Preparation and characteristics of composites of high‐crystalline cellulose with polypropylene: Effects of maleated polypropylene and cellulose content

Binary composites of high‐crystalline fibrous cellulose with polypropylene (PP) or maleic anhydride‐grafted polypropylene (MAPP) were prepared by melt‐mixing with different contents of cellulose from 0 to 60 wt %. Ternary composites of cellulose with PP and MAPP were also prepared to investigate the effects of MAPP as a compatibilizer between cellulose and PP. Scanning electron microscopy revealed that the addition of MAPP generates strong interactions between a PP matrix and cellulose fibers: All cellulose fibers are encapsulated by layers of the matrix and connected tightly within the matrix. Thus, the tensile strength and Young's modulus of MAPP‐containing composites increase with an increase in MAPP and cellulose content, in contrast to the decrease in tensile strength of a PP‐based binary composite with an increase in cellulose. Cellulose fibers act as a nucleating agent for the crystallization of PP, which is promoted by the addition of MAPP through an increase of the crystallization temperature of PP in the composite. Accordingly, both cellulose and MAPP facilitate the thermooxidative stability of PP composites in the following order: MAPP/cellulose > PP/MAPP/cellulose > PP/cellulose > PP. Relative water absorption increases with an increase in cellulose content, decreasing with the addition of MAPP. MAPP‐containing cellulose composites have high potential for applications as environmentally friendly materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 337–345, 2003     

Effects of silane coupling agent and maleic anhydride‐grafted polypropylene on the morphology and viscoelastic properties of polypropylene–mica composites

In this study, morphology, and dynamic and mechanical properties of polypropylene–mica (PP–Mica) composites were investigated. To enhance the adhesion between PP and mica, maleic anhydride‐grafted PP (MAPP) and treated mica with silane coupling agent were used. MAPP (as a compatibilizer) and silane coupling agent (as a filler surface modifier) caused an interfacial bonding in the mica filled polypropylene composites. The effect of mica content, MAPP, and treated mica with silane coupling agent on the morphological properties were investigated by Scanning Electron Microscopy (SEM). The results showed that with increasing MAPP or silane coupling agent, dispersion of filler and adhesion between PP and filler were improved. Mechanical data showed that with increasing MAPP and mica treated with silane coupling agent, tensile modulus and flextural strength of composites were enhanced. Dynamic rheological behavior of composites was also investigated within the domain of linear viscoelasticity. The rheological observations indicated that the complex viscosity, storage and loss moduli increased, and tan δ decreased with increasing mica content. POLYM. COMPOS. 27:491–496, 2006. © 2006 Society of Plastics Engineers.     

Kudzu fiber‐reinforced polypropylene composite

Kudzu fiber‐reinforced polypropylene composites were prepared, and their mechanical and thermal properties were determined. To enhance the adhesion between the kudzu fiber and the polypropylene matrix, maleic anhydride‐grafted polypropylene (MAPP) was used as a compatibilizer. A continuous improvement in both tensile modulus and tensile strength was observed up to a MAPP concentration of 35 wt %. Increases of 24 and 54% were obtained for tensile modulus and tensile strength, respectively. Scanning electron microscopy (SEM) showed improved dispersion and adhesion with MAPP. Fourier transform infrared (FTIR) spectroscopy showed an increase in hydrogen bonding with an increase in MAPP content. Differential scanning calorimetry (DSC) analysis indicated little change in the melting temperature of the composites with changes in MAPP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1961–1969, 2002     

Morphological,mechanical, and physical properties of composites made with wood flour‐reinforced polypropylene/recycled poly(ethylene terephthalate) blends

Wood flour (WF)‐filled composites based on a polypropylene (PP)/recycled polyethylene terephthalate (r‐PET) matrix were prepared using two‐step extrusion. Maleic anhydride grafted polypropylene (MAPP) was added to improve the compatibility between polymer matrices and WF. The effects of filler and MAPP compatibilization on the water absorption, mechanical properties, and morphological features of PP/r‐PET/WF composites were investigated. The addition of MAPP significantly improved mechanical properties such as tensile strength, flexural strength, tensile modulus, and flexural modulus compared with uncompatibilized composites, but decreased elongation at break. Scanning electron microscopic images of fracture surface specimens revealed better interfacial interaction between WF and polymer matrix for MAPP‐compatibilized PP/r‐PET/WF composites. MAPP‐compatibilized PP/r‐PET/WF composites also showed reduced water absorption due to improved interfacial bonding, which limited the amount of absorbable water molecules. These results indicated that MAPP acts as an effective compatibilizer in PP/r‐PET/WF composites. POLYM. COMPOS., 38:1749–1755, 2017. © 2015 Society of Plastics Engineers     

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     

Preparation and characteristics of polypropylene-graft-maleic anhydride anchored micro-fibriled cellulose: its composites with polypropylene

The surface modification of micro-fibriled cellulose (MFC) was carried out through the hydrolysis–condensation reaction using (3-aminopropyl)triethoxysilane (APS) and then was subsequently treated with polypropylene-graft-maleic anhydride (MAPP) to give desired MAPP-anchored MFC (MAPP-a-MFC). The confirmation of surface modification for the pristine MFCs was characterized by FTIR, EDX, and XPS measurements. The polypropylene (PP) composites with MAPP-a-MFC were prepared via typical melt-mixing method. The effects of MAPP-a-MFC on the physical properties of the PP composites were investigated. From the results of mechanical properties, thermal behaviors, and the morphology of the composites, it was found that there was an improved interfacial adhesion between the MAPP-a-MFC and PP matrix in the composites.     

Cellulose/polypropylene composites: Influence of the molecular weight and concentration of oxidatively degraded and maleated polypropylene compatibilizers on tensile behavior

To improve interactions between fibrous cellulose (FC) and polypropylene (PP), oxidatively degraded polypropylene (DgPP) and maleated polypropylene (MAPP) were studied as compatibilizers. Both compatibilizers had the same mechanism, using esterification between the OH group in FC and the reactive (γ‐lactone, acid, and maleic anhydride) groups in the compatibilizers. However, the adhesion style with the ester bond was considerably different because of the arrangements of the reactive groups. DgPP had reactive groups at the polymer chain end, and the tensile behavior of the FC/PP/DgPP composite exhibited comparatively ductile behavior. However, MAPP had inner reactive groups, and the tensile behavior of the FC/PP/MAPP composite was quite brittle. Observation of these fracture surfaces suggested that the adhesion performance of the interface between FC and PP was strongly influenced by the arrangements of the reactive group. In addition, the performance was influenced by the molecular weight of DgPP and by the content of maleic anhydride groups in MAPP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Milling‐induced esterification between cellulose and maleated polypropylene

The ball milling of cellulose and maleic anhydride grafted polypropylene (MAPP) induced the formation of ester bonds between OH groups of cellulose and maleic anhydride groups of MAPP, in marked contrast to the melt mixing of the original cellulose and MAPP, through which the esterification was hardly observed. This esterification was hardly dependent on the chemical structure of MAPP. In agreement with the enhanced interfacial adhesion due to the formation of ester bonds, a composite prepared via ball milling revealed an improvement in the tensile strength with respect to a melt‐mixed composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1703–1709, 2004     

Preparation and physical properties of wood/polypropylene/clay nanocomposites

Wood plastic composites (WPCs) are attracting a lot of interests because they are economic, environmentally friendly, and show fairly good performance. To improve the performance of a wood/polypropylene (PP) composite, an organoclay was incorporated as a nanosize filler in this work. WPCs were prepared by melt blending followed by compression molding, and their performance was investigated by universal testing machine, izod impact tester, dynamic mechanical analyzer, thermal mechanical analyzer, differential scanning calorimetry, and TGA. Maleic anhydride polypropylene copolymer (MAPP) was used to increase compatibility between the PP matrix and wood particles and also improve the dispersion and exfoliation of the organoclay in the PP matrix. XRD analysis showed that the matrix of the WPCs with organoclay had intercalated structure. The SEM images of the WPCs with MAPP showed improved interfacial adhesion between the matrix and wood particles. The degree of water absorption increased with immersion time, but it could be restrained by incorporating MAPP. The performance of the WPCs was improved by the incorporation of the organoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Silica‐filled polypropylene composites: The effect of ethylene diamine dilaurate and maleic anhydride grafted polypropylene on mechanical properties,water absorption,morphology, and thermal properties

The effect of two compatibilizers, i.e. ethylene diamine dilaurate (EDD) and maleic anhydride grafted polypropylene (MAPP) on the mechanical properties, water absorption, morphology, and thermal properties of silica‐filled polypropylene (PP/Sil) composites were studied. The results show that the tensile, impact and flexural strengths (up to 2 php), Young's modulus, and elongation at break (Eb) increased with increasing EDD content. However, increasing MAPP content increases the tensile strength, Young's modulus, impact and flexural strengths, and water absorption resistance. At a similar compatibilizer content, EDD exhibits higher Eb, impact and flexural strengths but lowers tensile strength, Young's modulus, and water absorption resistance compared with MAPP. Scanning electron microscopy study of tensile fractured surfaces exhibits the evidence of better silica‐PP adhesion with MAPP and EDD compared with the similar composites but without compatibilizer. Fourier transform infra red spectra provide an evidence of interaction between EDD or MAPP with PP/Sil composites. Termogravimetry analysis results indicate that the addition of EDD or MAPP slightly increases the thermal stability of PP/Sil composites. Differential scanning calorimetry also indicates that PP/Sil composites with EDD or MAPP have higher heat fusion (ΔH_f(com)) and crystallinity (X_com) than similar composites but without compatibilizer. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Properties of polypropylene/aluminum trihydroxide composites containing nanosized organoclay

Montmorillonite is a promising substitute for aluminum trihydroxide in flame‐retardant polypropylene/aluminum trihydroxide (PP/ATH) composites. Study was made of the partial substitution of organoclay for ATH in PP/ATH composites. The total concentration of filler was kept at 30 wt%. The composites were compatibilized with two types of compatibilizer: commercial maleic anhydride functionalized polypropylene (PP‐g‐MA) and hydroxyl‐functionalized polypropylene (PP‐co‐OH) prepared with metallocene catalyst. The effect of compatibilization on the morphology was studied by the transmission electron microscopy and the scanning electron microscopy. Mechanical properties were characterized by tensile and impact measurements, and flammability properties with a cone calorimeter. Addition of compatibilizer and stearic acid (SA) treatment of the ATH particles contributed to the dispersion of the fillers. Both compatibilizers produced organoclay with exfoliated structure and improved adhesion between the fillers and the matrix. Toughness improved and decomposition and flammability were reduced. POLYM. ENG. SCI. 45:1568–1575, 2005. © 2005 Society of Plastics Engineers     

Interfacial interaction,morphology, and tensile properties of a composite of highly crystalline cellulose and maleated polypropylene

A composite of highly crystalline cellulose was synthesized via a melt‐mixing method with maleic anhydride (MA)‐grafted polypropylene (PP), MAPP, which was prepared by melt‐mixing PP with 0.25–8.0 phr (part of reagent per hundred parts of PP) of MA, and the morphology and tensile properties were examined with respect to the interfacial interactions of MAPP and cellulose. The graft degree (G_d) of MAPP increases with an increase in the initial MA amount up to 2.5 phr, beyond which it decreases because of the remaining of more free MA monomers and/or the formation of more oligomers remaining in the matrix. The morphology and tensile properties of the composite are affected strongly by G_d as well as the presence of the free MA in the matrix. For the MAPP without any free MA, even the G_d value as small as 0.25–0.5 wt % yields a maximal tensile strength. The existence of free MA monomers in the MAPP decreases the tensile strength, probably because of interrupting the interactions of the grafted MA groups with the OH groups of cellulose. The tensile properties of the composite correlate with the interfacial adhesion as well as the dispersion of cellulose microfibers in the matrix, both of which are determined by the interactions of the OH groups on cellulose with the grafted MA groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3830–3841, 2006     

Optimal performances of ultrasound treated kenaf fiber reinforced recycled polypropylene composites as demonstrated by response surface method

Kenaf fiber (KF) reinforced recycled polypropylene (RPP) composites were produced by melt cast method. To improve interfacial adhesion between fiber and RPP matrix, fiber surface modification was carried out by means of ultrasound treatment. Maleic anhydride grafted polypropylene (MAPP) was used as a coupling agent. Composites were examined by mechanical test, melt flow indexing test, scanning electron microscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Water uptake analysis and accelerated weathering test were carried out to find the suitability of the composites in outdoor application. Among the raw fiber contents ranging 10?50 wt % in the composites, the maximum tensile strength (TS) was observed at 40 wt % KF loading without using MAPP. Treated KF‐based composite with MAPP promotes this maximum TS value, which is 57% higher than that of raw KF‐based composite. TGA and DSC analyses exhibit an enhancement of thermal stability in treated KF‐reinforced RPP composites with MAPP. Incorporation of MAPP in the composites shows higher activation energy, suggesting improved interfacial bonding between fibers and matrix. Response surface method was employed to demonstrate the optimal treatment parameters for TS, showing excellent agreement with the observed values. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Dynamic rheology,mechanical performance,shrinkage, and morphology of chemically coupled talc‐filled polypropylene

The oscillatory shear rheological properties, mechanical performance, shrinkage, and morphology of polypropylene (PP)‐talc composites chemically coupled by maleic‐anhydride‐grafted polypropylene (MAPP) were studied. The samples were prepared in a co‐rotating L/D = 40, 25 mm twin‐screw extruder. Tensile tests carried out on injection‐molded samples showed a reinforcing effect of talc up to 20 wt% on PP. Upon using MAPP, the mechanical performance of PP‐30% talc showed a maximum of about 10% increase in tensile strength at 1.5 wt% of MAPP. A Newtonian plateau (η₀) at the terminal zone was observed for the complex viscosity curve of pure PP and PP‐talc composites plotted against frequency up to 30 wt%. Upon increasing the talc content to 40 and 50 wt%, the complex viscosity at very low shear rates sharply increased and showed yield behavior that might be due to the formation of a network of filler agglomerates in the melt. Analysis of viscosity behavior in the power‐law region revealed that the flow behavior index‐n‐decreased from 0.45 for 10 wt% of talc down to about 0.4 for 40 wt% of talc. Upon increasing the talc content to 50 wt%, n decreased to a value even lower than that of the neat PP resin. The frequency of the crossover point represents molecular mobility and relaxation‐time behavior. The crossover frequency of the composites was nearly constant up to 30 wt% of talc and decreased at higher filler loadings. The optimum amount of coupling agent could be correlated with the minimum point in crossover frequency and crossover modulus. The shrinkage behavior of the composites with and without MAPP resin was studied and correlated with the rheological properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Isolation and characterization of betel nut leaf fiber: Its potential application in making composites

Betel nut leaf fiber (BNLF) is a new finding as cellulosic filler for polymer composites. Its main constituents are 75% α‐cellulose, 12% hemicelluloses, 10% lignin, and 3% others matter, viscosity average molecular weight 132,000 and degree of crystallinity 70%. In the present work, BNLF reinforced polypropylene (PP) composites were prepared using heat press molding method. 5–20 wt% short length fiber is taken for getting benefits of easy manufacturing and the fiber was chemically treated with NaOH, dicumyl peroxide (DCP), and maleic anhydride‐modified PP (MAPP) to promote the interfacial bond with PP. The extent of modification of fiber was assessed on the basis of morphology, bulk density, moisture absorption, thermal, and mechanical properties of untreated fiber, treated fiber, and their reinforcing PP composites. The tensile and flexural strength of composites increase with the increase of fiber loading up to 10 and 20 wt%, respectively. It was also observed that Young's modulus and flexural modulus increase with fiber loading. The thermal degradation behavior of resulting composites was investigated. Among the various treated fibers, MAPP‐treated fiber composite showed best interfacial interactions as well as mechanical and thermal properties. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Cellulose nanofibril‐reinforced polypropylene composites for material extrusion: Rheological properties

Polypropylene (PP) is not typically utilized in 3D printing material extrusion because PP shrinks and warps during the printing process. Cellulose nanofibrils (CNF) have the potential to make PP 3D printer processable and also enhance mechanical properties of PP printed parts. The rheological behavior of CNF‐PP composites during material extrusion requires study because it is different from injection molding and compression molding processes. This study revealed the effects of CNF contents (3 and 10 wt%) and maleic anhydride polypropylene (MAPP) coupling agent on the rheological properties of CNF–PP composites. Morphological analysis showed that CNF agglomerated during spray drying and a spherical structure was formed. Rheological tests showed that the elastic modulus, complex viscosity, viscosity, and transient flow shear stress of PP were increased by the addition of 10 wt% CNF, while the creep strain of PP was reduced. The damping factor and stress relaxation time remained the same when 10 wt% CNF was added to the PP. Incorporation of MAPP into the CNF–PP composites impacted the rheological properties of the CNF–PP composites. Flexural strength and modulus of PP were improved by 5.9% and 26.8% by adding 10 wt% CNF compared to the control. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Maleic anhydride grafted polypropylene as a coupling agent for polypropylene composites filled with ink‐eliminated waste paper sludge flour

Ink‐eliminated sludge flour (IESF), a waste residue from the recycling treatment of waste paper, is a promising new kind of filler for thermoplastic polymers with a good price/performance ratio and advantages for environmental protection. In this study, high‐impact polypropylene (PP) and maleic anhydride grafted polypropylene (MAPP) were chosen as a polymer matrix and a coupling agent, respectively, for the preparation of IESF/PP composites, and the structures and properties of the obtained composites were also investigated. The experimental results revealed that IESF not only induced the crystallization orientation of PP along the b axis but also had a restraining effect on the formation of the β phase during the recrystallization of PP from the melt; the addition of MAPP further strengthened this effect to some extent. In addition, the proper addition of MAPP was helpful for improving the thermal stability of the IESF/PP composites. With the strengthening of the interfacial interaction between the IESF and PP matrix by MAPP, the resultant efficient stress transfer from the PP matrix to the IESF particles led to increased tensile and flexural strength. However, the original greater rigidity of MAPP, with respect to PP, reduced the toughness of the composites and caused some negative effects on the impact strength and the elongation at break. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2320–2325, 2004     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Effect of MAPP on interfacial compatibility of wood flour/polypropylene composite evaluated with dielectric approach

To quantitatively evaluate the effect of maleic anhydride grafted polypropylene (MAPP) as a coupling agent on interfacial compatibility between wood and polymer in wood/polypropylene (PP) composite, the dielectric constant and dielectric loss factor were measured for poplar (Populus tomentasa Carr.) wood flour/polypropylene (PP) composites prepared with six MAPP loading levels (0.5, 1.0, 1.5, 2.0, 4.0, and 8.0%), and the Cole–Cole plots, the dielectric relaxation strength, the distribution of relaxation time and the activation thermodynamic quantities of the dielectric relaxation based on the reorientation of the methylol groups (CH₂OH) in the amorphous region of wood cell wall were further analyzed. The results showed that the dielectric relaxation strength decreased with the MAPP loading and dropped to the lowest at MAPP loading of 2.0%, after which it kept almost constant. It suggested that the internal bonding between wood and PP molecules was the strongest at 2.0% MAPP, therefore the reorientation of the methylol groups in wood became very difficult under the strong hindrance from the long‐chained PP molecules and the physical or/and chemical bonds between MAPP, wood flour, and PP in the composites. The activation free energy ΔE could be served as the indicator to quantitatively evaluate the effect of MAPP on interfacial compatibility of the wood/PP composites. ΔE of 2.0% MAPP modified composites showed the maximal value among all the tested conditions, which was 33.52 kJ mol⁻¹; while the values for 1.5 and 4.0% MAPP modified were 23.35 and 21.75 kJ mol⁻¹. Therefore, excessive MAPP was not beneficial to improve the internal compatibility of wood/PP composites, but had negative effect. POLYM. COMPOS., 35:489–494, 2014. © 2013 Society of Plastics Engineers