Self-replenishing ability of cross-linked low surface energy
polymer films investigated by a complementary experimentalsimulation approach
A.C.C. Esteves1*; K. Lyakhova1; J.M. van Riel1; L.G.J. van der Ven1,2; R.A.T.M. van
Benthem1,3; G. de With1*
SUPPORTING INFORMATION
SIMULATIONS
Parameterization: Parameterization of the coarse grained DPD beads is described in detail in
ref.[1] Beads of the same type repulsion parameter was taken a ij  25 (in units k B T ).[2] The
excess repulsion between beads was calculated using Flory-Huggins interaction parameters  .
The relations between a ij and a ii is aij  aii  3.49   [2]. The Flory-Huggins parameters  ij
were calculated via solubility parameters  ij  V0 ( i   j ) 2 / RT , where V 0 is the molar volume
of the solvent and  i and  j are self-solubility parameters. Solubility parameters  i were
obtained from group molar contributions[3]. For calculation of solubility parameters Molecular
Modelling Pro package was used[4].
The interaction between the artificial ‘void’ bead (V bead) and other beads was taken aVi  60
in order to insure the separation between polymer film and ‘air’ phase. The interaction
between CL-H beads and C-beads was taken a CL  H ,C  10 in order to increase probability of
cross-linking.
1
SM-TABLES
Table SM-1 Tri-functional polyester precursors (TMP-PCLx) and respective characterization.
TMP-PCLx
x
n
Mn
Mn
(3n)
(DP)
H1NMR
g/mol
GPC
PDI GPC
Mw/Mn
Mn
MALDI
g/mol
DSC
Tg
(°C)
DSC
Tm
(°C)
g/mol
TMP-PCL18
18
6
1590
2468
1.18
1650
-74
21
TMP-PCL24
24
8
2230
2480
1.19
2455
-72
35
TMP-PCL36
36
12
2892
4533
1.14
2683
-72
36
TMP-PCL48
48
16
3890
6428
1.11
3826
-71
41
Table SM-2: Polymeric dangling chains (F17C8-PCLy) and respective characterization.
y
F17C8-PCLy
(DP)
Ther.
Mn
Mn
Mn
H1NMR
g/mol
GPC
PDI
GPC
Mw/Mn
Mn
MALDI
g/mol
DSC
Tg
(°C)
DSC
Tm
(°C)
g/mol
F17C8-PCL8
8
1400
1648
2818
1.13
1415
-65
47
F17C8-PCL12
12
1800
1924
3191
1.17
2101
-66
50
F17C8-PCL16
16
2300
2042
3804
1.06
2329
-65
50
F17C8-PCL22
22
2800
2192
3781
1.12
2443
-64
50
Self-replenishing efficiency (SRE) calculation based on F/C and CA measurements:
errors consideration and estimation.
The unexpected increase of the F/C atomic ratios after damage may be explained by a possible
contribution from cross-contamination during the cryo-microtoming or XPS measurement. In
order to reduce this effect, the data points (and related error bars for sample standard deviation)
2
shown in Figure 4 a, are an average of the measurements collected at four different spots on
three film replicas.
For the CA measurements, several other aspects have also to be taken in consideration. The
caprolactone based systems, as used in this study, have been reported to have large CA
hysteresis due to surface-rearrangements[5]. Once the surfaces are damaged (at cryogenicconditions) they are exposed to some water upon returning to room temperature (from
condensation) which may induce changes on the surface composition or permanent damages on
the network, e.g. by hydrolyses of the ester bonds. In fact the receding CA recovery was
considerably lower than for the advancing (about 40 to 60 %, not shown). Moreover, although
the cryo-microtoming procedure should produce surfaces with a limited roughness and no
surface defects[6], the introduction of roughness, possible indentations of the knife and crosscontamination cannot be discarded as an additional source of errors.
The self-replenishing efficiency based on the F/C and CA experimental data calculated using
Equation 2 and 3, respectively. The error associated with these calculations was estimated
using Equation 4 and 5, respectively.
Estimated errors for SRE:
∆SRE 2
( SRE ) = (
∆SRE 2
( SRE ) = (
∆(FC after cut) 2
FC after cut
∆(CA after cut) 2
CA after cut
∆(FC original) 2
) +(
FC original
)
∆(CA original) 2
) +(
CA original
)
Eq. 4
Eq. 5
References
[ 1] Travis K.P. BM, Good K., Owens S.L. J ChemPhys 2007;127.
[ 2] Groot RD and Warren PB. J Chem Phys 1997;107:4423-4435.
3
[ 3] van Krevelen DW. "Properties of Polymers", 2nd ed. Amsterdam: 2nd edition , Elsevier,
1990.
[ 4] Molecular Modeling Pro, Norgwyn Montgomery Software Inc., 1992.
[ 5] Esteves ACC, Lyakhova, K, van der Ven, L. G. J.; van Benthem, R. A. T. M.; de With,
G. Macromolecules 2013;46:1993-2002.
[ 6] Dikic T, Ming W, van Benthem RATM, Esteves ACC, and de With G. Adv Mater
2012;24:3701-3704.
SI-FIGURE
original
after (60 µm) damage
0.32
0.28
0.24
0.20
0.16
F/C atomic ratio
0.12
0.08
a)
0.04
0.32
original
after damage
0.28
0.24
0.20
0.16
0.12
0.08
0.04
b)
16
20
24
28
32
36
40
44
48
TMP-PCLx
Figure SM-1. Experimental (a) and simulation (b): Fluorine/Carbon (F/C) atomic ratio as a
function of the length (DP) of the polymer network precursor (TMP-PCLx, x = 3·n CL units).
F17C8PCL16 dangling chains and 2 wt % of fluorine were used in the formulation. Errors bars
represent the sample standard deviation.
4