Synergistic effect of phytic acid and eggshell bio-fillers on the dual-phase fire-retardancy of intumescent coatings applied on cellulosic substrates.

Cellulosic substrates, including wood and thatch, have become icons for sustainable architecture and construction, however, they suffer from high flammability because of their inherent cellulosic composition. Current control measures for such hazards include applying intumescent fire-retardant (IFR) coatings that swell and form a char layer upon ignition, protecting the underlying substrate from burning. Typically, conventional IFR coatings are opaque and are made of halogenated compounds that release toxic fumes when ignited, compromising the roofing's aesthetic value and sustainability. In this work, phytic acid, a naturally occurring phosphorus source extracted from rice bran, was used to synthesize phytic acid-based fire-retardants (PFR) via esterification under reflux, along with powdered chicken eggshells (CES) as calcium carbonate (CaCO3) bio-filler. These components were incorporated into melamine formaldehyde resin to produce the transparent IFR coating. It was revealed that the developed IFR coatings achieved the highest fire protection rating based on UL94 flammability standards compared to the control. The coatings also yielded increased LOI values, indicative of self-extinguishing properties. A 17 °C elevation of the IFR coating's melting temperature and a significant ∼172% increase in enthalpy change from the control were observed, indicating enhanced fire-retardancy. The thermal stability of the coatings was improved, denoted by reduced mass losses, and increased residual masses after thermal degradation. As validated by microscopy and spectroscopy, the abundance of phosphorus and carbon groups in the coatings' condensed phase after combustion indicates enhanced char formation. In the gas phase, TG-FTIR showed the evolution of non-flammable CO2, and fire-retardant PO and P-O-C. Mechanical property testing confirmed no reduction in the adhesion strength of the IFR coating. With these results, the developed IFR coating exhibited enhanced fire-retardancy whilst remaining optically transparent, suggestive of a dual-phase IFR protective mechanism involving the release of gaseous combustion diluents and the formation of a thermally insulating char layer.

Facile Synthesis of Band Gap-Tunable Kappa-Carrageenan-Mediated C,S-Doped TiO2 Nanoparticles for Enhanced Dye Degradation.

Semiconducting nanoparticles (SNPs) have garnered significant attention for their role in photocatalysis technology, offering a cost-effective and highly efficient method for breaking down organic dyes. Of particular significance within SNP-based photocatalysis are tunable band gap TiO2 nanoparticles (NPs), which demonstrate remarkable enhancement in photocatalytic efficiency. In the present work, we introduce an approach for the synthesis of TiO2 NPs using kappa-carrageenan (κ-carrageenan), not just as a reducing and stabilizing agent but as a dopant for the resulting TiO2 NPs. During the synthesis of TiO2 NPs in the presence of sulfate-rich carrageenan, the process predominantly leaves residual sulfur and carbon. The presence of residual carbon, in conjunction with sulfur doping, as indicated by fast FTIR spectra, XPS, and EDX, leads to a significant reduction in the band gap of the resulting composite to 2.71 eV. The reduction of composite band gap yields remarkable degradation of methylene blue (99.97%) and methyl orange (97.84%). This work presents an eco-friendly and highly effective solution for the swift removal of environmentally harmful organic dyes.

Dopamine-Functionalized Gold Nanoparticles for Colorimetric Detection of Histamine.

Histamine, a primary biogenic amine (BA) generated through the decarboxylation of amino acids, concentration increases in protein-rich foods during deterioration. Thus, its detection plays a crucial role in ensuring food safety and quality. This study introduces an innovative approach involving the direct integration of dopamine onto gold nanoparticles (DCt-AuNP), aiming at rapid histamine colorimetric detection. Transmission electron microscopy revealed the aggregation of uniformly distributed spherical DCt-AuNPs with 12.02 ± 2.53 nm sizes upon the addition of histamine to DCt-AuNP solution. The Fourier-transform infrared (FTIR) spectra demonstrated the disappearance of the dicarboxy acetone peak at 1710 cm-1 along with the formation of well-defined peaks at 1585 cm-1, and 1396 cm-1 associated with the N-H bending modes and the aromatic C=C bond stretching vibration in histamine molecule, respectively, confirming the ligand exchange and interactions of histamine on the surface of DCt-AuNPs. The UV-vis spectra of the DCt-AuNP solution exhibited a red shift and a reduction in surface plasmon resonance (SPR) peak intensity at 518 nm along with the emergence of the 650 nm peak, signifying aggregation DCt-AuNPs with increasing histamine concentration. Notably, color transitions from wine-red to deep blue were observed in the DCt-AuNP solution in response to histamine, providing a reliable colorimetric signal. Dynamic Light Scattering (DLS) characterization showed a significant increase in the hydrodynamic diameter, from ∼15 to ∼1690 nm, confirming the interparticle cross-linking of DCt-AuNPs in the presence of histamine. This newly developed DCt-AuNP sensor provides colorimetric results in less than a minute that exhibits a remarkable naked-eye histamine detection threshold of 1.57 µM and a calculated detection limit of 0.426 µM, making it a promising tool for the rapid and sensitive detection of histamine.

Valorization of Agricultural Rice Straw as a Sustainable Feedstock for Rigid Polyurethane/Polyisocyanurate Foam Production.

Agricultural rice straw (RS), often discarded as waste in farmlands, represents a vast and underutilized resource. This study explores the valorization of RS as a potential feedstock for rigid polyurethane/polyisocyanurate foam (RPUF) production. The process begins with the liquefaction of RS to create an RS-based polyol, which is then used in a modified foam formulation to prepare RPUFs. The resulting RPUF samples were comprehensively characterized according to their physical, mechanical, and thermal properties. The results demonstrated that up to 50% by weight of petroleum-based polyol can be substituted with RS-based polyol to produce a highly functional RPUF. The obtained foams exhibited a notably low apparent density of 18-24 kg/m3, exceptional thermal conductivity ranging from 0.031-0.041 W/m-K, and a high compressive strength exceeding 250 kPa. This study underlines the potential of the undervalued agricultural RS as a green alternative to petroleum-based feedstocks to produce a high-value RPUF. Additionally, the findings contribute to the sustainable utilization of abundant agricultural waste while offering an eco-friendly option for various applications, including construction materials and insulation.

Development of High-Performance Coconut Oil-Based Rigid Polyurethane-Urea Foam: A Novel Sequential Amidation and Prepolymerization Process.

The utilization of coconut diethanolamide (p-CDEA) as a substitute polyol for petroleum-based polyol in fully biobased rigid polyurethane-urea foam (RPUAF) faces challenges due to its short chain and limited cross-linking capability. This leads to compromised cell wall resistance during foam expansion, resulting in significant ruptured cells and adverse effects on mechanical and thermal properties. To address this, a novel sequential amidation-prepolymerization route was employed on coconut oil, yielding a hydroxyl-terminated poly(urethane-urea) prepolymer polyol (COPUAP). Compared to p-CDEA, COPUAP exhibited a decreased hydroxyl value (496.3-473.2 mg KOH/g), an increase in amine value (13.464-24.561 mg KOH/g), and an increase in viscosity (472.4-755.8 mPa·s), indicating enhanced functionality of 34.3 mgKOH/g and chain lengthening. Further, COPUAP was utilized as the sole B-side polyol in the production of RPUAF (PU-COPUAP). The improved functionality of COPUAP and its improved cross-linking capability during foaming have significantly improved cell morphology, resulting in a remarkable 4.7-fold increase in compressive strength (132-628 kPa), a 3.5-fold increase in flexural strength (232-828 kPa), and improved insulation properties with a notable decrease in thermal conductivity (48.02-34.52 mW/m·K) compared to PU-CDEA in the literature. Additionally, PU-COPUAP exhibited a 16.5% increase in the water contact angle (114.93° to 133.87°), attributing to the formation of hydrophobic biuret segments and a tightly packed, highly cross-linked structure inhibiting water penetration. This innovative approach sets a new benchmark for fully biobased rigid foam production, delivering high load-bearing capacity, exceptional insulation, and significantly improved hydrophobicity.

Producing polyglycerol polyester polyol for thermoplastic polyurethane application: A novel valorization of glycerol, a by-product of biodiesel production.

The production of biodiesel generates glycerol as a by-product that needs valorization. Glycerol, when converted to polyglycerol, is a potential polyol for bio-based thermoplastic polyurethane (TPU) production. In this study, a novel polyglycerol polyester polyol (PPP) was developed from refined glycerol and coconut oil-based polyester polyol. Glycerol was first converted to glycerol acetate and then polymerized with coconut oil-based polyester polyol (CPP) as secondary polyol and phthalic anhydride. The resulting PPP polymerized at 220 °C and OH:COOH molar ratio of 2.5 exhibited an OH number of <100 mg KOH·g sample-1, an acid number of <10 mg KOH·g sample-1, and a molecular weight (MW) of 3697 g mol-1 meeting the polyol requirement properties for TPU (Handlin et al., 2001; Parcheta et al., 2020) [1-2]. Fourier-transform infrared (FTIR) spectroscopic characterization determined that higher reaction temperatures increase the polymerization rate and decrease the OH and acid numbers. Further, higher OH:COOH molar ratios decrease the polymerization rate and acid number, and increase the OH number. Gel permeation chromatography determined the molecular weight of PPP and suggested two distinct molecular structures which differ only in the number of moles of CPP in the structure. A differential scanning calorimetric (DSC) experiment on a sample of PPP-based polyurethane revealed that it was able to melt and remelt after 3 heating cycles which demonstrates its thermoplastic ability. The novel PPP derived from the glycerol by-product of biodiesel industries can potentially replace petroleum-derived polyols for TPU production.

Production of Bio-Based Polyol from Coconut Fatty Acid Distillate (CFAD) and Crude Glycerol for Rigid Polyurethane Foam Applications.

This study propounds a sustainable alternative to petroleum-based polyurethane (PU) foams, aiming to curtail this nonrenewable resource's continued and uncontrolled use. Coconut fatty acid distillate (CFAD) and crude glycerol (CG), both wastes generated from vegetable oil processes, were utilized for bio-based polyol production for rigid PU foam application. The raw materials were subjected to catalyzed glycerolysis with alkaline-alcohol neutralization and bleaching. The resulting polyol possessed properties suitable for rigid foam application, with an average OH number of 215 mg KOH/g, an acid number of 7.2983 mg KOH/g, and a Gardner color value of 18. The polyol was used to prepare rigid PU foam, and its properties were determined using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis/derivative thermogravimetric (TGA/DTA), and universal testing machine (UTM). Additionally, the cell foam morphology was investigated by scanning electron microscope (SEM), in which most of its structure revealed an open-celled network and quantified at 92.71% open-cell content using pycnometric testing. The PU foam thermal and mechanical analyses results showed an average compressive strength of 210.43 kPa, a thermal conductivity of 32.10 mW·m-1K-1, and a density of 44.65 kg·m-3. These properties showed its applicability as a type I structural sandwich panel core material, thus demonstrating the potential use of CFAD and CG in commercial polyol and PU foam production.

Coconut power: a sustainable approach for the removal of Cr6+ ions using a new coconut-based polyurethane foam/activated carbon composite in a fixed-bed column.

To attain efficient removal of hexavalent chromium (Cr6+) from aqueous solutions, a novel polyurethane foam-activated carbon (PUAC) adsorbent composite was developed. The composite material was synthesized by the binding of coconut shell-based activated carbon (AC) onto a coconut oil-based polyurethane matrix. To thoroughly characterize the physicochemical properties of the newly developed material, various analytical techniques including FTIR spectroscopy, SEM, XRD, BET, and TGA analyses were conducted. The removal efficiency of the PUAC composite in removing Cr6+ ions from aqueous solutions was evaluated through column experiments with the highest adsorption capacity of 28.41 mg g-1 while taking into account variables such as bed height, flow rate, initial Cr6+ ion concentration, and pH. Experimental data were fitted using Thomas, Yoon-Nelson, and Adams-Bohart models to predict the column profiles and the results demonstrate high breakthrough and exhaustion time dependence on these variables. Among the obtained R2 values of the models, a better fit was observed using the Thomas and Yoon-Nelson models, indicating their ability to effectively predict the adsorption of Cr6+ ions in a fixed bed column. Significantly, the exhausted adsorbent can be conveniently regenerated without any noteworthy loss of adsorption capability. Based on these findings, it can be concluded that this new PUAC composite material holds significant promise as a potent sorbent for wastewater treatment backed by its excellent performance, cost-effectiveness, biodegradability, and outstanding reusability.

A novel reaction mechanism for the synthesis of coconut oil-derived biopolyol for rigid poly(urethane-urea) hybrid foam application.

Coconut oil (CO) has become one of the most important renewable raw materials for polyol synthesis due to its abundance and low price. However, the saturated chemical structure of CO limits its capability for functionalization. In this study, a novel reaction mechanism via the sequential glycerolysis and amidation of CO triglycerides produced an amine-based polyol (p-CDEA). The synthesized biopolyol has a relatively higher hydroxyl value of 361 mg KOH per g relative to previously reported CO-based polyols with values ranging from 270-333 mg KOH per g. This primary hydroxyl-rich p-CDEA was used directly as a sole B-side polyol component in a polyurethane-forming reaction, without further purification. Results showed that a high-performance poly(urethane-urea) (PUA) hybrid foam was successfully produced. It has a compressive strength of 226 kPa and thermal conductivity of 23.2 mW (m-1 K-1), classified as type 1 for a rigid structural sandwich panel core and type 2 for rigid thermal insulation foam applications according to ASTM standards. Fourier-transform infrared (FTIR) spectroscopy was performed to characterize the chemical features of the polyols and foams. Scanning electron microscopy (SEM) analysis was also performed to evaluate the morphological structures of the synthesized foams. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were conducted to investigate the foam's thermal characteristics. Thus far, this work is the first to report a novel and effective reaction mechanism for the synthesis of a highly functional CO-derived polyol and the first CO-based polyol with no petroleum-based replacement that may serve as raw material for rigid PUA foam production. PUA hybrid foams are potential insulation and structural materials. This study further provided a compelling case for enhanced sustainability of p-CDEA PUA hybrid foam against petroleum-based polyurethane.