Comprehensive Analysis of Rheological, Mechanical, and Thermal Properties in Poly(lactic acid)/Oxidized Graphite Composites: Exploring the Effect of Heat Treatment on Elastic Modulus.

This study is focused on investigating the rheological and mechanical properties of highly oxidized graphite (GrO) incorporated into a poly (lactic acid) (PLA) matrix composite. Furthermore, the samples were annealed at 110 °C for 30 min to study whether GrO concentration has an effect on the elastic modulus (E') after treatment. The incorporation of GrO into PLA was carried out by employing an internal mixing chamber at 190 °C. Six formulations were prepared with GrO concentrations of 0, 0.1, 0.5, 1, 1.5, and 3 wt%. The thermal stability, thermomechanical behavior, and crystallinity of the composites were evaluated utilizing thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and differential scanning calorimetry DSC, respectively. The thermal stability (according to Tmax) of the PLA/GrO composites did not change substantially compared with PLA. According to DSC, the crystallinity increased until the GrO concentration reached 1 wt% and afterward decreased. Regarding the heat treatment of the PLA/GrO composites, the E' increased (by two orders of magnitude) at 80 °C with the maximum value achieved at 1 wt% GrO compared with the non-heat-treated composites.

Study of Geopolymers Obtained from Wheat Husk Native to Northern Mexico.

Agro-industrial wastes such as wheat husk (WH) are renewable sources of organic and inorganic substances, including cellulose, lignin, and aluminosilicates, which can be transformed into advanced materials with high added value. The use of geopolymers is a strategy to take advantage of the inorganic substances by obtaining inorganic polymers, which have been used as additives, e.g., for cement and refractory brick products or ceramic precursors. In this research, the WH native to northern Mexico was used as a source to produce wheat husk ash (WHA) following its calcination at 1050 °C. In addition, geopolymers were synthesized from the WHA by varying the concentrations of the alkaline activator (NaOH) from 16 M to 30 M, namely Geo 16M, Geo 20M, Geo 25M, and Geo 30M. At the same time, a commercial microwave radiation process was employed as the curing source. Furthermore, the geopolymers synthesized with 16 M and 30 M of NaOH were studied for their thermal conductivity as a function of temperature, in particular at 25, 35, 60, and 90 °C. The chemical composition of the WHA, determined by ICP, revealed a SiO2 content close to 81%, which is similar to rice husk. The geopolymers were characterized using various techniques to determine their structure, mechanical properties, and thermal conductivity. The findings showed that the synthesized geopolymers with 16M and 30M of NaOH had significant mechanical properties and thermal conductivity, respectively, compared to the other synthesized materials. Finally, the thermal conductivity regarding the temperature revealed that Geo 30M presented significant performance, especially at 60 °C.

Salivary Glucose Detection with Laser Induced Graphene/AgNPs Non-Enzymatic Sensor.

The tailoring of novel nanomaterials for sensitive glucose detection through a non-enzymatic mechanism is currently under intensive research. Here, we present a laser-induced graphene (LIG) electrode decorated with silver nanoparticles (AgNPs) as a catalytic element for the direct electrooxidation of glucose. The AgNPs were synthesized through cyclic voltammetry using LIG as a template, resulting in a porous tridimensional assembly with anchored nanostructures. The characterization corroborated the formation of LIG/AgNPs composite with distinctive peaks attributed to Ag2O and AgO interaction with glucose. The proposed non-enzymatic sensors were successfully applied for non-enzymatic amperometric detection, exhibiting a linear range from 1 to 10 mM in the first peak (+0.7 V) and a narrow range from 1 to 2 mM with higher sensitivity of 52.2 mA/mM and improved LOD of 45 µM in the second peak (+0.55 V). The applicability of the LIG/AgNPs sensor was evaluated with spiked artificial saliva in a PoC format using a smartphone potentiostat, showing an average recovery rate of 91%. The analysis was performed in a portable, mobile, and low-cost fashion using a simulated non-invasive sample, with promising results in clinical ranges.

Effect of the Addition of Different Natural Waxes on the Mechanical and Rheological Behavior of PLA-A Comparative Study.

In this study, poly(lactic acid) (PLA) blended with different natural waxes (beeswax, candelilla, carnauba, and cocoa) was investigated. Different wax amounts, 3, 5, 10, and 15 wt%, were incorporated into the PLA using a Brabender internal mixer. The blends were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), rotational rheometer (RR), dynamic mechanical analysis (DMA), and contact angle to observe the effect of the different waxes on the PLA physicochemical, rheological, mechanical behavior, and wetting properties. The complex viscosity of the blends was studied by employing a RR. The effect of the addition of the waxes on the mechanical properties of PLA was evaluated by DMA in the tension modality. A slight decrease in the thermal stability of PLA was observed with the addition of the waxes. However, in the case of the mechanical properties, the cocoa wax showed a considerable effect, especially in the elongation at break of PLA. Likewise, waxes had an essential impact on the water affinity of PLA. Specifically, with the addition of cocoa, the PLA became more hydrophilic, while the rest of the waxes increased the hydrophobic character.

Theoretical Study of Vinyl-Sulfonate Monomers and Their Effect as the Dopants of Polyaniline Dimers.

Establishing the structure-property relationships of monomers and polymers via theoretical chemistry is vital for designing new polymer structures with a specific application. Developing bifunctional monomers with selective polymerizable sites is one of the strategies employed to obtain complex polymeric systems. In this work, a theoretical study on anilinium 2-acrylamide-2-methyl-1-propanesulfonate (ani-AMPS) and anilinium 4-styrenesulfonate (ani-SS) monomers and their respective doped polyaniline dimer (PAni-d AMPS or PAni-d SS) was performed. The study focused on understanding the susceptibility of the vinyl group to a radical attack and the conformation changes resulting from the coordinated covalent bond between sulfonate and aniliniun. Applying Density Functional Theory with the B3LYP functional and a basis set of 6 - 31 + G(d,p), the structures of the ani-AMPS, ani-SS, PAni-d AMPS, and PAni-d SS were optimized, and the different chemical descriptors were determined. The simulation showed that the reactivity of the vinyl group in the ani-AMPS is slightly higher. The sulfonate group undergoes a conformational change when bonding with PAni-d AMPS or PAni-d SS compared to its respective bifunctional monomer. Additionally, the electronegativity of PAni-d depends on the dopant's structure. Thus, the bonded spacer between the vinyl and sulfonate groups (dopant) plays a notable role in the final characteristics of ani-AMPS, ani-SS, PAni-d AMPS, and PAni-d SS.

Brush-like Polyaniline with Optical and Electroactive Properties at Neutral pH and High Temperature.

In this research, a brush-like polyaniline (poly(2-acrylamide-2-methyl-1-propanesulfonate)-g-polyaniline)-b-poly(N-vinylcarbazole) (BL PAni) was developed as a strategy to overcome the limited processability and dedoping above pH 4 of conventional polyaniline (PAni). For the BL PAni synthesis, RAFT polymerization (homopolymer), RAFT-mediated surfactant-free emulsion polymerization (block copolymer), and interfacial oxidative polymerization were applied to graft the PAni chains. NMR and FT-IR spectroscopies were performed to confirm the structural elucidation of the reaction pathways, while the thermal properties were analyzed by TGA and DSC. Notably, the BL PAni presents absorption throughout the visible region and up to the near-infrared, showing dedoping resistance at up to 80 °C and at a neutral pH. The absorption range of the BL PAni, block copolymer, and homopolymer were studied by UV-Vis spectroscopy in solid-state and dispersion/solution, highlighting BL PAni and poly(anilinium 2-acrylamide-2-methyl-1-propanesulfonate)-b-poly(N-vinylcarbazole) (PAAMP-b-PVK) due to the π-stacking between the anilinium and carbazole groups. The cyclic voltammetry confirmed the persistence of electroactivity at a pH near 7.

Progress of Polyaniline Glucose Sensors for Diabetes Mellitus Management Utilizing Enzymatic and Non-Enzymatic Detection.

Glucose measurement is a fundamental tool in the daily care of Diabetes Mellitus (DM) patients and healthcare professionals. While there is an established market for glucose sensors, the rising number of DM cases has promoted intensive research to provide accurate systems for glucose monitoring. Polyaniline (PAni) is a conductive polymer with a linear conjugated backbone with sequences of single C-C and double C=C bonds. This unique structure produces attractive features for the design of sensing systems such as conductivity, biocompatibility, environmental stability, tunable electrochemical properties, and antibacterial activity. PAni-based glucose sensors (PBGS) were actively developed in past years, using either enzymatic or non-enzymatic principles. In these devices, PAni played roles as a conductive material for electron transfer, biocompatible matrix for enzymatic immobilization, or sensitive layer for detection. In this review, we covered the development of PBGS from 2015 to the present, and it is not even exhaustive; it provides an overview of advances and achievements for enzymatic and non-enzymatic PBGB PBGS for self-monitoring and continuous blood glucose monitoring. Additionally, the limitations of PBGB PBGS to advance into robust and stable technology and the challenges associated with their implementation are presented and discussed.

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives.

Renewable polymers possess the potential to replace monomers from petrochemical sources. The design and development of polymeric materials from sustainable materials are a technological challenge. The main objectives of this study were to study the microstructure of copolymers based on itaconic acid (IA), di-n-butyl itaconate (DBI), and lauryl methacrylate (LMA); and to explore and to evaluate these copolymers as pressure-sensitive adhesives (PSA). The copolymer synthesis was carried out through batch emulsion radical polymerization, an environmentally friendly process. IA was used in a small fixed amount as a functional comonomer, and LMA was selected due to low glass transition temperature (Tg). The structure of synthesized copolymers was studied by FTIR, 1H-NMR, Soxhlet extraction, and molecular weight analyses by GPC. Furthermore, the viscoelastic and thermal properties of copolymer films were characterized by DMA, DSC, and TGA. The single Tg displayed by the poly(DBI-LMA-IA) terpolymers indicates that statistical random composition copolymers were obtained. Moreover, FTIR and NMR spectra confirm the chemical structure and composition. It was found that a cross-linked microstructure and higher molecular weight are observed with an increase of LMA in the feed led. The Tg and modulus (G') of the copolymers film can be tuned with the ratio of DBI:LMA providing a platform for a wide range of applications as a biobased alternative to produce waterborne PSA.

Stiff-Elongated Balance of PLA-Based Polymer Blends.

In this study, polymer blends with a mechanical property balance based on poly(lactic acid) (PLA), stiff polymer, and elongated polymer were developed. First, the binary blends PLA-elongated polymer [ethyl vinyl acetate (EVA) or polyethylene], or PLA-stiff polymer [polystyrene or poly(styrene-co-methyl methacrylate) (SMMA)] blends were studied using dynamic mechanic analysis (DMA) and analyzed using Minitab statistical software to determine the factors influencing the elongation or stiffness of the blends. Then, ternary blends such as elongation-poly(lactic acid)-stiff, were made from the binary blends that presented optimal performance. In addition, three blends [EVA-PLA-SMMA (EPS)] were elaborated by studying the mixing time (5, 15, and 15 min) and the added time of the SMMA (0, 0, and 10 min). Specifically, the mixing time for EPS 1, EPS 2, and EPS 3 is 5 min, 15 min, and 15 min (first EVA + PLA for 10 min, plus 5 min PLA-EVA and SMMA), respectively. Mechanical, thermal, rheological, and morphological properties of the blends were studied. According to DMA, the results show an increase in elongation at break (εb) and do not decrease the elastic module of poly(lactic acid). Nevertheless, EPS 3 excels in all properties, with an εb of 67% and modulus of elasticity similar to PLA. SMMA has a significant role as a compatibilizing agent and improves PLA processability.

Role of the Anilinium Ion on the Selective Polymerization of Anilinium 2-Acrylamide-2-methyl-1-propanesulfonate.

The development of anilinium 2-acrylamide-2-methyl-1-propanesulfonate (Ani-AMPS) monomer, confirmed by 1H NMR, 13C NMR, and FTIR, is systematically studied. Ani-AMPS contains two polymerizable functional groups, so it was submitted to selective polymerization either by free-radical or oxidative polymerization. Therefore, poly(anilinium 2-acrylamide-2-methyl-1-propanesulfonic) [Poly(Ani-AMPS)] and polyaniline doped with 2-acrylamide-2-methyl-1-propanesulfonic acid [PAni-AMPS] can be obtained. First, the acrylamide polymer, poly(Ani-AMPS), favored the π-stacking of the anilinium group produced by the inter- and intra-molecular interactions and was studied utilizing 1H NMR, 13C NMR, FTIR, and UV-Vis-NIR. Furthermore, poly(Ani-AMPS) fluorescence shows quenching in the presence of Fe2+ and Fe3+ in the emission spectrum at 347 nm. In contrast, the typical behavior of polyaniline is observed in the cyclic voltammetry analysis for PAni-AMPS. The optical properties also show a significant change at pH 4.4. The PAni-AMPS structure was corroborated through FTIR, while the thermal properties and morphology were analyzed utilizing TGA, DSC (except PAni-AMPS), and FESEM.

Curing of Cellulose Hydrogels by UV Radiation for Mechanical Reinforcement.

The use of biomaterials as a replacement for thermoplastic polymers is an environmentally sound strategy. In this work, hydrogels of cellulose isolated from wheat husk were modified by UV irradiation (353 nm) to improve mechanical performance. The cellulose was dissolved with a solvent system N,N-dimethylacetamide/lithium chloride (DMAc/LiCl). Infrared spectroscopy showed that the peak height at 1016 cm-1, associated with the C-O bonds of the glycosidic ring, increases with irradiation time. It was determined that the increase in this signal is related to photodegradation, the product of a progressive increase in exposure to UV radiation. The viscoelastic behavior, determined by dynamic mechanical analysis and rotational rheometry, was taken as the most important parameter of this research, showing that the best results are recorded with 15 min of UV treatment. Therefore, at this time or less, the chemical crosslinking is predominant over the photodegradation, producing an increase in the modules, while with 20 min the photodegradation is such that the modules suffer a significant reduction.

Synthesis of Graphite Oxide with Different Surface Oxygen Contents Assisted Microwave Radiation.

Graphite oxide is synthesized via oxidation reaction using oxidant compounds that have lattice defects by the incorporation of unlike functional groups. Herein, we report the synthesis of the graphite oxide with diverse surface oxygen content through three (B, C, D) different modified versions of the Hummers method assisted microwave radiation compared with the conventional graphite oxide sample obtained by Hummers method (A). These methods allow not only the production of graphite oxide but also reduced graphene oxide, without undergoing chemical, thermal, or mechanical reduction steps. The values obtained of C/O ratio were ~2, 3.4, and ~8.5 for methodologies C, B, and D, respectively, indicating the presence of graphite oxide and reduced graphene oxide, according to X-ray photoelectron spectroscopy. Raman spectroscopy of method D shows the fewest structural defects compared to the other methodologies. The results obtained suggest that the permanganate ion produces reducing species during graphite oxidation. The generation of these species is attributed to a reversible reaction between the permanganate ion with π electrons, ions, and radicals produced after treatment with microwave radiation.

Synthesis and electrical properties of polyaniline/iota-carrageenan biocomposites.

Polyaniline/iota-carrageenan (ι-CGN) biocomposites were synthesized via in situ methodology using ammonium persulfate as the oxidizing agent. Both ionic (band at 1131 cm(-1)) and hydrogen bond (bands at 2500 and 3500 cm(-1)) interactions between polyaniline and ι-CGN were determined by infrared spectroscopy. Such intermolecular interactions provided the biocomposites with a cross-linked structure that provided the materials with hydrogel behavior. Biocomposite electro-conductivity, determined by the 4-probe technique, was in the range of semiconductors (10(-3) to 10(-2) S cm(-1)); whereas electro-activity, assessed by cyclic voltammetry, showed the oxidation-reduction transitions typical of polyaniline. Based on the properties of polyaniline and ι-CGN, some applications for the new materials in the field of biosensor design, electrochemical capacitors, or tissue engineering scaffolds are possible. It is worth saying that both electro-conductive and electro-active properties of polyaniline/ι-CGN biocomposites are reported here for the first time.