = 9E-12x4 - 7E-08x3 + 0,0002x2 - 0,088x
R = 0,9864
152
147 Hysteresis
Shear Stres (mPa)
142
y2= -2E-12x4 + 1E-08x3 - 4E-05x2 + 0,1022x
137 R = 0,9922
132
127
122
117
2000 2200 2400 2600 2800 3000 3200 3400
Shear Rate (1/s)
Hysteresis area calculated by the difference between the areas under loading unloading
curves. Loading and unloading equations and shear rate boundaries given to Matlab program
to calculate integration.
Hysteresis Area: 361870 mPa/s. The presence of a hysteresis area means that the sample
shows time dependent rheological behavior.
As the hysteresis area > 0, we can say that material is thixotropic, it means that viscosity of
the chitosan decreases with time.
Chitosan - Loading
162
157
152
Shear Stress (mPa)
147 Loading
142
122
117
2000 2200 2400 2600 2800 3000 3200 3400
Shear Rate (1/s)
Bingham model was where was shear stress, was shear rate, B
yield value, and Pl plastic viscosity. From the loading graph of chitosan sample above, the
linear equation found as y=0,0248x+74,086 where; the slope of the line is plastic viscosity
Pl = 0,0248 mPa.s and the intercept is yield value B = 74,086 mPa. The sample fits
Bingham Model.
2,18 R = 0,9491
2,16 Flow Index
2,14
2,12
2,1
2,08
2,06
3,3 3,35 3,4 3,45 3,5 3,55
log Shear Rate
From the log/log graph of stress-shear rate of the sample, the slop of the line gives the flow
index value as n=0,4778. As the n < 1, we can say that chitosan is pseudoplastic. Shear
thinning behavior observed.
Xylan Experiment:
7
Hysteresis
6 y1= 2E-10x4 - 9E-08x3 + 2E-05x2 + 0,0192x - 0,0571
R = 0,99
5
Shear Stress (mPa)
2 R = 0,998
0
0 50 100 150 200 250 300 350
-1
Shear Rate (1/s)
Loading Xylan
From the loading-unloading graph of Xylan above, hysteresis area found as 41,7896 mPa/s.
The presence of a hysteresis area means that the sample shows time dependent rheological
behavior and is calculated by the difference between the areas under loading unloading
curves. Loading and unloading equations and shear rate boundaries given to Matlab program
to calculate integration.
As the hysteresis area > 0, we can say that Xylan is thixotropic, it means that viscosity of the
material decreases with time.
Xylan Loading
7
6 y = 0,0201x - 0,0642
Shear Stress (mPa) 5 R = 0,999
4
3
2
1
0
0 50 100 150 200 250 300 350
-1
Shear Rate (1/s)
Bingham model was where was shear stress, was shear rate, B
yield value, and Pl plastic viscosity. From the loading graph of Xylan sample above, the
linear equation found as y=0,0201x-0,0642 where; the slope of the line is plastic viscosity
Pl = 0,0201 mPa.s and the intercept is B = -0,0642 mPa < 0. Therefore, the sample does not
fit Bingham Model.
Flow Index-Xylan
1
y = 1,001x - 1,7264
0,5 R = 0,937
Log Shear Stress
0
0 0,5 1 1,5 2 2,5 3
-0,5
-1
-1,5
-2
Log Shear Rate
From the log/log graph of stress-shear rate of the sample, the slop of the line gives the flow
index value as n=1,0011. As the n =1, we can say that Xylan is plastic, there is a resistance
to flow.
XMt-1,25 Experiment:
10
y1= 2E-11x4 + 1E-08x3 - 2E-05x2 + 0,0326x - 0,0477
Shear Stress (mPa)
8 R = 0,9996
4
y2 = -4E-10x4 + 2E-07x3 - 3E-05x2 + 0,0305x + 0,0159
2 R = 0,9995
0
0 50 100 150 200 250 300 350
-2
Shear Rate (1/s)
From the loading-unloading graph of XMt-1,25 above, hysteresis area found as -21.2138
mPa/s. The presence of a hysteresis area means that the sample shows time dependent
rheological behavior and is calculated by the difference between the areas under loading
unloading curves. Loading and unloading equations and shear rate boundaries given to Matlab
program to calculate integration.
As the hysteresis area < 0, we can say that material XMt-1,25 is rheopectic, it means that
viscosity of the material increases with time.
Loading -XMt 1,25
Loading -XMt 1,25 Dorusal (Loading -XMt 1,25)
Dorusal (Loading -XMt 1,25)
12
Shear Stress (mPa)
10
y = 0,0293x + 0,0714
8
R = 0,9993
6
4
2
0
0 50 100 150 200 250 300 350
Shear Rate (1/s)
Bingham model was where was shear stress, was shear rate, B
yield value, and Pl plastic viscosity. From the loading graph of XMt-1,25 sample above, the
linear equation found as y=0,0293x+0,0714 where; the slope of the line is plastic viscosity
Pl = 0,0293 mPa.s and the intercept ,which gives the yield stress, is B = 0,0714 mPa > 0.
Therefore, the sample fits Bingham Model.
1,5
1
y = 1,0525x - 1,6412
Log Shear Stress
0,5
R = 0,9847
0
0 0,5 1 1,5 2 2,5 3
-0,5
-1
-1,5
-2
Log Shear Rate
From the log/log graph of stress-shear rate of the sample, the slop of the line gives the flow
index value as n=1,0525. As the n >1, we can say that XMt-1,25 is dilatant, viscosity
increases with increasing shear rate. We can say that XMt-1,25 is a shear thickening fluid.
Mt-1,25 Experiment:
4
Shear Stress (mPa)
0
0 50 100 150 200 250 300 350
Shear Rate (1/s)
From the loading-unloading graph of Mt-1,25 above, hysteresis area found as 714.8472
mPa/s. The presence of a hysteresis area means that the sample shows time dependent
rheological behavior and is calculated by the difference between the areas under loading
unloading curves. Loading and unloading equations and shear rate boundaries given to Matlab
program to calculate integration.
As the hysteresis area > 0, we can say that material Mt-1,25 is thixotropic, it means that
viscosity of the material decreases with time.
Loading Mt-1,25
Loading Mt-1,25 Dorusal (Loading Mt-1,25)
5
y = 0,014x - 0,2373
Shear Stress (mPa)
4 R = 0,9811
0
0 50 100 150 200 250 300 350
-1
Shear Rate (1/s)
Bingham model was where was shear stress, was shear rate, B
yield value, and Pl plastic viscosity. From the loading graph of Mt-1,25 sample above, the
linear equation found as y=0,014x-0,2373 where; the slope of the line is plastic viscosity
Pl = 0,014 mPa.s and the intercept is B < 0. Therefore, the sample does not fit Bingham
Model.
0
0 0,5 1 1,5 2 2,5 3
-0,5
-1
-1,5
-2
-2,5
Log Shear Rate
From the log/log graph of stress-shear rate of the sample, the slop of the line gives the flow
index value as n=1,0311. As the n >1, we can say that Mt-1,25 is dilatant, viscosity increases
with increasing shear rate. We can say that Mt-1,25 is a shear thickening fluid.
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