## 3 Results and Discussions
### Characterization of Materials
Moreover, from \(\sigma_{\mathrm{s}}\) values, it seems that this coating around fibers allows to have similar conductivity that having a polymer layer, preserving flexibility of these materials. Figure 6 shows the 3D profilometer images for selected materials prepared with CPs solutions. The effect of processing can be observed when comparing PEDOT:PSS samples deposited on A substrate. From Sa values and 3D images, it can be seen that surface of PPsACt sample is practically flat comparing to PPsASP and the substrate, confirming that a layer of PEDOT:PSS is deposited on the substrate, making this conductive coating probably not convenient for a supercapacitor electrode, where high specific area is required. PEDOT:PSS conductive layer is not formed when processing by spray coating, which results in a low \(\sigma\) for PPsASP. Regarding to PDBProDOT samples, it is observed that processing the polymer by spray coating leads to a more homogeneous coating compared to PEDOT:PSS samples; however, in the real color  
Figure 4: \(\sigma_{\mathrm{s}}\) values of raw CPs (solid bars) and selected composite materials (patterned bars). Figure 5: SEM micrographs and 3D profilometer images of W composites prepared by in-situ polymerization. image of PPDASp, some small white holes can be seen, indicating that PDBProDOT does not cover the entire substrate. When PDBProDOT is processed by spray coating over C membranes, the real color image suggests a homogeneous coating just like in-situ polymerization samples; however, despite obtaining easy-processable CPs, low \(\sigma\) of raw PDBProDOT leads to a low \(\sigma\) of composite materials. Moreover, no differences in \(\sigma\) can be identified independently of the substrate and roughness (PPDASp and PPDCSp). Thus, materials whose \(\sigma_{\rm s}\) has not been possible to measure in general show low bulk \(\sigma\), which can be due to a not homogeneous coating or to a low \(\sigma\) of the deposited polymer. Those materials were not further studied, and only samples with a measured value of \(\sigma_{\rm s}\) were compared. Figure 7 shows the dependence of \(\sigma_{\rm s}\) with both the PEDOT mass loading (mg\(\cdot\)gr\({}^{-2}\)) (Figure 7a) and Sa roughness parameter (Figure 7b and Table 4). In-situ approaches were not as satisfactory as expected for all the substrates, for instance, A substrates have a strong interaction both with the solvent used for EDOT polymerization, as well as with the oxidizing agents obtaining composite materials very brittle with very poor mechanical properties. In cases using casting technique, the obtained composite material appeared completely disintegrated (Figure 1). However, the use of CPs solutions of PEDOT:PSS or PDBProDOT with A substrates have resulted composite materials with good flexibility. Aqueous PEDOT:PSS solutions have no chemical interaction with A substrates maintaining the dimensional morphology resulting in composite materials with very low roughness independently the processing methodology (Figure S10). Moreover, a slightly decrease of \(\sigma_{\rm s}\) can be observed as Sa increase due to the importance of the formation of high quality crystalline phase on conductivity, which has been previously studied for PEDOT:PSS deposited onto cellulose substrates (Table 3) [40]. Likewise, PDBProDOT dissolved in low boiling point solvents (DCM) and processed by spray coating has resulted in composite materials with similar Sa values compared with PEDOT:PSS derived composite materials. In this case, casting processing working with DCM or THF has resulted in the total disintegration of the substrate discarding this methodology for the preparation of this family of composite materials. Figure 6: 3D Surface profilometer images of selected composite materials prepared by CPs solutions. In the case of W substrates, a main dependence of \(\sigma_{\text{s}}\) is seen respect to the conjugated polymer used, where \(\sigma_{\text{s}}\) of PEDOT:Triflate is generally higher than PEDOT:Tosyllate composite materials, independently of Sa values.