Dynamics

of Dilute Polymer
Solutions
David C. Martin
milty@udel.edu
MSEG 609
 Shear Deformation
y
Δx

x
A
F
Δx
γ =
Δy

Δx
γ =
ΔyΔt

Δy F Δx
σ= =η = ηγ
A ΔyΔt

Stress: Pa = N/m2 = J/m3

z Viscosity: Pa-sec
 Stokes’ Law
Fd = 6πηs Rυ s

Einstein’s Law
η = ηs (1+ 2.5φ + 4φ 2 + ...)
 Intrinsic Viscosity
η = ηs (1+ c[η ] + kh c [η ] + ...)
2 2

⎛ η − ηs ⎞
[η ] ≡ lim ⎜ ⎟⎠ Units of 1/c (mL/gm)
c→0 ⎝ cη
s

c
φ= N avVh
M

5cN avVh 5N avVh

η = ηs (1+ + ...) [η ] =
2M 2M
 Mark-Houwink Equation
4π 3 Rg3 M 3v
Vh ~ Rg [η ] ~ ~ ~ M 3v−1
3 M M

[η ] = kM a a=0.5 Theta, a=0.8 good solvent

[η ] = kM ηa

⎛ ∑ N i M i1+a ⎞
1/a

Mη = ⎜ i ⎟
⎜ ∑ Ni M i ⎟ M n < Mη < M w
⎝ i ⎠
Viscosity Measurements
• Capillary Viscometer
⎛ 8 ΔV ⎞ η
Δt = ⎜ η = A ρΔt
⎝ π gR 4 ⎟⎠ ρ

Determine A by using
reference solution with known
viscosity
Dynamic Light Scattering
∂(δ c ) ∂ 2 (δ c)
= Dm Fick’s 2nd Law
∂t ∂x 2

T
1
C(t) = lim ∫ I s (t ′ ) I s (t ′ + t)dt ′ Autocorrelation function
T →∞ T
0

C(t) = ( I 2
s − Is
2
) e −2q 2 Dmt
+ Is
2

times over 100 ns to 100 sec

 Examples
• Latex spheres from 1 nm-1 micron, 488 nm
Argon laser, water, 30-150 degree scattering
angles. What are the Ds, times required?
4π n ⎛ θ ⎞ 4 ⋅ 3.14 ⋅1.33 ⎧ ⎛ 30 ⎞ ⎛ 150 ⎞ ⎫
q= sin ⎜ ⎟ = ⎨ sin ⎜ ⎟ − sin ⎜ ⎟ ⎬ = 0.0089 − 0.033nm −1
λ0 ⎝ 2⎠ 488 ⎪⎩ ⎝ 2 ⎠ ⎝ 2 ⎠ ⎪⎭

kT 1.4 ⋅10 −16 ⋅ 300

Dt = = = 2.2 ⋅10 −7 − 2.2 ⋅10 −9 cm 2 / sec
6πη Rh 6 ⋅ 3.14 ⋅ 0.01⋅(10 − 10 )
−6 −4

τ ≈ 4 ⋅10 −5 − 6 ⋅10 −2 sec

Size Exclusion Chromatography
MALDI-TOF-MS
MALDI spectrum