Engineering Lignocellulose Fibers with Higher Thermal Stability through Natural Fiber Welding

This study reveals how natural fiber welding (NFW) can be used to engineer biopolymer materials with improved thermal stability. First, it is shown how NFW without binders improves lignocellulose yarn thermal stability by ≈17 °C, primarily by condensing microfibril structure. Next, silanized‐cellulose nanofibrils (Si‐CNFs) are developed as NFW binders; this silanization process alters CNF physical and thermal properties. During pyrolysis, Si_x O_y networks form, which delay CNF decomposition (up to 37 °C), slow cellulose mass loss rates (up to 89%), and can enhance char yield more than twofold. When used as NFW binders, Si‐CNFs increase lignocellulose yarn thermal stability (up to 17 °C) proportional to siloxane amount, and can reduce cellulose mass loss rates (≈25% compared to welding without binder). These exciting results highlight the potential of NFW as a green‐engineering process to transform natural fibers into more thermally stable, biocomposite textile yarns.     

Preparation and thermal stability of new cellulose‐based poly(propylene imine) and poly(amido amine) hyperbranched derivatives

New cellulose‐based hyperbranched derivatives having different degrees of branching were prepared via reaction of cellulose with acrylonitrile followed by reduction of nitrile groups and successive reaction with acrylonitrile or methylacrylate. First‐ (G = 1) and half‐ (G = 0.5) generation cellulose‐based hyperbranched poly(propylene imine) or poly(amido amine) derivatives have been prepared with high reaction yield. The structure of the prepared derivatives was confirmed by Fourier transform infrared and ¹³C nuclear magnetic resonance (¹³C NMR). Thermal stability of the different cellulose‐based hyperbranched derivatives were examined using thermogravimetric analysis to study the effect of branching on the thermal decomposition parameters. The onset degradation temperature and the activation energy of the thermal degradation decreased with increasing the branching of the cellulose‐based hyperbranched derivatives. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2079–2087, 2006     

Thermal degradation of a phenolic resin,vegetable fibers,and derived composites

The thermal degradation behavior of resol, several vegetable fibers (two types of cotton fibers, sisal and sugar cane bagasse) and derived polymer composites have been investigated using thermogravimetric analysis (TGA). The initial thermal degradation temperature T_ONSET, the temperature at the maximum degradation rate TD_M, and the char left at 500°C corresponding to the crosslinked resol were higher than the values measured for the fibers and their composites. Thus, the addition of the fibers reduced the thermal resistance of the phenolic thermoset. The polymer and the fiber‐composites showed a complex degradation involving different thermal decomposition processes. For that reason, the DTG curves were deconvoluted and a phenomenological kinetic expression was found for each individual peak. The overall thermal decomposition curve was recalculated adding each degradation process weighted according to its contribution to the total weight loss. An increase in the activation energy corresponding to the cellulose degradation was observed in the composites, highlighting the protective action of the resin encapsulating the fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of polychloroprene nanocomposites with cellulose nanofibers from oil palm empty fruit bunches as a nanofiller

Cellulose nanofibers (CNFs) from oil palm empty fruit bunches were chemically modified by acetylation with acetic anhydride and pyridine (as the solvent and catalyst). The acetylated CNFs showed good dispersion in a polychloroprene (PCR) matrix. The tensile strength and modulus of neat PCR were improved, whereas its elongation at break decreased with increasing nanofiber content. Above the glass‐transition temperature (T_g), the dynamic mechanical analysis profiles showed that the storage modulus of the PCR–cellulose nanocomposites was higher than that of neat PCR. Meanwhile, the thermal stability was still maintained, and the T_g was close to the neat PCR at the 5 wt % addition level of CNFs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40159.     

Synthesis,characterization and properties of cellulose‐grafted glycine derivatives

Novel Schiff base cellulose derivatives were successfully prepared by a bridge‐coupling reaction from dialdehyde cellulose (DAC), which was obtained by the selective oxidation of sodium periodate to cotton fibers, in which the glycine (Gly) was bonded onto the DAC chains by a Schiff base reaction with p‐nitrobenzaldehyde as a bridge. The structures of the graft copolymer (DAC‐g‐Gly) were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, solid‐state NMR, and scanning electronic microscopy. The thermodynamic properties were analyzed by thermogravimetric analysis and differential scanning calorimetry, and the biodegradability was also tested by the microbial degradation and the active sludge method. The results indicate that Gly was connected to DAC by chemical bonding, which changed the thermal stability, and that DAC‐g‐Gly could be biodegraded significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40929.     

Thermal,spectral and morphological studies on cellulose,cellulose ethylthiophosphate and its metal complexes in air

Metal complexes of thiophosphorylated cellulose, when heated, give rise to high char yields. These and related observations suggest that such derivatisation may give rise to novel flame retardant treatments for cellulosic materials. The kinetics of thermal degradation of cellulose, cellulose ethylthiophosphate (CESP) and metal complexes of the CESP have been studied by thermogravimetry (TG) and differential thermal analysis (DTA) from ambient temperature to 700°C in dynamic air to investigate the potential flame retardance of the CESP and its metal complexes. Various parameters such as energy, entropy, enthalpy and free energy of activation have been calculated using the Broido method and transition state theory. For the decomposition stage of thermal degradation, the activation energies of the CESP samples lie in the range 53-133 kJmol^?1 and of the metal complexes, 108-177kJmol^?1, which are found to be lower than that of cellulose (187 kJmol^?1). Scanning electron micrographs of the CESP show that the fibrillar structure of cotton has become more evident and chars retain the general morphology of the original fibre although severe, localised zones of damage reflect the gross chemical and physical changes occurring during pyrolysis. The IR spectra of chars of modified samples indicate formation of compounds containing C=O, C=C and P=O groups. The mechanisms of thermal degradation of the CESP and its metal complexes have been proposed.     

Thermal degradation of cellulose and cellulose esters

Cellulose, cellulose diacetate (CDA), cellulose triacetate (CTA), cellulose nitrate (CN), and cellulose phosphate (CP) were subjected to dynamic thermogravimetry in nitrogen and air. The thermostability of the cellulose and its esters was estimated, taking into account the values of initial thermal degradation temperature T_d, the temperature at the maximum degradation rate T_dm, and char yield at 400°C. The results show that these polymers may be arranged in the following order of increasing thermostability: CN < CP < regenerated cellulose < filter cotton < CDA < CTA. The activation energy (E), order (n), and frequency factor (Z) of their degradation reactions were obtained following the Friedman, Chang, Coats–Redfern, Freeman–Carroll, and Kissinger methods. The dependence of T_d, T_dm, E, n, Ln Z, and char yield at 400°C on molecular weight and test atmosphere is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:293–304, 1998     

Preparation and performance study of cordierite/mullite composite ceramics for solar thermal energy storage

The employment of solar energy in recent years has reached a remarkable edge. It has become even more popular as the cost of fossil fuel continues to rise. Energy storage system improves an adjustability and marketability of solar thermal and allowing it to produce electricity in demand. This study attempted to prepare cordierite/mullite composite ceramics used as solar thermal storage material from calcined bauxite, talcum, soda feldspar, potassium feldspar, quartz, and mullite. The thermal physical performances were evaluated and characterized by XRD, SEM, EPMA, and EDS. It was found that the optimum sintering temperature was 1280°C for preparing, and the corresponding water adsorption was 11.25%, apparent porosity was 23.59%, bulk density was 2.10 mg·cm^?3, bending strength was 88.52 MPa. The residual bending strength of specimen sintered at 1280°C after thermal shock of 30 times decreased to be 57 MPa that was 36% lower than that before. The thermal conductivity of samples sintered at 1280°C was tested to be 2.20 W·(m·K)^?1 (26°C), and after wrapped a PCM (phase change materials) of K₂SO₄, the thermal storage density was 933 kJ·kg^?1 with the temperature difference (ΔT) ranged in 0‐800°C. The prepared cordierite/mullite composite ceramic was proved to be a promising material for solar thermal energy storage.     

Polyaniline‐modified cellulose nanofibrils as reinforcement of a smart polyurethane

Segmented polyurethanes exhibiting shape memory properties were modified by the addition of polyaniline (PANI)‐coated cellulose nanofibrils (CNFs). The two‐phase structure of the polymer is responsible for the material's ability to ‘remember’ and autonomously recover its original shape after being deformed in response to an external thermal stimulus. PANI was grown on the surface of the CNFs via in situ polymerization. Modified nanocrystals were added to the segmented polyurethane in concentrations ranging from 0 to 15 wt%. The changes in the material properties associated with the percolation of the coated fibrils appear at higher concentrations than previously observed for non‐modified CNFs, which suggests that fibril agglomeration is occurring due to the PANI coating. The shape memory behavior of the composites is maintained at about the same level as that of the unfilled polyurethane only up to 4 wt% of fibrils. At higher concentrations, the rigidity of the nanofibrils as well as their interaction with the hard‐segment phase and the increasing difficulty of dispersing them in the polymer collaborate to produce early breakage of the specimens when stretched at temperatures above the melting point of the soft segments. Copyright © 2010 Society of Chemical Industry     

Preparation and properties of the single‐walled carbon nanotube/cellulose nanocomposites using N‐methylmorpholine‐N‐oxide monohydrate

Single‐walled carbon nanotube (SWNT)/cellulose nanocomposite films were prepared using N‐methylmorpholine‐N‐oxide (NMMO) monohydrate as a dispersing agent for the acid‐treated SWNTs (A‐SWNTs) as well as a cellulose solvent. The A‐SWNTs were dispersed in both NMMO monohydrate and the nanocomposite film (as confirmed by scanning electron microscopy) because of the strong hydrogen bonds of the A‐SWNTs with NMMO and cellulose. The mechanical properties, thermal properties, and electric conductivity of the nanocomposite films were improved by adding a small amount of the A‐SWNTs to the cellulose. For example, by adding 1 wt % of the A‐SWNTs to the cellulose, tensile strain at break point, Young's modulus, and toughness increased ～ 5.4, ～ 2.2, and ～ 6 times, respectively, the degradation temperature increased to 9°C as compared with those of the pure cellulose film, and the electric conductivities at ? (the wt % of A‐SWNTs in the composite) = 1 and 9 were 4.97 × 10^?4 and 3.74 × 10^?2 S/cm, respectively. Thus, the A‐SWNT/cellulose nanocomposites are a promising material and can be used for many applications, such as toughened Lyocell fibers, transparent electrodes, and soforth. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

CHARACTERIZATION OF POLYMER COMPLEXES BY THERMAL AND IR SPECTRAL ANALYSES

The characterization of polymer complexes were studied by thermal and infrared (IR) spectral analyses from room temperature to 1000°C and from wave number 4000 cm^?1 to 200 cm^?1, respectively. The polymer complexes were those prepared from cellulose ether (e.g., carboxymethyl cellulose and hydroxyethyl cellulose) with some transition metals (e.g., CrCl₃, FeCl₃, CuCl₂, CoCl₂, and NiCl₂). The thermal analysis measurements, such as activation energy (E_a ) and order of degradation (n), were calculated from nonisothermal thermogravimetric analysis, using the Coats-Redfern equation and the least squares method. The results obtained show that the complexation of cellulose ether with most mentioned metal ions improved their thermal stabilities. There is a relationship between the measurements of thermal analysis and the degree of ligand–metal–σ bond (nephlauxetic parameter, β), electronegativity of the metal cation, and the chelating sites of the ligand. The IR-spectra measurements, such as the shift of the band maximum, correspond to the stretching vibration of OH, the mean strength of the hydrogen bond, and the degree of crystallinity, evidence to some extent of the results of thermal analysis, especially the case of carboxymethyl cellulose–metal complexes.     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Sonochemically Prepared GdWNFs/CNFs Nanocomposite as an Electrode Material for the Electrochemical Detection of Antibiotic Drug in Water Bodies

The work demonstrates the development of an electrochemical sensor for quantification of Chloramphenicol (CA) using pencil graphite electrode (PGE) modified with Gadolinium tungstate nano flakes and carbon nano fibers composite (PGE/GWNfs/CNFs). The composite was further characterized and confirmed by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, transmission electron microscopy analysis. The prepared GWNfs/CNFs nano composite was fabricated by drop casting method to get PGE/GWNfs/CNFs working electrode. The modified electrode is then analyzed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) methods for its electrochemical and electrocatalytic property. The electrochemical investigation of developed sensor shows enhanced activity towards electro-oxidation of CA. The DPV studies revealed high efficacy characteristics such as sensitivity in the range 0.03984 µA µM^?1 cm^?2, selectivity, good linear range (5–50 μM), and low detection limit (0.4 μM). The study benchmarks the use of GWNfs/CNFs as an excellent transducer material in electrochemical sensing of CA in standard samples thus, it finds an efficient potential application in the analysis of CA in environment sample analysis.

     

Effects of Carbon Nanofiber on Dielectric Properties of PMN/CNFs/EP Composites

A kind of new composite material composed of piezoelectric ceramic lead magnesium niobate-lead zirconate-lead titanate (PMN)/carbon nanofibers (CNFs)/epoxy resin (EP) were prepared by a resin casting method. The effects of carbon nanofibers on dielectric properties of PMN/CNFs/EP composites were investigated in this paper. The concetration of CNFs had significant effects on dielectric constant, dielectric loss, dielectric frequency dependence and dielectric temperature dependence of PMN/CNFs/EP composites. When the content of CNFs increased from 0 to 0.8 wt% of the epoxy resin, the dielectric constant at 1 kHz increased sharply from 13.6 to 158, and the dielectric loss increased from 0.0524 to 2.59. In plots of the dielectric constant against frequency and dielectric loss against frequency, the dielectric constant and dielectric loss reduced dramatically at lower frequency ranging from zero to about 10⁵ Hz, then approach to be stable at frequency higher than 10⁵ Hz. Moreover, as to the effects of temperature on dielectric constant and dielectric loss of PMN/CNFs/EP composites, the dielectric constant of composite increased ranging from 25°C to 160°C, and the dielectric loss of composite also showed increase besides that with CNFs content 0.8 wt%.     

Thermal and mechanical characterization of EVA/banana fiber-derived cellulose composites

Composite films based on poly(ethylene-co-vinyl acetate) (EVA) and cellulose derived from banana plant waste have been prepared and characterized. Cellulose whiskers isolated from, banana fibers, by an acid hydrolysis method and were incorporated into the EVA matrix by solution casting technique. The composite films were subsequently examined by scanning electron microscopy, thermogravimetry, differential scanning calorimetry, and FTIR spectroscopy. Compared with pure EVA and cellulose, the EVA/cellulose composite systems showed superior thermal stability. The mechanical testing of the composite films revealed that the tensile strength and elastic modulus were increased after cellulose incorporation into EVA. Among the EVA/cellulose composites, 7.5% cellulose loaded EVA showed the highest tensile strength. The percentage strain at break of the EVA/cellulose composite systems was found to be decreased which has been attributed to the restricted mobility of the polymer matrix by the presence of cellulose. X-ray diffraction studies showed that the EVA/cellulose composites were more crystalline than EVA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dual action bactericides: Quaternary ammonium/N‐halamine‐functionalized cellulose fiber

Bi‐functional antibacterial material was prepared by co‐grafting N‐halamine and quaternary ammonium salt monomers from cellulose fiber. The grafted fiber was characterized by Fourier transform infrared spectra, and X‐ray photoelectron spectra. The N‐halamine derived from the precursor 4‐[(acryloxy)methyl]‐4‐ethyl‐2‐oxazolidinone via chlorination treatment and the oxidative chlorine (Cl⁺) leaching behavior were investigated. The antibacterial activities of singly (only QAs‐functionalized or only Cl⁺‐releasing) and dual (QAs‐functionalized and Cl⁺‐releasing) functional cellulose fibers were tested against Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. Compared to singly functionalized formulations, the bi‐functional cellulose fiber exhibited excellent and rapid bactericidal performance against both E. coli and S. aureus. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40070.     

Melt processing of polyamide 12 and cellulose nanocrystals nanocomposites

The fabrication of nanocomposites of polyamide 12 (PA12) and cellulose nanocrystals (CNCs) isolated from cotton and tunicates is reported. Through a comparative study that involved solution‐cast (SC) and melt‐processed materials, it was shown that PA12/CNC nanocomposites can be prepared in a process that appears to be readily scalable to an industrial level. The results demonstrate that CNCs isolated from the biomass by phosphoric acid hydrolysis display both a sufficiently high thermal stability to permit melt processing with PA12, and a high compatibility with this polymer to allow the formation of nanocomposites in which the CNCs are well dispersed. Thus, PA12/CNC nanocomposites prepared by melt‐mixing the two components in a co‐rotating roller blade mixer and subsequent compression molding display mechanical properties that are comparable to those of SC reference materials. Young's modulus and maximum stress could be doubled in comparison to the neat PA12 by introduction of 10% (CNCs from tunicates) or 15% w/w (CNCs from cotton) CNCs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42752.     

In situ polymerization of aniline on acrylamide grafted cotton

In this article, polyaniline (PANI)/cotton composite were prepared by in situ polymerization on the grafted cotton. First, acrylamide was grafted onto cotton cellulose using a radical graft polymerization process and some influencing factors were studied. Then polyaniline/cotton conductive composite fabrics were prepared by chemical in situ polymerization on the grafted cotton. The influences of the concentration of ammonium persulfate, aniline, hydrochloric acid, and the reaction time to the conductivity and K/S of composite fabric were studied. By contrasting, graft brought on an improvement of about one order of magnitude to the conductivity of composite fabric. The strength, TG, FTIR‐ATR, and SEM of prepared fabric were measured. The thermal stability and tear strength of composite fabric reduced, whereas PANI exhibited a rough but uniform, coherent PANI coating on surface of cotton fiber. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Noncovalent functionalization of boron nitride and its effect on the thermal conductivity of polycarbonate composites

Polycarbonate (PC) is an engineering thermoplastic with excellent insulation and mechanical properties. However, the low thermal conductivity restricted its application in electronic devices. Hexagonal boron nitride (h ‐BN) microparticle, a promising material with high thermal conductivity, was functionalized with cationic polyacrylamide (CPAM) and introduced into PC matrix to improve the thermal conductivity. SEM and XRD analysis showed that the modified BN (CBN) particles oriented and formed thermal conductive pathways within PC matrix. The formation of large‐area oriented CBN significantly improved the thermal conductivity and thermal stability of composites. At 20 wt % CBN loading, the thermal conductivity of 0.7341 Wm^?1 K^?1 and the temperature for 5% weight loss (T ₅) of 498.6 °C were obtained, which was 3.1 times and 77 °C higher than that of pure PC, respectively. Furthermore, outstanding electrical insulation property of matrix was retained in the composites. These results revealed that PC/CBN composite was a promising material for thermal management and electrical enclosure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44978.     

Synthesis of cellulose/reduced graphene oxide/polyaniline nanocomposite and its properties

A series of conductive nanocomposites cellulose/reduced graphene oxide/polyaniline (cellulose/RGO/PANi) were synthesized via in situ oxidative polymerization of aniline on cellulose/RGO with different RGO loading to study the effect of RGO on the properties of nanocomposites. The results showed that when RGO is inserted into cellulose/PANi structure, its thermal stability and conductivity are increased. So that adding of only 0.3 wt% RGO into the cellulose/PANi structure, its conductivity is increased from 1.1 × 1 10^?1 to 5.2 × 110^?1 S/cm. Scanning electron microscopy results showed that the PANi nanoparticles are formed a continuous spherical shape over the cellulose/RGO template; this increases the thermal stability of nanocomposite.