Extraction and Characterization of Novel Lignocellulosic Fibers From Thespesia Lampas Plant

In this work, the lignocellulosic fibers from the plant Thespesia lampas were extracted and investigated in detail. The prime objective of this work was to study the effect of alkali treatment on the chemical composition, tensile properties, morphological and structural changes, and thermal degradation of Thespesia lampas fibers. Chemical analysis, FT-IR, and ¹³C CP-MAS NMR spectroscopic studies indicated lowering of amorphous hemicellulose content on alkali treatment. Wide-angle X-ray diffraction studies indicated increase in crystallinity of the fibers on alkali treatment. The tensile strength and modulus of the fibers and thermal stability increased on alkali treatment. Scanning electron micrographs revealed roughening of the surface of the fibers due to the removal of the hemicellulose layer on alkali treatment. Tensile properties of Thespesia fibers were compared to those of other important natural fibers, and it was indicated as an alternative suitable source for composite construction.     

Tensile,thermal, and antibacterial characterization of composites of cellulose/modified Pennisetum purpureum natural fibers with in situ generated copper nanoparticles

Eco-friendly all cellulose composites were developed using cellulose as matrix and nanocomposite (in situ generated copper nanoparticles modified Napier Grass Fibers (NGFs)) as fillers for the antibacterial applications. The content of the nanocomposite filler was increased from 1?wt.% to 5?wt.% in the cellulose matrix. All these composites were characterized by Scanning Electron Microscopy (SEM), Tensile, Thermo Gravimetric Analysis (TGA), and antibacterial tests. SEM-EDX analysis revealed the in situ generation of copper nanoparticles on the surface of the films. Further, all cellulose composites showed good thermal stability. A minimum of 30% increase in char residue was observed in all cellulose nanocomposites compared to matrix. Antibacterial analysis indicated an excellent clear zone formation against both Gram Negative (Escherichia coli) and Gram Positive (Staphylococcus) bacteria. Hence, all these cellulose nanocomposite films can be considered as antibacterial packaging and dressing materials in medical field.     

Preparation and Characterization of Polypropylene Carbonate Bio-Filler (Eggshell Powder) Composite Films

In recent years, biodegradable polymer composites have attracted considerable attention due to inadequate and depleting petroleum resources and to replace nonbiodegradable synthetic polymers posing environment problems. In the present work, biodegradable composites based on polypropylene carbonate (PPC)/eggshell powder (ESP) were prepared by the solution-casting method using chloroform as the solvent. Polypropylene carbonate was loaded with 1 to 5 wt% of eggshell powder (particle size < 40 µm). Characterization of the composites was accomplished by Fourier transform-infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), and X-ray diffraction (XRD) analysis, and morphological studies were carried out by optical microscopy (OM) and scanning electronic microcopy (SEM). The tensile properties of the composite films were found to be higher than those of neat PPC matrix and increased with ESP content up to 4 wt.% and then decreased. This work offers an easy path to manufacture ecofriendly PPC/eggshell powder composite films with improved properties, and reducing, in some cases, the demand for petroleum-based plastics such as polyolefins.     

Tensile and Thermal Properties of Poly(lactic acid)/Eggshell Powder Composite Films

Biodegradable composite films of poly(lactic acid) (PLA)/eggshell powder (ESP) were prepared by the composite film casting method using chloroform as the solvent. ESP was loaded in PLA in 1 to 5 wt.%. The films were subjected to tensile, FT-IR spectral, thermogravimetric, X-ray, and microscopic analyses. The tensile strength and modulus of the composite films were found to be higher than those of PLA and increased with ESP content up to 4 wt.% and then decreased. A reverse trend was observed in the case of percentage elongation at break. The X-ray diffractograms of the composite films indicated an increase in crystallinity with ESP content. The optical micrographs indicated uniform distribution of ESP particles in the composite films. However, the fractographs indicated agglomeration of ESP particles at 5 wt.% loading. The FT-IR spectra revealed no specific interactions between PLA and ESP. The thermal stability of the composite films increased with ESP content.     

Preparation and Properties of Biodegradable Spent Tea Leaf Powder/Poly(Propylene Carbonate) Composite Films

The aim of the present work is to develop novel bio-based lightweight material with improved tensile and thermal properties. Spent tea leaf powder (STLP) was used as a filler to improve the tensile and thermal properties of polypropylene carbonate (PPC). Tea is an important material used in hotels and households, and spent tea leaf is a resulting solid waste. Composite films with STLP were obtained by the solution casting method. These films were characterized by optical and scanning electron microscopy, Fourier transform-infrared spectroscopy, thermogravimetric analysis, and tensile testing to examine the effect of filler content on the properties of the composites. The results showed that composite films have increased tensile strength due to enhanced interfacial adhesion between the filler and the matrix. In addition, the composite films also exhibited higher thermal degradation temperatures than pure polypropylene carbonate. The morphology results indicate that there is a good interface interaction between STLP and PPC. Results of the study reveal STLP to be a promising green filler for polymer plastics.     

Biodegradable aliphatic polyesters. Part I. Properties and biodegradation of poly(butylene succinate-co-butylene adipate)

A series of aliphatic homopolyesters and copolyesters was prepared from 1,4 butanediol and dimethylesters of succinic and adipic acids through a two-step process of transesterification and polycondensation. The synthesized polyesters were characterized by means of nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and mechanical property measurements. The homopolymer poly(butylene succinate) exhibited the highest tensile strength, which decreased with increasing adipate unit content, passed through a minimum at copolyester composition close to equimolarity and then increased towards the value of poly(butylene adipate). It is interesting to note that in contrast to tensile strength, the elongation at break increased for adipate unit content of 20-40 mol%. The biodegradation of the polymers was investigated by soil burial and enzymatic hydrolysis using three enzymes, Candida cylindracea lipase, Rhizopus delemar lipase, and Pseudomonas fluorescens cholesterol esterase. It appears that the key factor affecting material degradation was its crystallinity.     

Biodegradable aliphatic polyesters. Part II. Synthesis and characterization of chain extended poly(butylene succinate-co-butylene adipate)

Poly(butylene succinate-co-butylene adipate) was obtained from 1,4-butanediol and dimethyl esters of succinic and adipic acids through a two step process of transesterification and polycondensation. High molecular weight polyesters were synthesized using hexamethylene diisocyanate as chain extender. The effect of chain extension reaction time and chain extender content on polyester molecular weight, thermal and mechanical properties, was investigated. Polyesters were characterized by means of nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and mechanical property measurements. Chain extension reaction had as a result the significant increase of polyester molecular weight leading to increased tensile strength. Polyester crystallinity, as calculated from XRD and DSC analysis, and melting temperature decreased upon chain extension, while glass transition temperature increased. Polyester biodegradation was investigated by soil burial and enzymatic hydrolysis using the enzyme Pseudomonas fluorescens cholesterol esterase. It appears that biodegradation was affected by polyester crystallinity, rather than by its molecular weight.     

Processing of poly(lactic acid): Characterization of chemical structure, thermal stability and mechanical properties

The processing of poly(lactic acid) (injection and extrusion/injection) as well as annealing of processed materials were studied in order to analyze the variation of its chemical structure, thermal degradation and mechanical properties. Processing of PLA was responsible for a decrease in molecular weight, as determined by GPC, due to chain scission. The degree of crystallinity was evaluated by means of differential scanning calorimetry and X-ray diffraction. It was found that mechanical processing led to the quasi disappearance of crystal structure whereas it was recovered after annealing. These findings were qualitatively corroborated by means of FTIR. By analyzing ¹H NMR and ¹³C NMR chemical shifts and peak areas, it was possible to affirm that the chemical composition of PLA did not change after processing, but the proportion of methyl groups increased, thus indicating the presence of a different molecular environment. The thermal stability of the various materials was established by calculating various characteristic temperatures from thermograms as well as conversion and conversion derivative curves. Finally, the mechanical behaviour was determined by means of tensile testing (Young modulus, yield strength and elongation at break).     

Effect of Chemical Treatment and Fiber Loading on Mechanical Properties of Borassus (Toddy Palm) Fiber/Epoxy Composites

The aim of the present study was to investigate and compare the mechanical properties of untreated and chemically modified Borassus fiber–reinforced epoxy composites. Composites were prepared by the hand lay-up process by reinforcing Borassus fibers with epoxy matrix. To improve the fiber-matrix adhesion properties, alkali (NaOH) and alkali combined with silane (3-aminopropyltriethoxysilane) treatment of the fiber surface was carried out. Examinations through Fourier transform-infrared spectroscopy and scanning electron microscopy (SEM) were conducted to investigate the structural and physical properties of the Borassus fibers. Tensile properties such as modulus and strength of the composites made with chemically modified and untreated Borassus fibers were studied using a universal testing machine. Based on the experimental results, it was found that the tensile properties of the Borassus-reinforced epoxy composites were significantly improved as compared with the neat epoxy. It was also found that the fiber treated with a combination of alkali and silane exhibited superior mechanical properties to alkali-treated and untreated fiber composites. The nature of the fiber/matrix interface was examined through SEM of cryo-fractured samples. Chemical resistance of composites was also found to be improved with chemically modified fiber composites.     

Preparation and Properties of Cellulose/Waste Leather Buff Biocomposites

The aim of the present work was to utilize waste leather buff (WLB) as filler in cellulose and make biocomposites for packaging applications such as wrappers. Cellulose was dissolved in the environmentally friendly ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). To this solution, WLB was added in amounts of 5 to 25 wt.% of cellulose. The cellulose and cellulose/WLB composite films were prepared by regenerating the corresponding cast solutions in a water coagulation bath followed by washing and drying. These films were tested for their tensile properties, thermal stability, and morphology. The tensile modulus and strength of the composite films were lower than those of the matrix. The lowering of the tensile modulus and strength with increasing WLB loading was attributed to the random orientation of the leather fibers of WLB in the composites. However, the % elongation at break of the composite films was found to be higher than that of the matrix and increased with increasing WLB content. The possible interaction between the matrix and WLB filler was probed using FT-IR analysis. The thermal stability of the composite films was higher than that of the matrix. The increase in thermal stability of the composite films was attributed to cross-linked collagen protein leather fibers in WLB. The fractographs of the composite films indicated good interfacial bonding between cellulose and leather fibers of WLB. These composite films may be considered for packaging and wrapping applications.     

Thermal degradation and crystallisation studies of reactively compatibilised polymer blends

The thermal degradation and crystallisation behaviours of polyamide12/isotactic polypropylene (PA12/PP) blends were studied. Effects of blend ratio and compatibiliser concentration on the thermal degradation properties of the blends were analysed. The activation energy for degradation in compatibilised and uncompatibilised blends computed using Horowitz-Metzger equation was reported. The blend ratio as well as the presence of compatibiliser has significant effect on the thermal stability of the blends. Phase morphology was found to be one of the decisive factors that affected the thermal stability of both uncompatibilised and compatibilised blends. Melting and crystallisation behaviours of the blends in the presence and absence of compatibiliser were evaluated. It was observed that blending has no significant effect on the melting and crystallisation properties of PA12 and PP. Compatibilisation of 70/30 and 50/50 PA12/PP blends didn't affect the crystallisation and melting behaviours of PA12 and PP even though some discrepancies were observed.     

Thermal degradation kinetics of poly(methylvinylsilylene-co-styrene)

Thermal degradation kinetics of poly(methylvinylsilylene-co-styrene) copolymers, viz., PMVSS-I to PMVSS-V obtained by reacting methylvinyldichlorosilane (MVDCS) and styrene in 1:0.25, 1:0.5, 1:1, 1:3 and 1:7 mole ratios under dechlorination conditions, using sodium, was studied by thermogravimetry. The homopolymer, poly(methylvinylsilane) (PMVS), synthesized from MVDCS using sodium was also subjected to the above study for comparative evaluation. The kinetic parameters for thermal degradation, viz., activation energy (E) and pre-exponential factor (A) for the above polymers were estimated by non-isothermal kinetic methods such as Mac Callum-Tanner (M-T), Horowitz-Metzger (H-M), Madhusudhanan-Krishnan-Ninan (MKN) and Coats-Redfern (C-R). The order for thermal degradation of PMVS was found to be almost 0. In the case of the copolymers, the order was 1 for PMVSS-I and 2 for PMVSS-II to PMVSS-V. The observed difference in the order for thermal degradation of PMVSS-I when compared to the other copolymers is attributed to the presence of polysilyl linkages in PMVSS-I. It was found that the activation energy and pre-exponential factor showed an increase in trend with increase in concentration of styrene in the copolymer system.     

Thermal degradation of poly(vinyl chloride)

This paper presents an initial attempt at describing poly(vinyl chloride) (PVC) thermal degradation through a semi-detailed and lumped kinetic model. A mechanism of 40 species and pseudocomponents (molecules and radicals) involved in about 250 reactions permits quite a good reproduction of the main characteristics of PVC degradation and volatilization. The presence of the two step mechanism—the first step of which corresponds to dehydrochlorination and the second to the tar release and residue char formation—are correctly predicted both in quantitative terms and in the temperature ranges. The model was validated by comparison with several thermo gravimetric analyses, both dynamic at different heating rates, and isothermal. When compared with the typical one step global apparent degradation models, the approach proposed here spans quite large operative ranges, especially when it comes to predicting product distributions. The initial results of these product predictions, even though quite preliminary, are encouraging and confirm the validity of the model.     

Thermal and Morphological Properties of Octa(maleimido phenyl) Silsesquioxane (OMPS)-Reinforced Polybenzoxazine Hybrid Nanocomposites

We prepared an octa maleimido functionalized POSS, namely octa(maleimido phenyl) silsesquioxane (OMPS)-reinforced polybenzoxazine hybrid nanocomposites, by using four different types of benzoxazines (BZ-Cy-DDM, BZ-Cy-DDE, BZ-Cy-DDS, and BZ-Cy-Ani). They were synthesized from 1,1-bis(3-methyl-4-hydroxyphenyl) cyclohexane, paraformaldehyde, and aromatic amines (4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 4,4′-diaminodiphenylsulphone, and aniline) by the Mannich reaction. We used 10 wt.% OMPS in all four polybenzoxazine matrices in order to compare the effect of OMPS on various benzoxazines. They were polymerized through thermal ring-opening polymerization at identical conditions. The thermal properties of the resulting OMPS-reinforced polybenzoxazine hybrid nanocomposites were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dispersion of OMPS in the polybenzoxazine and nanostructure of the composites were confirmed by X-ray diffraction analysis, transmission electron microscopy, and atomic force microscopy.     

Thermal degradation of poly(vinylpyridine)s

The thermal stability and the temperature at which maximum degradation yields are detected were quite similar for both poly(2-vinylpyridine) (P2VP) and poly(4-vinylpyridine) (P4VP). However, considerable differences among the thermal degradation products of both polymers were detected indicating a correlation between the polymer structure and the degradation mechanism. Direct pyrolysis mass spectrometry analyses revealed that P2VP degrades via a complex degradation mechanism, yielding mainly pyridine, monomer, and protonated oligomers, whereas depolymerization of P4VP takes place in accordance with the general thermal behaviour of vinyl polymers. The complex thermal degradation behaviour for P2VP is associated with the position of the nitrogen atom in the pyridine ring, with σ-effect.     

Thermal and thermo-oxidative degradation of poly(hydroxy ether of bisphenol-A) studied by TGA/FTIR and TGA/MS

The nature and the extent of degradation of poly(hydroxy ether of bisphenol-A) phenoxy resin were analysed by thermogravimetry (TGA/DTGA) under nitrogen and air atmosphere. Decomposition kinetics were elucidated according to Flynn-Wall-Ozawa, Friedman and Kissinger methods. The evolved gases during degradation were inspected by a thermogravimetry analyser coupled with Fourier Transform Infrared Spectrometer (TGA/FTIR) and also with a TGA coupled to a Mass Spectrometer (TGA/MS). Mass spectra showed that chemical species evolved in phenoxy decomposition in air were very similar to those assigned from degradation in nitrogen (water, methane, CO, CO₂, phenol, acetone, etc.). However, these species appear in different amount and at different temperatures in both atmospheres. FTIR analysis of the evolved products showed that water and methane were the beginning decomposition products, indicating that decomposition is initiated by dehydration and cleavage of C-CH₃ bond in the bisphenol-A unit of phenoxy resin. After this initial stage, random chain scission is the main degradation pathway. Nevertheless, in air atmosphere, previously the complete decomposition of the phenoxy obtaining fundamentally CO₂, and water, the formation of an insulated surface layer of crosslinked structures has been proposed.     

Thermal decomposition of microbial poly(γ-glutamic acid) and poly(γ-glutamate)s

The thermal decomposition of poly(γ-glutamic acid), poly(α-methyl γ-glutamate) and ionic complexes of the polyacid with alkyltrimethyl ammonium salts was studied by TGA, GPC, and FTIR and NMR spectroscopies. It was found that both poly(γ-glutamic acid) and poly(α-methyl γ-glutamate) depolymerised above 200 °C by unzipping mechanism with generation of pyroglutamic acid and methyl pyroglutamate, respectively. On the other hand, the ionic complexes degraded through a two-stage process, the first stage being cyclodepolymerisation of the poly(γ-glutamate) main chain along with decomposition of the ionic complex promoted by the adsorbed water. Decomposition of the previously generated alkyltrimethyl ammonium compound followed by unspecific cracking of the resulting nitrogenated compounds accounted for the second degradation step, at higher temperatures. Mechanisms explaining the decomposition of the three studied systems were proposed according to collected data.     

Characterization of monumental carbonate stones by thermal analysis (TG, DTG and DSC)

Thermogravimetry (TG), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC), were found to be suitable instrumental techniques for the study of monumental rocks because they need small amounts of sample and provide extensive qualitative and quantitative information. From DTG curves, the calcite/dolomite ratio in the samples as well as the differences between limestones and dolomites can be quantitatively determined. DSC curves are adequate for the identification of the degradation products in the monumental stones since they are usually salts (sometimes hydrates) which present first-order processes under 600°C. This technique makes it possible to carry out quantitative and semiquantitative analysis of the degradation of monumental rocks since it provides data about its mineralogic composition.     

Synthesis,Characterization, Thermal Property of Si(c‐C5H9NH)4 and Its Potential as CVD Precursor for SiC Film

Silicon(IV) amide Si(c‐C₅H₉NH)₄ ( 1 ), was synthesized and characterized by ¹H, ¹³C, and ²⁹Si NMR spectroscopy, EI‐MS, elemental analysis, and X‐ray diffraction. Its thermal stability and volatility were also investigated. The as‐grown film, which was characterized by SEM, AFM, XRD and XPS, was deposited using 1 as single precursor through a low‐pressure chemical vapor deposition (LPCVD) process at a temperature as low as 600 °C. The results demonstrated that silicon(IV) amides can be promising single‐precursor for deposition of low‐temperature SiC films.     

Thermal, mechanical and electrical properties of copper powder filled low-density and linear low-density polyethylene composites

Low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) with different copper contents were prepared by melt mixing. The copper powder particle distributions were found to be relatively uniform at both low and high copper contents. There was cluster formation of copper particles at higher Cu contents, as well as the formation of percolation paths of copper in the PE matrices. The DSC results show that Cu content has little influence on the melting temperatures of LDPE and LLDPE in these composites. From melting enthalpy results it seems as if copper particles act as nucleating agents, giving rise to increased crystallinities of the polyethylene. The thermal stability of the LDPE filled with Cu powder is better than that for the unfilled polymer. The LLDPE composites show better stability only at lower Cu contents. Generally, the composites show poorer mechanical properties (except Young's modulus) compared to the unfilled polymers. The thermal and electrical conductivities of the composites were higher than that of the pure polyethylene matrix for both the LDPE and LLDPE. From these results the percolation concentration was determined as 18.7 vol.% copper for both polymers.