Conversion of plastic/cellulose waste into composites. I. Model of the interphase

This article proposes a mechanism for a significant improvement in the mechanical performance of a simulated waste fraction, composed of an immiscible low-density polyethylene (LDPE) and high-impact polystyrene (HIPS) blend (70:30 proportion), when chemithermomechanical pulp (CTMP) fibers and maleic acid anhydride grafted styrene–ethylene/butylene–styrene block copolymer (MAH-SEBS) were added. SEM micrographs of composites showed an increased contact between the continuous LDPE phase and CTMP fibers when the functionalized compatibilizer (MAH-SEBS) was used. By employing a model study using LDPE and regenerated cellulose, we investigated the interphase properties between the plastic phase and the cellulosic component. The model study utilized ESCA, FTIR, and contact angle analysis to follow the reaction between the cellulose surface and the functionalized compatibilizer. All three methods showed that MAH-SEBS was bonded to the surface of the cellulose. The single-fiber fragmentation test showed that the adhesion between cellulose fibers and the plastic matrix was significantly improved for MAH-SEBS–modified samples. The effect of enhanced adhesion on increased mechanical properties of cellulose composites is also discussed, and a prediction of composite strength given, based on interfacial adhesion promotion and fiber properties. © 1995 John Wiley & Sons, Inc.     

The nature of adhesion in composites of modified cellulose fibers and polypropylene

Cellulose fibers were surface modified with polypropylene–maleic anhydride copolymer. The physical properties of such fibers were characterized by contact angle measurements, and the chemical structure was identified with ESCA and FTIR. ESCA showed that the modifying agent was localized at the surface of the fibers. The modified fibers were compounded with polypropylene, and composites with various amount of fibers were manufactured by injection molding. All mechanical properties were improved when treated fibers were used. SEM showed improved dispersion, wetting of fibers, and adhesion. The nature of adhesion was studied using FTIR. It was found that the surface modifying agent is covalently bonded to the fibers through esterification. The degree of esterification is enhanced by activating the modifying agent before fiber treatment. This study has shown the effects of treatment conditions on activation of reactive species and chemical reaction between fiber and modifying agent. Moreover, a better understanding has been achieved of the nature of adhesion for the system.     

Surface chemical modification of natural cellulose fibers

Simple esterification and etherification reactions were applied to steam‐exploded Flax (Linum usitatissimum) with the aim of changing the surface properties through modification of fiber surface chemistry. Native and chemically modified cellulose fibers were characterized in terms of thermal stability, surface chemistry, morphology, and crystal structure. Independent of the substituent nature, chemically modified fibers exhibited a thermal stability comparable to that of native cellulose. Introduction of the desired chemical groups at the fiber surface was demonstrated by TOF‐SIMS analysis, whereas FTIR showed that the substitution reaction involved only a small fraction of the cellulose hydroxyls. No change of the native crystalline structure of cellulose fibers was caused by chemical modification, except in the case where ether substitution was carried out in water‐isopropanol medium. Cellulose fibers with unchanged structure and morphology and carrying at the surface the desired chemical groups were obtained for reinforcing applications in polymer composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 38–45, 2002     

Surface modification of microfibrillated cellulose for epoxy composite applications

Microfibrillated cellulose (MFC) possessing a ‘web-like’ morphology was successfully modified with three different coupling agents: 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and a titanate coupling agent (Lica 38). The surface modification was confirmed using infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), and contact angle measurements. These modifications changed the surface character of MFC from hydrophilic to hydrophobic. The untreated and treated MFC were successfully incorporated into an epoxy resin system using acetone as the solvent. Better and stronger adhesion between the microfibrils and the epoxy polymer matrix was observed for the treated fibers, which resulted in better mechanical properties of the composite materials.     

Surface modification of cellulose fibers. II. The effect of cellulose fiber treatment on the performance of cellulose–polyester composites

Cellulose fibers treated with different coupling agents based on trichloro-s-triazine have been evaluated in terms of their reinforcement effect on unsaturated polyesters. The treatment with coupling agents containing double bonds resulted in what we believe to be the formation of covalent bonds between fiber and matrix. This has been compared with a treatment, which can only lead to formation of close interfacial molecular contact by wetting. The tensile properties of composites prepared from treated and untreated fibers were studied before and after exposure to water. It was found that all types of fiber treatment decreased water absorption and the reduction of mechanical properties in wet conditions, but that the degradation at the fiber/matrix interface which occurs from immersion in water and drying could only be avoided through the development of covalent bonds between fiber and matrix. Scanning electron microscopy was used to study the adhesion between fiber and matrix. An explanation of the reduction of mechanical properties of cellulose-fiber reinforced polymers in wet conditions is proposed.     

Chemical modification of hemp fibers by silane coupling agents

Natural hemp fibers were chemically modified using silane coupling agents to reduce their hydrophilic character. The existence of a chemical bond between coupling agents and hemp fibers was confirmed by ATR‐FTIR spectroscopy, ²⁹Si Nuclear Magnetic Resonance (NMR), thermogravimetric analysis (TGA), energy dispersive spectroscopy (EDS), and BET surface area measurements. It was shown that the initial concentration and the chemical structure of the organosilane coupling agent have an effect on the grafted quantity on the hemp fiber surfaces. The grafted quantity increased proportionally to the initial concentration of silane molecules. The presence of polar amino end group (NH₂) in silane structure can cause an increase in the grafted quantity, compared with results obtained in the case of silane molecules containing methacryloxy groups. This effect is attributed to the formation of hydrogen bonds between NH₂ and unreacted hydroxyl groups of hemp fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface energy of untreated and surface-modified cellulose fibers

Average advancing and receding contact angles made against cotton and glass fibers by a set of probe liquids are determined using the Wilhelmy technique. The dispersive and polar components of the surface energy are calculated from the measured contact angles using both the geometric and the harmonic mean methods. It is found that these components are similar for untreated cellulose and glass fibers, and that they both have a high polar component, corresponding to a hydrophilic surface. Changes in surface energy caused by treatment of the cellulose fiber surfaces with melamine, polyethyleneimine (PEI), and a silane coupling agent are reported. It is found in particular that polyethyleneimine treatment of cellulose significantly reduces the polar component of its surface energy. While treatment of glass fibers with a silane coupling agent reduces the polar component and increases the dispersive component of the surface energy it shows little effect on the surface energy of cellulose.     

Surface modification of PBO fibers by argon plasma and argon plasma combined with coupling agents

The methods of argon plasma and argon plasma combined with coupling agents were employed to modify the poly[1,4‐phenylene‐cis‐benzobisoxazole] (PBO) fiber surface. The interfacial shearing strength (IFSS) of PBO fibers/epoxy resin was measured by the single fiber pull‐out test. The surface chemical structure and surface composition of PBO fibers were determined by FTIR and X‐ray photoelectron spectroscopy respectively. The morphology of the fiber surface was investigated by scanning electron microscopy and the specific surface area of the fibers was calculated by B.E.T. equation. Furthermore, the wettability of PBO fibers was confirmed by the droplet profile analysis method. The results showed that the elemental composition ratio of the fiber surface changed after the modification. The IFSS increased by 42 and 78% when the fibers were treated by argon plasma and argon plasma combined with the coupling agents, respectively. Meanwhile, the specific surface areas of the treated fibers were improved. In addition, compared with the modification of argon plasma, the modification of argon plasma combined with the coupling agents inhibited the attenuation phenomena of the IFSS and the wettability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1428–1435, 2006     

Viscose fiber/polyamide 12 composites: Novel gas‐phase method for the modification of cellulose fibers with an aminosilane coupling agent

The objective of this study was to improve the adhesion between viscose fibers and polyamide 12 and, thereby, the mechanical properties of the corresponding composites. The cellulose fiber surface was chemically modified in the vapor phase with a silyl coupling agent, aminosilane [(3‐aminopropyl) triethoxysilane]. This new gas‐phase treatment for cellulose fibers proved to be highly effective. Relative to composites without the coupling‐agent treatment, the tensile strength of the composites (40/60 wt % fiber/polymer) increased from 49.3 to 87.4 MPa; the improved adhesion between the fibers and matrix induced by the coupling agent was observed under a scanning electron microscope. The presence and bonding of the coupling agent on the fibers after the reaction was confirmed by solid‐state ²⁹Si‐NMR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4478–4483, 2006     

Silicone-modified cellulose. Crosslinking of the cellulose acetate with 1,1,3,3-tetramethyldisiloxane by Pt-catalyzed dehydrogenative coupling

Cellulose acetate was reacted with different amounts of 1,1,3,3-tetramethyldisiloxane in presence of Karstedt’s catalyst, in solution, by using dry acetone as a solvent. A dehydrocoupling reaction between Si-H and C-OH groups with H₂ evolving and the formation of Si-O-C bond occured, as proved by FTIR and NMR spectra, having as a result the crosslinking of cellulose derivative. A model reaction was followed online by ¹H NMR spectroscopy. Morphological changes as a result of the siloxane coupling to the cellulose derivative were emphasized by Environmental Scanning Electron Microscopy (ESEM). The surface (water contact angle and water vapor sorption capacities) and mechanical properties (breaking strength, breaking strain and Young modulus) of the networks processed as films were investigated and the results were correlated with the reactants ratios.     

Preparation and characterization of chitosan coatings onto regular cellulose fibers with ultrasound technique

Regenerated cellulose fibers—viscose fibers—were coated with chitosan using an ultrasound technique to improve their accessibility, reactivity and sorption properties. The main purpose of our research was to study the modification of viscose fibers and to determine the effect of the application of chitosan onto viscose fibers. Samples were obtained by treating the fibers with chitosan in a dilute acetic acid solution in an ultrasonic bath. The influences of the chitosan coating on the changes in morphology, supramolecular structure, sorption and tensile properties were studied. The spectra (FTIR analysis) of the treated viscose fibers showed changes and new absorption bands that revealed the existence of the chemical interactions with the chitosan. The scanning electron microscope images confirmed that the surface of the fibers was covered with the chitosan. A decrease in the water retention value and increase in the absorption and moisture content with an increasing concentration of chitosan was noted. Furthermore, the differences in tensile behavior were analyzed using an Instron tensile testing machine. The chitosan coating had no effect on the tensile strength of the viscose fibers, but influenced the tensile strain. Some changes, though not significant, were noted in the structure (crystallinity, orientation) of the treated viscose fibers.     

Development and evaluation of surface treatments to enhance the fiber-matrix adhesion in PAN-based carbon fiber/liquid crystal polymer composites. Part I: Coupling agent and amine surface treatments

Several surface treatments, using both commercially available coupling agents and reagents containing multiple amines, were applied to commingled continuous as-received AS4 carbon reinforcing fiber/liquid crystal polymer (LCP) matrix fibers. Unidirectional composites (normally 60 vol% carbon fiber) were prepared from as-received and treated commingled fibers and characterized. To estimate the effect the effect of the treatments on fiber-matrix adhesion, short beam shear (SBS) tests were conducted, the failure surfaces were examined, and spectroscopic studies wee performed. The mean SBS strength of the as-received unidirectional AS4 carbon fiber/LCP matrix composite system was 49 MPa. The best coupling agent and amine treatments yielded increases in composite shear strength of ∼ 10 to 20%, relative to the as-received AS4/LCP system. For the amine treatments, ESCA and FTIR analyses suggested of both the carbon and LCP fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers (both with coupling agents and amines) showed that strong fiber-matrix adhesion was present. That is, failure occurred in the LCP matrix material.     

Surface treatment of cellulose fibers with methylmethacrylate for enhanced properties of in situ polymerized PMMA/cellulose composites

Cellulose micro/nanofibers (CNF), prepared from jute fibers were surface treated with methyl methacrylate (MMA) for better dispersion into poly methyl methacrylate (PMMA) matrix. PMMA/cellulose composites were prepared by in situ suspension polymerization technique. The surface treatment of CNF was confirmed by Fourier transform infrared spectroscopy (FTIR) and Nuclear magnetic resonance (NMR) analysis. MMA‐treated cellulose micro/nanofibers (MCNF) demonstrated improved affinity and dispersion in MMA monomer as well as in the PMMA/cellulose composites. Thermal properties of the cellulose composites were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The glass transition temperature (T_g) of PMMA increased by nearly 19°C in the in situ cellulose composites compared to that of unreinforced PMMA as indicated by DSC. TGA showed increased thermal stability of the cellulose composites. Enhanced tensile properties as well as significantly lower moisture uptake were observed in the in situ prepared PMMA/cellulose composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39808.     

Plasma surface treatments on carbon fibers. II. Mechanical property and interfacial shear strength

Carbon fiber are surface treated by oxygen, argon, and styrene plasma to study the effects on fiber strength and interfacial shear strength with PPS resin. Interfacial shear strength between carbon fiber and high melting temperature thermoplastic resins is successfully measured with the microbond pull-out test with the help of scanning CO₂ laser beam which solved the difficulties in preparing PPS microspheres. Tensile tests show that etching by oxygen plasma and deposition with plasma–PS increase strength of the fibers in some cases. ESCA spectra deconvolutions demonstrate that the improved interfacial strength is strongly related to the hydroxyl, ether, or aromatic groups on the surface. On the other hand, hydrocarbon segments are detrimental to the interface. Surface area and roughness have little influences on the interfacial strength of carbon fiber/PPS composites.     

Morphological and grafting modification of natural cellulose fibers

Crystal structure and mechanical properties of cellulose fibers were studied to investigate the effect of chemical treatment on the fiber. Pretreatment by acetone extraction, mercerization with 3–20% wt/v sodium hydroxide (NaOH), and acrylonitrile (AN) grafting initiated by azo‐bis‐isobutylonitrile were performed. From Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction quantitative measurements, the pretreated fibers showed an induced slight decrease of crystallinity index. The structural transformation of the fibers from cellulose I to cellulose II was observed at high NaOH concentration of 10–20% wt/v. The amount of grafting, 1.56, 2.94, 6.04, 8.34, or 10.46%, was dependent upon the initiator concentration and the volume of monomer in the reactor. The AN grafted fibers had no transformation of crystalline structure as observed after mercerization. Only a variation of X‐ray crystallinity index with grafting amount was observed. Moisture regain of pretreated and modified fibers depended on the structure of the fiber and the amount of grafting. The mechanical properties performed by a single fiber test method were strongly influenced by the cellulose structure, lateral index of crystallinity, and fraction of grafting. Scanning electron microscopy was used for analysis of surface morphologies of treated fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2456–2465, 2004     

Surface characterization of silane-treated industrial glass fibers

The adsorption of silane coupling agents onto glass fiber surfaces has been investigated. The type of adsorption was elucidated using electron spectroscopy for chemical analysis (ESCA or XPS). The surface charging was recorded using streaming potential analysis. The silane bond strength was tested by boiling the silanized fibers in water for 2 h. Thereafter the conductivity of the water was measured in order to estimate the capability of the silane surface film to prevent ion dissolution from the glass. ESCA provided information on the amount adsorbed and indicated that substantial rearrangement in the surface film structure occurred as a function of the silane concentration. The aminosilane produced a strong positive charge on the glass fibers, while the nonionic silanes were only partly condensed, giving rise to a substantial enhancement of the negative charge. The conductivity measurements indicated that the silane films were present as a loose patchlike silane network on the surface of the E-glass fibers. This conclusion is in accordance with the results obtained with all the techniques used.     

Biocompatible regenerated cellulose/halloysite nanocomposite fibers

Regenerated cellulose (RC) bio-nanocomposite fibers reinforced with halloysite nanotubes (HNT) were fabricated through wet spinning technique via ionic liquid as a green solvent. Mechanical properties, water uptake, thermal stability, and cytocompatibility of the obtained fibers were examined. FTIR spectra indicated the uniform dispersion of HNT in the cellulose network. XRD analysis, together with FE-SEM images indicated that HNT was dispersed homogenously in the polymer. Moreover, mechanical and thermal stabilities of the nanocomposite fibers were notably increased through the addition of HNT. Eventually, human skin fibroblasts proliferation on nanocomposite fibers demonstrated good cyto-compatibility. These findings highlight the potential of HNT nanocomposite fibers for biological and biomedical applications.     

Effects of cellulose fibers in polypropylene composites

A systematic study of the effect of surface pretreatment of cellulosic fibers and the processing time and temperature on the mechanical properties of the cellulose-containing polypropylene was undertaken. Using non-treated fibers, the elastic modulus increased gradually with the cellulose content, typically doubling its value at 30 phr fiber content. Treatment of fibers with coupling agent improves significantly the interfacial adhesion and therefore the mechanical properties of composite. Scanning electron micrographs reveal that the shear stress is sufficiently high to break and delaminate the cellulosic fibers. Addition of maleic anhydride modified polypropylene also improves the properties of resulting composites.     

Functional hybrid fibers of cellulose/microcrystalline chitosan. I. Manufacture of viscose/microcrystalline chitosan fibers

Blends of microcrystalline chitosan (MCCh) with cellulose xhanthate alkaline solutions were prepared to investigate the effects of aqueous MCCh gel concentration and additives on the spinnability of hybrid cellulose/chitosan fibers and their properties. The properties of the spinning solution were mainly dependent on the concentration of MCCh in the aqueous gel‐like dispersion and the amount mixed into the cellulose xhanthate solution. Sodium alginate chemically close to cellulose and chitosan was used as an additive to improve the miscibility of chitosan due to the ionic bonds formed with chitosan 2‐amino groups. Using an optimized ratio of 2 : 1 of MCCh to the sodium alginate, a maximum of 6% of MCCh calculated from alpha‐cellulose content could be introduced into the sodium xhanthate solution containing originally 9% of alpha‐cellulose. The yield of MCCh in the resulting fibers was dependent on the molecular mass, and varied between 73–82%. The strength, elongation, and color of the resulting hybrid fibers were only slightly changed and the WRV remarkably increased compared to standard fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1725–1730, 2000     

Hydrophobic cellulose fibers via ATRP and their performance in the removal of pyrene from water

In the present work, cellulose fibers were modified by grafting with poly(lauryl acrylate) and poly(octadecyl acrylate). The grafted materials were prepared by polymerization of the corresponding monomers via surface initiated atom transfer radical polymerization, starting from cellulose papers previously modified with 2‐bromoisobutyryl groups. The polymerizations were carried out in the presence of ethyl‐2‐bromoisobutyrate, as a sacrificial initiator, added to control the molecular weight of the anchored segments, and polymerization kinetics. The grafting of both polymers was confirmed by infrared spectroscopy and elemental analysis. The effect of grafting these polymers on the thermal stability, morphology, and surface properties of cellulose fibers was studied using thermogravimetric analysis, scanning electron microscopy, and measuring water contact angle, respectively. The results reveal that grafting poly(lauryl acrylate) and poly(octadecyl acrylate) to cellulose confers the filter paper a hydrophobic character, and increases its affinity with pyrene, allowing the removal of this pollutant from water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44482.