## 2 Experimental Section
### Measurements  
Molecular weight was estimated by gel permeation chromatography (GPC) using a liquid chromatograph (Shimadzu, model LC-8A, Tokyo, Japan) equipped with an Empower computer program (Waters, Massachusetts, MA, USA). A PL HFIP gel column (Polymer Lab, Agilent Technologies Deutschland GmbH, Boblingen, Germany) and a refractive index detector (Shimadzu RID-10A) were employed. The polymer was dissolved and eluted in 1,1,1,3,3,3-hexafluoroisopropanol containing CF3 COONa (0.05 M) was employed as solvent and elution medium. Flow rate was 0.5 mL/min, the injected volume 100 \(\upmu\)L, and the sample concentration 2 mg/mL. Polymethyl methacrylate standards were employed to determine the number and weight average molecular weights and molar-mass dispersities. A Focused Ion Beam Zeiss Neon40 microscope (Oberkochen, Germany) operating at 5 kV was employed to get SEM micrographs of micro-molded specimens. Carbon coating was accomplished with a Mitec K950 Sputter Coater (Oberkochem, Germany) was used to coat all samples, which were then viewed at an accelerating voltage of 5 kV. A FTIR 4100 Jasco spectrophotometer dotted with an attenuated total reflectance accessory (Specac MKII Golden Gate Heated Single Reflection Diamond ATR, Jasco International Co. Ltd., Tokyo,Japan) and a thermal controller was employed to get the FTIR spectra. Samples were placed in an attenuated total reflectance accessory with thermal control and a diamond crystal. X-ray photoelectron spectroscopy (XPS) was performed with a SPECS system (Berlin, Germany) dotted with an XR50 source of Mg/Al (1253 eV/1487 eV) operating at 150 W. Analyses were performed in a SPECS system equipped with a high intensity twin-anode X-ray source XR50 of Mg/Al (1253 eV/1487 eV) operating at 150 W. A Phoibos 150 MCD-9 XP detector (Berlin, Germany) was employed. The overview spectra were taken with an X-ray spot size of 650 and pass energy of 25 eV in 0.1 eV steps at a pressure below 6 \(\times\) 10\({}^{-9}\) mbar. Surface composition was determined through the N 1s and Si 2p peaks at binding energies of 399.2 and 103.2 eV, respectively. Distribution of micro/nanoparticles in the composites was evaluated by means of a Philips TECNAI 10 electron microscope (Philips Electron Optics, Eindhoven, Holland) at an accelerating voltage of 80 kV. Samples were prepared by embedding the nanocomposite specimens. A low-viscosity, modified Spurr epoxy resin was employed to embed the specimens before curing and cutting in small sections. A Sorvall Porter-Blum microtome (New York, NY, USA) equipped with a diamond knife was employed in this case. The thin sections were collected in a trough filled with water and lifted onto carbon-coated copper grids. Thermal degradation was performed in a Q50 thermogravimetric analyzer of TA Instruments (TA Instruments, New Castle, DE, USA). Experiments were carried out at a heating rate of 10 \({}^{\circ}\)C/min with 5 mg samples and under a flow of dry nitrogen. Growth rates of spherulites were measured by optical microscopy using a Zeiss Axioscopy 40 Pol light polarizing microscope (Oberkochen, Germany). This was equipped with a Linkam temperature control system configured by a THMS 600 heating and freezing stage connected to an LNP 94 liquid nitrogen system. Spherulites were isothermally crystallized at the selected temperature from homogeneous melt thin films. These were prepared by melting 1 mg of the polymer between microscope slides. Subsequently, small sections of the obtained thin films were pressed between two cover slides for microscopy observations. Samples were kept at the hot stage at 90 \({}^{\circ}\)C for 5 min to eliminate sample history effects, and then rapidly cooled to the selected temperatures. A Zeiss AxiosCam MRC5 digital camera (Munich, Germany) was employed to follow the diameter evolution of spherulites by taking micrographs at different times. Nucleation was evaluated by counting the number of active nuclei that appeared in the micrographs.