S) El aborto puede considerarse como un “mal menor”
3. Análisis exegético del proyecto de ley sustitutivo de
A comparison of the capacitance measurement during wetting and RTIL assisted drying step can be seen in Figure 7.10. It can be observed that the sample L3 displayed the least capacitance for both the wetting and the drying stages compared to sample L1 and L2.
Sample L2 displayed the highest capacitance at saturation during the wetting as well as drying cycle.
Figure 7.10: Capacitance results for L series GC based coatings as a function of immersion time for samples L1, L2 and L3 at a) 5 wt % NaCl and b) in room temperature ionic liquid.
An influence of polymer structure on the capacitance or the water uptake behavior of the coating is observed. A diffusion coefficient of 6.24x10-13 m2/sec and 6.15 x10-13 m2/sec was calculated for L1 and L2 for the wetting stage whereas comparatively low diffusion coefficient of 9.43 x10-14 m2/sec was obtained for sample L3 indicating that L3 was more resistant to electrolyte penetration compared to L1 and L2. A plot of diffusion coefficient (D) vs wt. % non-polar hydrocarbon (NPH) content as observed in Figure 7.11 reveals that D, during wetting, decreases with increase in wt. %NPH. Similar diffusion coefficient values of 2.03x10-13 m2/sec and 2.69 x10-13 m2/sec and 2.49 x10-13 m2/sec were
a) b)
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calculated for sample L1, L2 and L3 during drying step, indicating that the rate of water release (egress) from the coatings in the presence of RTIL were not much different.
56 57 58 59 60 61 62 63 64 65 66
Figure 7.11: Diffusion coefficients as a function of wt. % NPH for L series samples during a) wetting and b) during drying.
The capacitance trend displayed by L series coatings seems to have a direct correlation with the wt. % non polar hydrocarbon (NPH) content in the coating, calculated from the coating compositions, as seen in Table 2. The coating L3 with the highest NPH (65 wt. %) displayed the lowest capacitance compared to the coatings L1 and L2 as observed in Figure 7.12. Higher non-polar hydrocarbon content in the coating resists the aqueous electrolyte diffusion and hence low water uptake as shown in the capacitance plots.
Figure 7.12: Capacitance at saturation as a function of wt. % NPH for L series samples.
a) b)
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Figure 7.13 displays the Bode modulus along with the phase angle plot for the coating system L1, L2 and L3. Coating L3 displays a high |Z|0.01Hz value with purely capacitive |Z|( ) behavior after 2 hours with no any change even after 7 days constant immersion in 5 wt% NaCl indicating its excellent barrier performance. Coating L1 and L2 displayed impedance much lower than L3 with |Z|0.01Hz values of around three orders of magnitude less than L3. When compared to L1, L2 displayed a slightly higher |Z|0.01Hz
value.
Figure 7.13: EIS Bode plots for coatings L1, L2 and L3 after a) 2 hours and b) 7 days constant immersion in 5 wt. % NaCl.
500 550 600 650 700 0
Figure 7.14: Wet Tg as a function of epoxy equivalent weight (EEW) for L series samples.
a) b)
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Table 7.5: Wet and dry Tg of L coatings.
Coatings Dry Tg (°C) Wet Tg (°C)
L1 20 1
L2 18 9
L3 57 45
The higher the wet Tg higher is the barrier performance of the coating as observed for the coatings. Wet Tg was determined by wetting the coating film overnight and performing DSC on the wet film. Dry Tg was obtained by performing DSC on the dry sample. A particular composition of L series GC polymer, L-C, resulted in the highest NPH, the highest EEW, and the highest Tg (Table 7.3 and Table 7.5 and Figure 7.14 ) of the L3 coating. The highest EEW of L3 system indicated the lowest amine requirement for crosslinking and lower extent of generation of hydrophilic groups such as hydroxyl and tertiary amine during crosslinking (epoxy-amine reactions). Thus the highest impedance of the L3 coating could be correlated to the highest NPH and the highest EEW of the L-C polymer and the highest Tg of the L3 coating.[25]
7.3.2.2. Coating stability characterization in Wet-Dry cycling by single frequency EIS In an attempt to investigate the utility of SF-EIS in ranking the stability of coating system, cyclic EIS was also performed on all the three L series coatings. The cyclic SF-EIS consisted of a wetting stage in which capacitance of the coating was monitored under constant immersion condition in 5 wt. % NaCl for 48 hours. This was followed by the drying step in which the absorbed electrolyte during the wetting step was desorbed using
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ionic liquid and the capacitance of the coating during desorption was measured. This was also performed for 48 hours. After the drying step, the wetting step was repeated followed
0 10 20 30 40 50
Figure 7.15: Cycles of capacitance as a function of immersion time for coatings a) L1 during wetting b) L1 during drying c) L2 during wetting d) L2 during drying e) L3 during wetting and f) L3 during drying.
a) b)
c) d)
e) f)
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by drying and so on. L1_W1 corresponds to the first wetting cycle followed by the drying cycle L1_D1. This was followed by the second wetting cycle L1_W2 and so on. Four such wet-dry cycles were run for all the coatings as seen in the Figure 7.15. The fourth dry cycle for coating L1 could not be measured due to instrumental problems at the time of measurement.
Capacitance behavior as shown in Figure 7.15 reveals important information. In the wetting step coating L2 and L3 displays similar capacitance trend for all the cycles but for coating L1, a slight decrease in the capacitance is observed after every cycle. This might be due to change in the coatings molecular structure or molecular orientation due to coating plasticization by water influencing the water uptake behavior. [46, 47] Coating plasticization can be observed from decrease in Tg measured for wet coating samples as compared to their respective dry samples as seen in Table 7.5. The slight decrease in the capacitance behavior of coating L1 after every cycle compared to coating L2 and L3 indicates that coating L2 and L3 are more stable compared to coating L1.