Diffuse reflectance Fourier transform infrared spectra of wood fibers treated with maleated polypropylenes

The esterification reaction between wood fibers and maleated polypropylenes was investigated. The reaction was conducted in a reactor in the presence of xylene used as a solvent and sodium hypophosphite as catalyst. The reaction between wood fibers and pure maleic anhydride was also investigated. The appearance of an infrared absorption band near 1730 cm⁻¹ indicated that maleated polypropylene chemically reacted by esterification with bleached Kraft cellulose. However, no direct evidence of an esterification reaction was obtained between thermomechanical pulp and maleated polypropylene. The Fourier transform infrared (FTIR) studies showed also that both bleached Kraft cellulose and thermomechanical pulp reacted with maleic anhydride with the formation of ester links. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1163–1173, 1997     

Synthesis and characterization of polypropylene reinforced with cellulose I and II fibers

Recently, cellulose fiber–thermoplastic composites have played an important role in some applications. Plastics reinforced with cellulose and natural fibers have been widely studied. However, composites with regenerated cellulose have rarely been investigated. In this study, the lyocell fiber of Lenzing AG (cellulose II) and its raw material a bleached hardwood pulp (cellulose I) were used as reinforcement materials. The mechanical and thermal properties of polypropylene (PP) reinforced with pulp and lyocell fibers were characterized and compared with regard to the content of the fiber and the addition of maleated polypropylene (MAPP). PPs with cellulose I or II as a reinforcement material had similar mechanical properties. However, when MAPP was used as coupling agent, the mechanical properties of the composites were different. The crystallinity of the composites were determined by differential scanning calorimetry. Cellulose I (pulp) promoted the crystallization of PP, whereas cellulose II did not. MAPP reduced this effect in cellulose I fibers, but it induced crystallization when cellulose II (lyocell) was used as a reinforcement material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 364–369, 2006     

Crystallization of fiber-reinforced poly(phenylene sulfide) composites. I. Experimental studies of crystallization rates and morphology

The isothermal crystallization from the melt of unreinforced poly(phenylene sulfide) (PPS) and of model carbon, aramid, and glass-fiber-reinforced PPS composites was studied by differential scanning calorimetry and optical microscopy. Crystallization was studied as a function of temperature, and the fiber contents in the composites were varied over a wide range. The results indicate that the influence of fibers on PPS crystallization is not only fiber specific, but also strongly dependent on the surface treatment (size). In general, fiber-reinforced systems crystallized faster than unreinforced (PPS), and the degree of crystallinity was less under comparable crystallization conditions. It was also observed that the rate of crystallization was enhanced in those systems which exhibited transcrystallinity in thin PPS film/single fiber composites as compared to those systems which did not exhibit transcrystallinity. Furthermore, the degree of crystallinity showed a nonlinear crystallization temperature dependence for those systems that exhibited transcrystallinity.     

Biodegradable natural composites. I. Processing and properties

This paper presents an investigation of the properties of composites of bacteria-produced polyesters reinforced with wood cellulose. Although cellulose fibers improved the strength and stiffness of the polyhydroxybutyrate (PHB), the samples were very brittle. The impact strength and elongation at break of these composites were significantly improved when PHB copolymers with increased amounts of hydroxyvalerate (HV) were used as the matrix. Dynamic mechanical properties of PHB copolymers of varying compositions and of cellulose-filled composites were investigated. The introduction of cellulose resulted in a decreased loss factor owing to restrictions of the chain mobility in the amorphous phase. An improvement was observed in the dynamic modulus, which was seen to be greatest at elevated temperatures. An excellent dispersibility of cellulose fibers was achieved in the PHB matrix as compared with such synthetic matrices as polystyrene or polypropylene. The degree of dispersibility was strongly affected by processing conditions. The defibrillation observed on extracted fibers suggests a possible hydrolysis of cellulose by crotonic acid formed in situ as a result of the thermal decomposition of the PHB matrix.     

The effects on mechanical properties and crystallization of poly (l‐lactic acid) reinforced by cellulosic fibers with different scales

Bacterial cellulose (BC), microcrystalline cellulose (MCC), and bamboo cellulosic fibers (BCFs) were used to reinforce poly(l ‐lactic acid) (PLLA) based bio‐composites. The mechanical properties and crystallization of the composites were studied through mechanical testing, differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and polarizing microscope. The incorporation of all three kinds of cellulose increased the stiffness of the composites compared to pure PLLA. The reinforcing effect of the MCC in the composites is most significant. The Young's modulus and impact toughness of the MCC/PLLA composites were increased by 44.4% and 58.8%, respectively. The tensile strength of the MCC/PLLA composites was increased to 71 MPa from 61 MPa of PLLA. However, the tensile strength of the composites reinforced with BCF or BC was lower than PLLA. The three kinds of cellulosic fibers improved the crystallization of PLLA. The BC with smallest size provided the composites with smallest grain and highest crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41077.     

Study on cellulose and xylan filled polypropylene composites

The thermal and viscoelastic properties of polypropylene (PP)/cellulose as well as PP/Xylan composites were investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermoanalysis (DMTA). Morphological aspects were available by using polarizing light microscopy and scanning electron microscopy (SEM). Three types of fillers were incorporated in PP: xylan fillers (XL), cellulose microfibers (CM) and short fibers of spun cellulose (CS). The compatibilizer maleic anhydride modified PP (MAPP) was added to the composites. The crystallization temperature and crystallinity of PP apparently increased in the presence of all fiber types. The cellulose fiber surfaces act as nucleating agents for PP, resulting in the formation of transcrystalline regions around the fibers. The DMTA spectra of PP/filler composites revealed a significant increase in the stiffness and a remarkable decrease of the damping values. This effect was stronger for PP/CS than for the other composites. The results verify that improved compatibility and interfacial adhesion between fiber and matrix markedly contribute to an improvement of the mechanical properties. Received: 30 October 1997/Revised version: 11 December 1997/Accepted: 12 December 1997     

Physical and functional characterization of PHASCL membranes

Dense semicrystalline membranes of polyhydroxyalkanoates with medium change length (PHA_SCL), polyhydroxybutyrate (PHB) and poly β (hydroxybutyrate-co-hydroxyvalerate) [P(βHB-co-XβHV)] were characterized using wide-angle X-ray (WAXS) and scanning electron microscopy. PHB membranes showed a more rugged surface than those of copolymers (0-22%HV). Properties such as swelling capacity, vapor permeability and selectivity were investigated. Swelling percentage in water-ethanol mixtures was 34% for PHB as compared to 14% for copolymers membranes. The ethanol/water selectivity (α_s) of PHB was 5.8 which shows that it is more selective than copolymers.The water vapor and ethanol vapor permeability were determined by a gravimetric technique at different temperatures by static and dynamic methods. PHB permeability was 69.5 Barrer at 30 °C and a discreet increment was observed at temperatures (30-50 °C). The difference in permeability between PHB and [P(βHB-co-X%βHV)] could be interpreted in terms of the crystallization rate, crystallite size and distribution which impact to transport properties of amorphous phase.     

Wood fibers as reinforcing fillers for polyolefins

Wood pulp fibers possess strength and modulus properties which compare favorably with glass fibers when the differences in fiber densities are considered. Softwood pulp fibers with fiber aspect ratios near 100 are readily dispersed into high-density polyethylene or isotactic polypropylene with the aid of carboxyic dispersing agents to form mixtures containing 50 weight-percent wood pulp which can be readily injection molded. The mechanical properties of the molded specimens were similar for all types of pulp including Kraft (bleached and unbleached), mechanical and chemical-mechanical pulps, waste pulps, and reclaim newspapers. Comparisons of the stiffness/weight efficiencies revealed that pulp composites equal or exceed the stiffness of most traditional materials of construction including steel, aluminum, glass-fiber composites, and talefilled polyolefins, while retaining a major material cost advantage. The measured strength values of the pulp composites were less than the theoretically predicted values due to the presence of voids created by the formation of volatiles during processing. Mechanical pulps which were available in dry form were preferred because of lower cost and ease of handling. Wood fibers are non-abrasive so that relatively large concentrations may be incorporated into polyolefins without causing serious machine wear during mixing and fabrication.     

Durability of thermomechanical pulp fiber-cement composites to wet/dry cycling

Previous research efforts on pulp fiber-cement composites have largely concentrated on kraft pulp fiber composites. In this research program, thermomechanical pulp (TMP) fibers were investigated as an economical alternative to kraft pulp fibers as reinforcement in fiber-cement composites. Prior to wet/dry cycling, TMP composites exhibited increased first crack strength, but lower peak strength and lower post-cracking toughness, as compared to unbleached and bleached kraft pulp composites at equivalent fiber volume fractions. It is believed that this behavior can be attributed to the lower tensile strength and shorter fiber length of TMP fibers as compared to kraft fibers. After 25 wet/dry cycles, TMP composites showed losses in first crack (peak) strength and post-cracking toughness. However, TMP composites exhibited a slower progression of degradation during wet/dry cycling than composites containing bleached or unbleached kraft fibers.     

Bleached extruder chemi‐mechanical pulp fiber‐PLA composites: Comparison of mechanical,thermal, and rheological properties with those of wood flour‐PLA bio‐composites

An environmentally friendly bleached extruder chemi‐mechanical pulp fiber or wood flour was melt compounded with poly(lactic acid) (PLA) into a biocomposite and hot compression molded. The mechanical, thermal, and rheological properties were determined. The chemical composition, scanning electron microscopy, and Fourier transform infrared spectroscopy results showed that the hemicellulose in the pulp fiber raw material was almost completely removed after the pulp treatment. The mechanical tests indicated that the pulp fiber increased the tensile and flexural moduli and decreased the tensile, flexural, and impact strengths of the biocomposites. However, pulp fiber strongly reinforced the PLA matrix because the mechanical properties of pulp fiber‐PLA composites (especially the tensile and flexural strengths) were better than those of wood flour‐PLA composites. Differential scanning calorimetry analysis confirmed that both pulp fiber and wood flour accelerated the cold crystallization rate and increased the degree of crystallinity of PLA, and that this effect was greater with 40% pulp fiber. The addition of pulp fiber and wood flour modified the rheological behavior because the composite viscosity increased in the presence of fibers and decreased as the test frequency increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44241.     

Cellulose fiber‐reinforced polylactic acid

Polymer composites from polylactic acid (PLA) and two types of cellulose fibers obtained either by acid hydrolysis of microcrystalline cellulose (HMCC) or by mechanical disintegration of regenerated wood fibers (MF) were prepared and characterized. To enhance the compatibility of the cellulose fibers with PLA matrix, a surface treatment based on 3‐aminopropyltriethoxysilane (APS) was performed. The Fourier Transform Infrared (FTIR) spectroscopy was used to determine the chemical groups involved in the surface modification reaction. The silanization treatment resulted in different modifications on both types of cellulose fibers because of their different structural and morphological characteristics. The composites were prepared by incorporating 2.5% of the treated or untreated HMCC and MF into a PLA matrix using a melt‐compounding technique. An improved adhesion between the two phases of the composite materials was observed by scanning electron microscopy thanks to treatment. The dynamic mechanical thermal analyses showed that both untreated and silane treated fibers led to an improvement of the storage modulus of PLA in the glassy state. A higher enhancement of the storage modulus in the case of PLA/HMCC composites than the composites containing MF was obtained as a result of the high aspect ratio of these fibers which allows better matrix‐to‐filler stress transfer. Furthermore, the storage modulus of PLA composites was enhanced by silanization even at higher temperatures especially after thermal treatment. The cellulose fibers addition in PLA matrix modified significantly the relaxation phenomenon as observed in tan δ curves, emphasizing strongly modified molecular mobility of PLA macromolecules and crystallization changes. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and starch acetate

The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm^-1 and 1724cm^-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI     

Crystallization kinetics of PPS composites and quantification of fiber nucleation density using a computer simulation

Differential scanning calorimetry and hot-stage optical microscopy were used to study the isothermal crystallization kinetics of unreinforced poly(phenylene sulfide) (PPS) and PPS reinforced with aramid, carbon, and glass fibers. The influence that fibers have on the crystallization kinetics of PPS was found to depend on the characteristics of the fiber as well as the type of PPS used. For one kind of PPS, fibers enhanced the crystallization rate, while for another type of PPS, reinforcing fibers had a moderate depressing effect on the polymer crystallization rate. To clarify these effects, we used a new method of quantifying the nucleation process in fiber-reinforced composites that employs a 3-D computer simulation of spherulitic crystallization. Using this method, the nucleation density in the bulk polymer, N_b, and the nucleation density on fiber surfaces, N_f, were calculated for PPS composites as a function of crystallization temperature. The calculated values of N_b and N_f were used to explain differences in the effectiveness of the fibers as well as differences in the nucleating characteristics of the two polymers. © 1995 John Wiley & Sons, Inc.     

Extrusion processing of green biocomposites: Compounding,fibrillation efficiency,and fiber dispersion

The efficiency of twin‐screw extrusion process to fibrillate cellulose fibers into micro/nanosize in the same step as the compounding of green bionanocomposites of thermoplastic starch (TPS) with 10 wt % fibers was examined. The effect of the processing setup on micro/nanofibrillation and fiber dispersion/distribution in starch was studied using two types of cellulose fibers: bleached wood fibers and TEMPO‐oxidized cellulose fibers. A composite with cellulose nanofibers was prepared to examine the nanofiber distribution and dispersion in the starch and to compare the properties with the composites containing cellulose fibers. Optical microscopy, scanning electron microscopy, and UV/Vis spectroscopy showed that fibers were not nanofibrillated in the extrusion, but good dispersion and distribution of fibers in the starch matrix was obtained. The addition of cellulose fibers enhanced the mechanical properties of the TPS. Moisture uptake study revealed that the material containing TEMPO‐oxidized fibers had higher moisture absorption than the other composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39981.     

Influence of casting substrate on the acid–base interaction energies of various polyesters

The acid–base surface characteristics of four polyesters: poly( -lactic acid) (PLLA), poly( -lactic acid) (PDLLA), polyhydroxybutyrate (PHB) and copoly(hydroxy butyrate–20% hydroxyvalerate)P(HB–20% HV) have been determined from contact angle and surface tension experimental data. Smooth surfaced polyester films were prepared by solution casting against a number of substrates ranging from high surface energy (aluminium, mercury, glass and freshly-cleaved mica) to low surface energy (poly(ethyleneterephthalate)(PET), poly(tetrafluoroethylene)(PTFE) and dry nitrogen gas).

Results show that the acid–base interaction energy of the polyester surface is dependent on the casting substrate and ageing time. For a particular casting substrate, the equilibrium acid–base interaction energy between a polyester surface and an acidic liquid decreases in the order: PDLLA; PLLA; PHB; P(HB–20%HV).

The time dependence of the acid–base interaction energy is interpreted in terms of orientation of surface acidic or basic sites. Furthermore, detailed results suggest that the initial acidic or basic character of the cast polyester surface is influenced by the acid/base surface properties of the casting substrates.     

Influence of pulp bleaching and compatibilizer selection on performance of pulp fiber reinforced PLA biocomposites

This article focuses on the effect of pulp bleaching and emerging commercial compatibilizers on physical performance of pulp fiber reinforced poly(lactic acid) (PLA) biocomposites. Industrially bleached and unbleached hardwood kraft pulp fibers are treated with several additive types, and compounded with PLA to fiber content of 30 wt %. After injection molding, the produced biocomposites are evaluated by their mechanical performance and fiber–matrix adhesion. For selected materials, fiber surface and fiber properties are reflected to composite performance by analyzing the compositions, dimensions, and lignin coverage of original fibers, as well as fiber dispersion and dimensions after melt processing. As a conclusion, unbleached kraft pulp fibers provide significant improvement in physical properties of PLA/pulp fiber composites. Of the screened compatibilizers, epoxidated linseed oil has a clear positive effect on performance when bleached kraft pulp fibers are used. The improvements correspond to enhanced fiber–matrix adhesion and differences in remaining fiber length distributions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47955.     

Preparation and characterization of poly(hydroxybutyrate‐co‐hydroxyvalerate)–organoclay nanocomposites

This study describes the microstructure and thermal and mechanical properties of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHB/HV)–organoclay nanocomposites prepared by melt intercalation using Cloisite 30B, a monotallow bis‐hydroxyethyl ammonium‐modified montmorillonite clay. X‐ray diffractometry and transmission electron microscopy analyses clearly confirm that an intercalated microstructure is formed and finely distributed in the PHB/HV copolymer matrix because PHB/HV has a strong hydrogen bond interaction with the hydroxyl group in the organic modifier of Cloisite 30B. The nanodispersed organoclay also acts a nucleating agent, increasing the temperature and rate of crystallization of PHB/HV; therefore, the thermal stability and tensile properties of the organoclay‐based nanocomposites are enhanced. These results confirm that the organoclay nanocomposite greatly improves the material properties of PHB/HV. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 525–529, 2003     

The morphology and degradation behavior of electrospun poly(3‐hydroxybutyrate)/Magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/Magnetite composites

Electrospinning of biodegradable poly(3‐hydroxybutyrate) (PHB)/magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/magnetite composites in 2,2,2‐trifluoroethanol (TFE) and chloroform are investigated to develop nonwoven nanofibrous structure. Ultrafine PHB/magnetite fibers are obtained and the resulting fiber diameters are in the range of 690–710 nm and 8.0–8.4 µm for the polymer dissolved in TFE and chloroform. The surface of PHB composites fiber fabricated in chloroform contains porous structures, which are not observed for the sample of PHB composites fiber dissolved in TFE. The fiber diameters for PHBV5/magnetite composites are in the range of 500–540 nm and 2.3–2.5 µm, depending on the use of TFE and chloroform. The average diameters of PHBV5/magnetite composite fibers are smaller than those of PHB/magnetite composites fiber. All electrospun PHB/magnetite and composite fibers are superparamagnetic. The degradation behaviors of PHB/magnetite and PHBV5/magnetite composite fibers were investigated using Caldimonas manganoxidans. For the fabricated composite fibers, it is found that the degradation rate increased with the increasing loading of magnetite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41070.     

Some properties of poly(3-hydroxybutyrate)–poly(3-hydroxyvalerate) blends

The melting, crystallization and dynamic mechanical behaviour of blends of bacterially produced poly[D (–)-3-hydroxybutyrate] (PHB) and poly[D (–)-3-hydroxyvalerate] (PHV) have been investigated. Results showed that melt-pressed PHB–PHV blends contained phase-separated domains in the melt which subsequently crystallized as PHB and PHV type spherulites respectively. The two melting regions detected by DTA related to separate melting of PHB and PHV crystallites, which were almost unaffected by the blend composition. The mechanical behaviour of a random copolymer of PHB/HV was compared with that of a blend of almost the same composition, and found to be markedly different.     

The influence of fibers on the crystallization of poly(ethylene terephthalate) as related to processing of composites

The effect of fiber reinforcement on the isothermal crystallization of poly(ethylene terephthalate) (PET) was investigated using differential scanning calorimetry (DSC). Unidirectional fiber composites were prepared using glass and aramid fibers in PET. The rate of crystallization, as reflected by crystallization half-time, and the degree of crystallinity of PET are seen to depend on the type of reinforcing fiber as well as on crystallization temperature. Crystallization kinetics are also analyzed using an Avrami model for the volume of polymer crystallized as a function of time. The crystalline morphology of PET in fiber-reinforced systems was studied using polarized light microscopy. Results concerning nucleation densities and growth morphologies are used in explaining differences seen in crystallization kinetics in fiber-reinforced systems.