Nanostructure of potato starch. II. Structure of a highly crystalline gel obtained by retrogradation using X‐ray diffraction techniques

A highly crystalline gel (65% crystal portions) was prepared by retrogradation of injection‐molded potato starch in humid atmosphere. The different components of the nanostructure were identified by means of successive melting processes using “in situ” simultaneous wide and low angle X‐ray diffractions. At low temperatures, structural changes such as annealing phenomena or evaporation of water, giving rise to a thickening of the gel, are observed. In the range of 55–75°C, a first transition due to melting of a layered structure of concentric sphere‐like alternating crystalline and amorphous lamellar shells (amylopectine, AP, being the crystalline component) is detected. Analysis of results reveals that the AP crystallization contributes 25% to the overall crystal fraction. A spherulitic structure of alternating radial lamellae from amylose (AM) or AP melts in a higher temperature region between 75 and 86°C. This modification represents the major contribution to crystallinity of about 40%. Unexpectedly, the crystalline blocks of such a structure are abnormally anisometric; i.e., they are thicker than their width. This has been related to a contraction of the AMAP‐co‐spherulite due to an excessive growth of the AP‐shell crystals. The anisometry of the blocks of the AMAP lamellae vanishes at the beginning of the melting of the AP shell crystals, just when the total crystallinity decreases below 50% at 60°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 689–696, 2007     

Structural changes of injection molded starch during heat treatment in water atmosphere: Simultaneous wide and small‐angle X‐ray scattering study

Native starches with wide varying amylose content were processed by injection molding. The injection‐molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide‐ and small‐angle X‐ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection‐molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form V_h. After wet conditioning, WAXS of the injection‐molded samples shows again the appearance of the crystal forms A or B, and crystallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rapidly decreases until its disappearance at 85–90°C, the invariant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystallinity (form B), presumably stabilized by the presence of the V_h structure (12–15%). Real‐time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystallization of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301–309, 2004     

Mechanical enhancement of amine‐functionalized TiO2 reinforced polyimine composites

Polyimine vitrimers are known for their malleability, which endows these materials with properties such as self‐healing, recycling, and reshaping. To enhance the mechanical properties of the polyimine vitrimers, composites were fabricated by incorporating amine‐functionalized TiO₂ microspheres (amTiO₂MS) into polyimine matrix. The pure polyimine matrix and polyimine composites hybridized with TiO₂ microspheres (TiO₂MS) without surface modification were also obtained and examined as the controls in characterization. X‐ray powder diffraction, scanning electron microscopy, and energy dispersive X‐ray spectroscopy were employed to demonstrate the presence and distribution of amTiO₂MS and TiO₂MS in the polyimine matrices. The investigation of mechanical properties of the amTiO₂MS enhanced polyimine composites and control samples indicated that incorporation of amTiO₂MS and TiO₂MS exhibited different characteristic distribution, which strongly affected the performance of the composites. The optimal filling concentration of amTiO₂MS was found to be 3%, with which the microspheres were uniformly distributed in the polyimine matrix. The self‐healing behavior of the polyimine‐amTiO₂‐X was also studied. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46446.     

A DMA study of the interfacial changes on injection‐molded iPP/mica composites modified by a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene

Present work concerns to the study of the dynamic mechanical and thermal responses of selected polypropylene (iPP)/mica composites with a modified interface from the matrix side by using a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene, coming from a byproduct of industrial polymerization reactors. Thus, the study is mainly focused on the 75/25 iPP/mica ratio since it was identified in previous works as providing the maximum inter mica particle distance to assure they should participate in the overall process of dissipation of the mechanical energy supplied to the composites. Hence, the present dynamic mechanical analysis discussion tries to correlate the damping responses of the injection‐molded composites with those previously obtained but over compression molded composites as the basis of further studies all along the compositional iPP/mica map. Therefore, the latter let us, on the one hand, to follow how the main values of the different dynamic mechanical analysis parameters vary because of the interfacial modifier presence, and on the other, to develop a robust correlation between them and the corresponding macroscopic mechanical parameters. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45366.     

The effect of a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene interface agent on the impact properties of iPP/mica composites

The present article is twofold. One of the purposes of this work lies in the study of the impact behavior of the polypropylene/mica system incorporating an interface modifier obtained from an industrial polymerization byproduct. The interface agent used was a p‐phenylen‐bis‐maleamic grafted atactic polypropylene (aPP‐pPBMA) obtained in our labs. The other objective is to obtain a mathematical model capable of forecasting the composite properties accurately. Consequently, this work has been undertaken by using a statistical Box‐Wilson experimental design in order to model the behavior of the composite system in terms of Charpy impact parameters. Two independent variables have been considered, the amount of mica particles and of interface agent. Impact strength, maximum force, and deformation were the dependent variables in the models. The existence of critical values in mica and interface agent optimizing the impact behavior is established. Additionally, an excellent correlation between the impact strength and the strength results coming from flexural and tensile tests is found. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44619.     

Correlation of nanostructural parameters and macromechanical behaviour of hyperbranched‐modified polypropylene using time‐resolved small‐angle X‐ray scattering measurements

Polypropylene (PP) is modified utilizing a poly(ester amide)‐based hyperbranched polymer (PS). A maleic‐modified PP is used to enhance the compatibility. Usual tensile experiments are carried out. The nanocrystalline structure is studied using small‐angle X‐ray scattering (SAXS) while a uniaxial mechanical load is simultaneously applied. SAXS patterns are analysed using procedures written in PV‐WAVE. The chord distribution function (CDF) is calculated and nanostructural parameters such as long period (l_p) and nanodeformation (?_Nano) are extracted. The correlations between macromechanical parameters and nanostructures are studied. Mechanical results show that PS has a plasticizing effect. Reactively blended samples demonstrate enhanced mechanical properties. SAXS patterns reveal a well‐known structure of PP as a peculiar architecture of the nanostructure. Crystalline branching occurs in a geometry that is known as a mother–daughter crystal lamellar structure, also called a crosshatching structure. It is concluded that adding PS distorts the stacking of crystalline domains. The structural information from SAXS patterns in reciprocal space is visualized in real space in the calculated CDFs. The CDFs indicate that in simple blends, l_p of the crystalline stacks increases compared to blank PP. Nevertheless, reactively blended samples show an increase of l_p compared to blank PP; however, they possess smaller l_p compared to simple blends. © 2012 Society of Chemical Industry     

Mechanical properties and densification behavior of β‐spodumene/anorthite composites

Although β‐spodumene/anorthite composites are interesting systems, little research work has been done to study their properties. This study aims at investigating the preparation and properties of β‐spodumene/anorthite composites containing β‐spodumene proportions ranging between 10 and 25 mass %. X‐ray diffraction analysis (XRD), Scanning electron microscopy (SEM), and the coefficient of thermal expansion (CTE) were used to characterize the effect of addition of β‐spodumene on the phase relations, microstructure, and thermal expansion behavior of resultant composites. The results show that the presence of β‐spodumene significantly reduces the porosity and reduces the densification temperature. It reduces thermal expansion and enhances the mechanical properties of anorthite‐containing composites.     

Monitoring of nylon 6,6/carbon fiber composites processing by X‐ray diffraction and thermal analysis

This work reports a study made to obtain carbon fiber/nylon 6,6 prepreg composites by hot‐compression molding. Thermogravimetric analysis (TG) and crystallinity degree determination were carried out to monitor the nylon 6,6 behavior during the different steps of the composite processing. The homogeneity of the carbon fiber/polymer matrix distribution was verified using microscopic analyses and the fiber content was determined by the acid‐digestion method. The results show that the processing parameters employed were adequate, allowing the manufacture of laminates with good texture and an adequate reinforcement/matrix relation (60/40). However, improvements need be done to minimize the pullout effect observed in the tensile specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3114–3119, 2002     

Nanostructure development in wet amorphous amylopectin as revealed by in situ X‐ray scattering methods

Completely amorphous, transparent bars of amylopectin were prepared by injection molding of pure native semicrystalline samples (Waxy Maize). The formation of a semicrystalline morphology was studied during annealing treatment at various temperatures in a wet atmosphere, using simultaneous WAXS and SAXS. Amylopectin samples crystallized during 20 days in a humid atmosphere at room temperature and subjected to a successive melting process were also studied by X‐ray scattering. Results indicate that individual molecules crystallize independently from each other, similar to the case of native amylopectin grains. During the first stages of crystallization, the changes in the SAXS pattern suggest that uncorrelated crystal blocks are formed, which may arrange to lamellae (if a secondary network of double‐helix net‐points is hydrothermally dissociated). At the beginning of the crystallization process, only few amylopectin molecules (about 10%) are incorporated into the nanostructure. A shell‐like structure of semicrystalline layers, comparable to that of a native grain, develops. When crystallization proceeds further, the initially thin shell layers thicken. This causes the amorphous interlayers to be subjected to inner tensions, leading to a decrease in the melt temperature. After a storage time of 20 days in a humid atmosphere, amylopectin reaches a crystallinity level of 54%, only slightly lower than that of the initial native grains. Upon heating the retrograded amylopectin, immediately before complete melting, the long‐period shows a value of 15 nm with a crystal thickness, derived from WAXS, of only 4 nm. Such a structure, which has not been reported before, is due to the relaxations of the inner tensions during melting, which lead to a disappearance of inserted interlamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3832‐3839, 2006     

Characterization of polymer‐layered silicate (clay) nanocomposites by transmission electron microscopy and X‐ray diffraction: A comparative study

Several polymer‐layered silicate (clay) nanocomposites (PLSNs) were analyzed by transmission electron microscopy (TEM) and wide‐angle X‐ray diffraction (XRD) in an effort to characterize the nanoscale dispersion of the layered silicate. The PLSNs investigated included thermoset (cyanate esters) and thermoplastic polymers (polystyrene, nylon 6, and polypropylene‐g‐maleic anhydride). The results of this study reveal that the overall nanoscale dispersion of the clay in the polymer is best described by TEM, especially when mixed morphologies are present. XRD is useful for the measurement of d‐spacings in intercalated systems but cannot always observe low clay loadings (<5%) or be used as a method to identify an exfoliated nanocomposite where no XRD peaks are present (constituting a negative result). Most importantly, the study showed that XRD is not a stand‐alone technique, and it should be used in conjunction with TEM. Our studies suggest that new definitions, or a clarification of existing definitions, are needed to properly describe the diversity of PLSN nanostructures seen in various materials. Published 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1329–1338, 2003     

Investigation of mechanical properties of alumina nanoparticle‐loaded hybrid glass/carbon‐fiber‐reinforced epoxy composites

This research work investigates the tensile strength and elastic modulus of the alumina nanoparticles, glass fiber, and carbon fiber reinforced epoxy composites. The first type composites were made by adding 1–5 wt % (in the interval of 1%) of alumina to the epoxy matrix, whereas the second and third categories of composites were made by adding 1–5 wt % short glass, carbon fibers to the matrix. A fourth type of composite has also been synthesized by incorporating both alumina particles (2 wt %) and fibers to the epoxy. Results showed that the longitudinal modulus has significantly improved because of the filler additions. Both tensile strength and modulus are further better for hybrid composites consisting both alumina particles and glass fibers or carbon fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39749.     

Effects of postcure temperature variation on hygrothermal‐mechanical properties of an out‐of‐autoclave polymer composite

The effects of cure temperature variation on the properties of an out‐of‐autoclave polymer composite manufactured using Cycom 5320 8HS prepreg were investigated using different postcure temperatures of a two‐stage cure cycle. In addition, the effects of adverse environmental conditions on the cure temperature variation were studied by conditioning the samples in an environmental chamber until they reached moisture equilibrium. The state of cure was obtained using a differential scanning calorimeter and dynamic mechanical analyzer. The mechanical properties were obtained using short‐beam shear (SBS) and combined loading compression (CLC) test methods. The state of cure obtained showed increases in total heat of reaction, degree of cure, and glass transition temperature as the postcure temperature increased. The SBS and CLC strengths showed an increasing trend as postcure temperature increased. Good correlations were obtained between the material's cure temperatures, state of cure, and mechanical properties for room temperature dry and hot wet conditions. The study showed that the state of cure can be used to define, monitor, and verify the cure quality. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3090–3097, 2013     

Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

Thermal and mechanical properties of polypropylene/wood‐flour composites

In this research, polypropylene/wood‐flour composites (WPCs) were blended with different contents of wood and/or maleated polypropylene (MAPP) and clay. We found that the addition of MAPP or clay in the formulation greatly improved the dispersion of the wood fibers in the composite; this suggested that MAPP or clay may have played the role of an adhesion promoter in the WPCs. The results obtained with clay indicate that it also acted as a flame retardant. The thermal tests carried out with the produced samples showed an increased crystallization temperature (T_c), crystallinity, and melting temperature (T_m) with wood loading. The increase of the two former parameters was explained by the incorporation of wood flour, which played the role of nucleating agent and induced the crystallization of the matrix polymer. On the other hand, the T_m increase was ascribed to the insulating properties of wood, which hindered the movement of heat conduction. The effects of UV irradiation on T_m and T_c were also examined. T_c increased with UV exposure time; this implied that UV degradation generated short chains with low molecular weight that could move easily in the bulk of the sample and, thus, catalyze early crystallization. The flexural strength and modulus increased with increasing wood‐flour content. In contrast, the impact strength and tensile strength and strain decreased with increasing wood‐flour content. All of these changes were related to the level of dispersion of the wood flour in the polymeric matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structural aspects of mechanical properties of iPP‐based composites. I. Composite iPP fibers with VGCF nanofiller

Nanocomposite fibers consisting of isotactic polypropylene (iPP) as a matrix filled with vapor grown carbon nanofibers (VGCF) have been prepared and their fine crystalline structure and mechanical properties characterized. The obtained results point out that the VGCF oriented along the fiber extrusion direction induce crystallization in the surrounding iPP matrix in a special way leading to the formation of oriented iPP α‐transcrystallite layers. The VGCF content and the draw ratio (DR) affect the textural properties of the composite material and lead to the formation of an anisotropic structure. The improvements of the mechanical properties of the composite fibers in both undrawn and drawn states are attributed to the VGCF aligning effect during extrusion, which produces highly oriented iPP crystalline structure, rather than to the reinforcing effect of the nanofibers. A new detailed scheme explaining the changes in tensile strength from the structural point of view is proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41865.     

An X‐ray scattering study of water‐conditioned injection‐molded starch during isothermal heating

The in situ structure variation of injection‐molded starch (as processed and after water conditioning) during heat treatment was investigated by means of wide‐angle X‐ray scattering using synchrotron radiation. Results confirm that the crystal structure of potato starch is destroyed after injection molding, while as‐processed corn starch preserves some degree of crystallinity. This residual crystallinity in corn starch is related to the crystalline Vh‐form, made of complexes of amylose with lipids. Furthermore, it is shown that both starch types can develop crystallinity by water conditioning: potato starch yields the crystal B‐form, while corn starch yields the crystal A‐form coexisting with the persistent Vh‐form. Upon isothermal heating of samples under vacuum, a rapid decrease of crystallinity, which is a function of both time and treatment temperature, is detected. Crystallinity variations are discussed in terms of water evaporation, the leveling‐off values of crystallinity being dependent on the temperature of the isothermal treatment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 17–21, 2003     

Recycled car bumpers' impact resistance investigated by wide‐angle X‐ray diffraction

The recycled polyolefinic product from discarded standard car bumpers collected from Rio de Janeiro suburb shops was characterized by mechanical and wide‐angle X‐ray scattering (WAXS) methods. We found that the recycled plastic mixture is composed mainly of polypropylene (PP), containing ethylene‐propylene‐diene (EPDM) terpolymers and a minor proportion of high‐density polyethylene (HDPE), and is highly resistant to impact. The results were compared with the corresponding data obtained from binary and ternary blends of virgin PP, EPDM, and HDPE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 999–1004, 2000     

Physical properties and enzymatic hydrolysis of poly(L‐lactide)–TiO2 composites

Amorphous poly(L ‐lactide) (PLLA) composite films with titanium dioxide (TiO₂) particles were prepared by solution‐casting using methylene chloride as a solvent, followed by quenching from the melt. The effects of surface treatment, volume fraction, size, and crystalline type of the TiO₂ particles on the mechanical properties and enzymatic hydrolysis of the composite films were investigated. The tensile strength of the PLLA composite films containing TiO₂ particles except for anatase‐type ones with a mean particle size of 0.3–0.5 μm was lowered and the Young's modulus became higher with increasing the content of TiO₂ particles. The tensile strength of the composite films containing anatase‐type TiO₂ with a mean particle size of 0.3–0.5 μm at contents of 20 wt % or less was almost the same as that of the pure PLLA film. The enzymatic hydrolysis of PLLA matrix was accelerated by the addition of the hydrophilic anatase‐type TiO₂ particles (nontreated or Al₂O₃ treated) with a mean particle size of 0.3–0.5 μm at relatively high contents such as 20 wt %. On the other hand, the enzymatic hydrolysis of PLLA matrix was inhibited by composite formation with the hydrophobic rutile‐type TiO₂ particles (Al₂O₃‐stearic acid treated, or ZrO₂‐Al₂O₃‐stearic acid treated). These results suggest that the mechanical properties and enzymatic hydrolyzability of the PLLA can be controlled by the kind and amount of the added TiO₂ particles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 190–199, 2005     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber composites

The influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber (SBR) composites was investigated. When the starch particles were directly melt‐mixed into rubber, the stress at 300% elongation and abrasion resistance decreased evidently with increasing starch amount from 5 to 20 phr. Scanning electron microscopy observations of the abrasion surface showed that some apparent craters of starch particles were left on the surface of the composite, which strongly suggested that the starch particles were large and that interfacial adhesion between the starch and rubber was relatively weak. To improve the dispersion of the starch in the rubber matrix, starch/SBR master batches were prepared by a latex compounding method. Compared with the direct mixing of the starch particles into rubber, the incorporation of starch/SBR master batches improved the abrasion resistance of the starch/carbon black/SBR composites. With starch/SBR master batches, no holes of starch particles were left on the surface; this suggested that the interfacial strength was improved because of the fine dispersion of starch. Dynamic mechanical thermal analysis showed that the loss factor at both 0 and 60°C increased with increasing amount of starch at a small tensile deformation of 0.1%, whereas at a large tensile strain of 5%, the loss factor at 60°C decreased when the starch amount was varied from 5 to 20 phr. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009