Dataset of operating conditions to Isolate Cellulose Nanocrystalline from Sugarcane Bagasse and Pinewood Sawdust as Possible Material to Fabricate Polymer Electrolyte Membranes

The data shown in this document provides all the experimental data that complement the article published in Carbohydrate Polymers entitled “Influence of operating conditions on Proton Conductivity of Nanocellulose films using two Agroindustrial Wastes: Sugarcane Bagasse and Pinewood Sawdust” [1]. The data of this paper are the result of a large series of experiments to optimize the extraction of cellulose nanocrystalline (CNC) from these two agro-industrial wastes: sugarcane Bagasse (SCB) and pinewood sawdust (PSW). The conditions of pretreatment (5 wt.% or 10 wt.% of NaOH) and hydrolysis temperature (60, 75 and 90°C) in an aqueous solution of 45 wt.% of H2SO4 were analyzed exhaustively. The data includes the characterization by Fourier transform infrared (FT-IR), Differential Scanning Calorimetry/Thermogravimetric Analysis (DSC/TGA), Dynamic Light Scattering (DLS), X-ray diffraction (XRD) patterns, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) micrographs with their corresponding SAED patterns and nanoindentation tests. Additionally, photographs during the isolation of cellulose nanocrystalline in dependence of the syntheses parameters. It is also included the data that complement the molecular dynamic simulation generated by GLYCAM carbohydrate builder based on the coordinates for alpha and beta cellulose considering a microfibril of 5, 10 and 20 glucosyl residues (degree of polymerization, DP). Overall data have not been previously published and are available contributing to a better understanding of the CNCs isolation through different pretreatment concentrations and temperatures of processing.


a b s t r a c t
The data shown in this document provides all the experimental data that complement the article published in Carbohydrate Polymers entitled "Influence of operating conditions on Proton Conductivity of Nanocellulose films using two Agroindustrial Wastes: Sugarcane Bagasse and Pinewood Sawdust" [1] . The data of this paper are the result of a large series of experiments to optimize the extraction of cellulose nanocrystalline (CNC) from these two agro-industrial wastes: sugarcane Bagasse (SCB) and pinewood sawdust (PSW). The conditions of pretreatment (5 wt.% or 10 wt.% of NaOH) and hydrolysis temperature (60, 75 and 90 °C) in an aqueous solution of 45 wt.% of H 2 SO 4 were ana-lyzed exhaustively. The data includes the characterization by Fourier transform infrared (FT-IR), Differential Scanning Calorimetry/Thermogravimetric Analysis (DSC/TGA), Dynamic Light Scattering (DLS), X-ray diffraction (XRD) patterns, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) micrographs with their corresponding SAED patterns and nanoindentation tests. Additionally, photographs during the isolation of cellulose nanocrystalline in dependence of the syntheses parameters. It is also included the data that complement the molecular dynamic simulation generated by GLYCAM carbohydrate builder based on the coordinates for alpha and beta cellulose considering a microfibril of 5, 10 and 20 glucosyl residues (degree of polymerization, DP). Overall data have not been previously published and are available contributing to a better understanding of the CNCs isolation through different pretreatment concentrations and temperatures of processing.
© 2020 The Author(s

Value of the data
• The data are useful since show the importance of adjust the NaOH pretreatment concentration and temperature of acid hydrolysis (H 2 SO 4 ) to isolate cellulose nanocrystalline. • The data help to understand the connection between the crystallinity, proton conductivity and mechanical properties. • The agroindustrial sector can be helped to process, the by-products into products of high added value, for example during the fabrication of polymer electrolyte membranes. • The data show the MD simulation from which the researchers can evaluate the behavior of the donor-acceptor of CNCs under the conditions of this research.

Data description
In the present article, we report the data related to the nanocellulose production from two agroindustrial waste materials: SCB and PWS. Fig. 1 shows photographs of isolate cellulose nanocrystalline at each experimental conditions of isolation. The photographs show changes in the appearance in dependence of processing parameters. The dataset includes FT-IR spectra that were plotted from the 950 to 850 cm −1 (wavenumber) vs the transmittance (%) that correspond to different treatments applied to SCB and PWS ( Fig. 2 a-c). The spectra were shown for each temperature of acid hydrolysis (5 wt. % of NaOH and 45 wt.% of H 2 SO 4 ) at 60 °C ( Fig. 2 a), 75 °C ( Fig. 2 b) and 90 °C ( Fig. 2 c). For comparison, it is presented the FT-IR spectra of commercial cellulose (CC). The Fig. 3 displays particle size distribution histograms of crystalline nanocellulose obtained from DLS measurements. The inset figures also showed deconvolution of FT-IR spectra in the 380 0-30 0 0 cm −1 region for all the samples where it can be observed the inner components of hydrogen-bonded OH stretching. Fig. 4 depicts the XRD patterns scanned from 10-40 °in θ -2 θ arrangement that includes the results of the SCB raw ( Fig. 4 a), CNC isolated from SCB with 5 wt.% ( Fig. 4 b) and 10 wt.% ( Fig. 4 c) of NaOH followed of the acid hydrolysis with 45 wt.% of H 2 SO 4 at 75 °C, respectively. The structural comparison was realized with commercial cellulose ( Fig. 4 d). The quantification of amorphous and crystalline phases in dependence of synthesis parameters was carried out by the Shirley background substation with a Gaussian-Lorentzian profile. The Figs. 5 and 6 show the deconvolution of the as-received raw materials, commercial cellulose and the CNCs isolated from each agroindustrial waste. To verify chemical changes in FT-IR bands related with the H-bonds that compose the -OH stretching bands, in the region from 3800 to 30 0 0 cm −1 , it was realized an analysis using a second derivative ( Fig. 7 a-f). This figure shows the second derivative as a function of the evaluate parameters. The DSC/TGA analysis for a typical sample of cellulose nanocrystalline extracted from SCB at 75 °C is shown in Fig.  8 . A comparison of the crystallinity computed from FT-IR and XRD measurements was shown in Fig. 9 . In Figs. 10 and 11 , it is presented the morphology of crystalline films on slide glass using a wet film of 120 μm. The microstructural aspects of this films were analyzed by TEM images with their corresponding selected area of electron diffraction (SAED) patterns ( Figs. 12 and  13 ). The mechanical properties of cellulose membranes were performed with a nanoindentation Tester NHT 3 using a Poisson's ratio of 0.38 [2] . Overall samples were measured 5 times on dif-  α-1,4 and β-1,4 linkages of cellulose is displayed in Fig. 15 . Donor-acceptor

Experimental design, materials, and methods
The main information on the extraction and experimental equipment used to obtain the nanocellulose samples from PWS and SBC is reported in reference [1] .
The FT-IR spectra of CNCs obtained from CC, PSW and SCB were acquired in a spectrum one (Perkin Elmer) spectrometer in transmittance mode. Samples were scanned 20 times at the maximum resolution (4.0 cm −1 ) in the range of 40 0 0-50 0 cm −1 . As reference, commercial cellulose acquired from Sigma-Aldrich (type 20, 20 μm) was also analyzed.
Particle size distribution of the as-prepared CNCs samples was determinate by Dynamic Light Scattering (DLS) using a Litesizer 500 equipment (40 mW semiconductor laser of 658 nm wavelength; Particle Analyzer, Anton Paar). The nanocellulose was dispersed in pharmaceutical water (PISA), and adjusted to a concentration of 1 g L −1 ; the sample was sonicated for 20 min to achieve a good dispersion; after, it was diluted at different concentrations (0.05 mg mL −1 ).
DSC/TGA studies were realized in a LAB SYS EVO SETARAM instrumentation. 3 mg of sample was placed in a crucible. The experiments were carried out in an inert atmosphere (Ar) from 30 to 250 °C in an aluminum pan with a heating and cooling rate of 5 °C min −1 followed by cooling to 30 °C to eliminate the thermal history of the materials. Then, they were heated again until 250 °C.
The cellulose nanocrystalline membranes were prepared with the extracted solution of the acid hydrolysis, which was previously maintained in sonication for 2 h to minimize agglomeration. The resulting solution was then left at room temperature for 2 h for the removal of possible bubbles trapped within the solution. Thereafter, the membranes were casted with a 120 μm casting knife (film applicator, Elcometer 3580) onto a glass plate at room temperature and 80% of air humidity. The polymeric film was peeled off from the glass plate and introduced in a separate water bath for 3 h to eliminate residues. Then, the film was dried for 24 h before characterization.
The structure of the samples (membranes) was determined by X-ray diffraction (XRD) with a Bruker D8 Advance diffractometer equipped with a Lynxeye detector and Cu K α radiation ( λ = 1.5405 Å ) at 40 kV and 35 mA. Data were collected at room temperature in the 2 θ range of 5-50 °with a step of 1 °min −1 . Data were plotted and analyzed from 10 to 40 °(2 θ ).  The morphology of selected membranes was studied by scanning electron microscopy (SEM) using a JEOL JSM-6701F microscope (5 kV of acceleration voltage) with no conductive coating. TEM images and SAED patterns were taken in a JEOL JEM-20 0 0 FX at 200 kV.
Mechanical properties were analyzed on rectangular membranes (25.4 × 38.1 mm) using an Anton Paar Nanoindentation Tester NHT 3 with the Oliver & Pharr method. A Poisson's ratio of 0.38 was used for the evaluation [2] . A loading of 8 mN min −1 was applied until reaching a maximum load of 40 mN. The load was held for 10 s in order to account the creep effects and then the indenter was unloaded. Five measurements were acquired to obtain representative values.
Molecular dynamic (MD) simulations were performed to model the formation of cellulose type I or II based on of the number of glucosyl residues and reaction temperature. The simulated system consisted of micro-fibrils of 5, 10 and 20 glucosyl residues as a measurement of the cellulose polymerization degree (C 6 H 10 O 5 ) n . Carbon atoms are in six-membered ring of each glucose group, being linked each other by common oxygen (O) atom (ester bond), glucose groups are polymerized into a large polymer where each molecule is interacting mainly by hydrogen bonding. Model fibrils were subjected to energy minimization (250,0 0 0 steps of minimization; 500 of steepest descent), followed by heating at 60, 75 and 90 °C. All primary structures were produced using the GLYCAM carbohydrate builder based on the coordinates for cellulose 1,4alpha and beta, prior AMBER (Assisted Model building and Energy Refinement) minimization. All simulations were carried out with SHAKE algorithm using a 2 fs time step and Langevin dynamics for temperature control [3] and for simplicity, water was used as simulated medium. The systems were stabilized by the transferable intermolecular potential 3P (TIP3P).The total potential energy of cellulose is partitioned into several energy terms. These contributions include non-bonding energies, bond stretching energies, angle bending energies, torsion angle energies, out-of-plant bending energies and coulombic interaction energies.