Assignment - 6
Q1. a) Table-1 shows the data of normalized autocorrelation function (𝑔2 (𝜏) = 1 + 𝑏 ∗ exp(−𝑡/𝜏))
obtained from Dynamic Light Scattering measurements for a polymer-grafted nanoparticle (PGNP)
dissolved in solvent-A and solvent-B. Use the data to obtain the estimate of hydrodynamic size of
PGNP for both cases. Other information: λ=642 nm, viscosity of both solvent are roughly equal to
𝑘 𝑇
𝑏
water-viscosity (10-3 Pa.s) . Stokes-Einstein equation: 𝐷 = 6𝜋𝜇𝑅 , where 𝑘𝑏 = 1.380649 × 10−23 joule/K.
ℎ
All DLS measurements done at T=298K (Hint: rearrange expression of 𝑔2 (𝜏) in linearized form).
b) “Good solvent” the polymer chain prefers more stretched configuration whereas in “bad solvent”
the polymer chain shrinks within itself. Based on this definition, explain your estimates of
hydrodynamic size and the type of solvent for A and B. (Use the graph paper given on the second last
page for plotting if required)
Table-1
Solvent- Solvent-
A B
τ(s) g2(τ) – 1 g2(τ) – 1
0.000335 0.930165 0.99948
0.000872 0.711163 0.857335
0.00136 0.557156 0.745734
0.001849 0.436501 0.64866
0.002304 0.347584 0.569492
0.002711 0.283617 0.507009
0.003362 0.204838 0.420978
0.00398 0.150367 0.352811
0.004501 0.115903 0.304045
0.004972 0.091545 0.265699
0.005395 0.074093 0.23545
0.006795 0.036807 0.15786
0.00795 0.020658 0.113483
0.008389 0.016584 0.100097
Q2. Relaxation modulus decay data for a polymer melt at four different temperatures is given below:
Temperature 323K 298K 233K 214K
t (s) G(t) (Pa) t (s) G(t) (Pa) t (s) G(t) (Pa) t (s) G(t) (Pa)
0.01879 134231.2 0.00321 217720.5 0.005 368306.8 0.00161 3.72E+06
1.37084 31456.95 0.10992 152281.8 0.30161 252247.1 0.11708 537766
14.14764 5491.943 3.31549 77698.2 1.28703 217720.5 0.26586 435782
32.12546 1691.648 36.44542 32808.11 6.63616 172759.8 5 305781
a) Demonstrate time-temperature superposition by creating a master curve. Use the shift factor data
given in Table-2. (crate the master curve on log-log scale graph given on the last page of question
paper).
Table-2
T (Kelvin) Horizontal
Shift factors
214 1
233 93
298 13953.5
323 302325.6
b) Create the relaxation modulus decay plot (up to 105s) at 233K using the master curve. Hence,
explain the advantage of time-temperature superposition.
Q3. Figure below shows strain evolution during a creep-recovery test.
a) Mark the following in the above diagram: instantaneous elastic strain, viscoelastic strain,
instantaneous elastic strain-recovery, viscoelastic strain recovery, permanent strain.
b) Suggest a model to capture the above shown strain evolution during creep-recovery test.
c) Obtain the strain as a function of time during creep (over time 0 to t1) and during recovery
(t>t1).
Short Answer type questions (answer briefly and precisely in few lines)
4) Describe the experimental profile to obtain dynamic and static yield stress.
5) In case of Electrorheological Fluids, explain the effect of electric field strength on yield stress.
6) Concentrated aqueous solution of few long polymers show rod-climbing effect. Which rheological
property is responsible for such phenomenon? Explain the physics of this phenomenon?
7) A polymer solution is undergoing cross linking reaction to form a gel. Define gel physically (in terms
of microstructure)?
As a rheologist you have chosen to measure the gel point as the cross over time of storage and loss
modulus measure as a function of time at a given frequency. Such gel-point is called apparent gel-
point. Explain why the word “apparent” is used ? Plot qualitatively the apparent gel-point as function
of frequency. Suggest a more accurate rheological test to measure true gel-point and justify it?
8) Plot qualitatively the relaxation modulus decay to compare concentrated aqueous dispersion of
bare silica particle, Polymer grafted silica nanoparticle with low grafting density, Polymer grafted silica
nanoparticle with very high grafting density (all dispersion have identical concentration in vol/vol%).
Explain your plot.