Micro‐contact reconstruction of adjacent carbon nanotubes in polymer matrix through annealing‐Induced relaxation of interfacial residual stress and strain

Thermoplastic polyurethane (TPU)/multi‐walled carbon nanotubes (CNT) nanocomposites were prepared by twin‐screw extrusion and micro injection molding. The electrical conductivity of micro injection molded polymer nanocomposites exhibits a low value and uneven distribution in the micromolded samples. Real‐time tracing of electrical conductivity was conducted to investigate the post thermal treatment on the electrical conductivity of microinjection molded composites. The results show that postmolding thermal treatment leads to a significant increase in the electrical conductivity by over three orders of magnitude for 5 wt % CNT‐filled TPU composites. In‐situ Transmission electron microscopy confirms the conductive CNT network does not change at the micron/sub‐micron scale during thermal treatment. TEM image analysis by a statistical method was used to determine the spatial distribution of CNT in the sample and showed that the average distance between adjacent CNT reduced slightly at the nanometer scale after postmolding thermal treatment. A new conductive mechanism is proposed to explain the enhancement of electrical conductivity after thermal treatment, i.e. micro‐contact reconstruction of adjacent CNT in the polymer matrix through annealing‐induced relaxation of interfacial residual stress and strain. Raman spectra and small angle X‐ray scattering curve of annealed samples provide supporting evidence for the proposed new conductive mechanism. The electron tunneling model was used to understand the effect of inter‐particle distance on the conductivity of polymer composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42416.     

Crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 nanocomposites

This article presents the effects of nanoclay and supercritical nitrogen on the crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 (PA6) nanocomposites with 5 and 7.5 wt% nanoclay. Differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and polarized optical microscopy (POM) were used to characterize the thermal behavior and crystalline structure. The isothermal and nonisothermal crystallization kinetics of neat resin and its corresponding nanocomposite samples were analyzed using the Avrami and Ozawa equations, respectively. The activation energies determined using the Arrhenius equation for isothermal crystallization and the Kissinger equation for nonisothermal crystallization were comparable. The specimen thickness had a significant influence on the nonisothermal crystallization especially at high scanning rates. Nanocomposites with an optimal amount of nanoclay possessed the highest crystallization rate and a higher level of nucleation activity. The nanoclay increased the magnitude of the activation energy but decreased the overall crystallinity. The dissolved SCF did not alter the crystalline structure significantly. In contrast with conventionally injection‐molded solid counterparts, microcellular neat resin parts and microcellular nanocomposite parts were found to have lower crystallinity in the core and higher crystallinity near the skin. POLYM. ENG. SCI., 46:904–918, 2006. © 2006 Society of Plastics Engineers     

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     

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     

Effect of thermal conductivity and heat transfer on crystallization,structure, and morphology of polypropylene containing different fillers

The crystallization behavior, structure, and morphology developed was investigated for polypropylene containing different fillers such as silica, calcium carbonate, talc, mica, graphite, etc. by using compression‐molded samples prepared at several cooling rates. It was observed that the crystallinity obtained for any given composition depended on the thermal conductivity of the filler and the PP composite containing it as well as the cooling rate to which it was subjected. These composites exhibited skin‐core type of morphology and the skin layer thickness was found to depend not only on the cooling rate but also on the type of filler, its thermal conductivity, etc. These various experimental findings were discussed in light of the phenomenological model described in our earlier work, which correlates thermal conductivity and degree of crystallinity for various compositions of PP containing additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 615–623, 2004     

Combined effect of shear and nucleating agent on the multilayered structure of injection‐molded bar of isotactic polypropylene

Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallinity,thermal diffusivity,and electrical conductivity of carbon black filled polyamide 46

Polyamide 46 (PA 46) with carbon black (CB) has been subjected to a heat treatment. Crystallinity, specific heat capacity, crystalline melting peak temperature, thermal diffusivity, and electrical conductivity were measured. The crystallinity increases with duration of thermal treatment. The maximum value is dependent on the filler fraction. A lower CB content leads to a higher crystallinity at maximum tempering time. The crystalline melting peak temperature increases with decreasing filler fraction and duration of thermal treatment due to different crystal types and/or diverging geometric forms of the crystals. Thermal diffusivity and electrical conductivity act positively proportional to each other and increase with CB content and tempering time. The thermal diffusivity decreases with increasing temperature. The volume resistance of PA 46 is lowered by heat treatment. By CB addition in combination with a tempering process, the PA 46 can be transferred into a conductor. CB is moved by PA 46 crystals into amorphous regions forming conductive pathways. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48882.     

Rubber‐toughened polyamide‐6 with a low thermal expansion coefficient: effect of preferential distribution of rubber and inorganic filler

The effects of morphological changes on the thermal expansion, toughness and heat resistance of polyamide‐6 (PA)/styrene–ethylene–butylene–styrene (SEBS)/polyphenylene ether (PPE) blends were investigated. Compared with the typical ‘sea (PA matrix)–island (PPE domain)–lake (SEBS in PPE domain)’ morphology, an injection‐molded ternary blend with a preferential distribution of SEBS component at the interface between PA and PPE exhibited a low coefficient of linear thermal expansion (CLTE) in the flow direction. This low CLTE was ascribed to the deformation of SEBS and PA into a co‐continuous microlayer network structure during injection molding. Consequently, the expansion preferentially occurred towards the thickness direction. Further CLTE reduction either by a change in PA viscosity or by the selective location of an inorganic filler was examined, and its influences on impact strength and heat resistance are discussed based on transmission electron microscopy observations. © 2015 Society of Chemical Industry     

Injection molding of syndiotactic polystyrene/clay nanocomposites

This study aims at exploring the effect of a commercial organoclay montmorillonite (MMT) on the final properties of syndiotactic polystyrene (sPS) injection‐molded samples. To this goal, injection‐molded specimens made from neat sPS and commercial MMT modified with various organic compounds were prepared in different molding conditions. Dispersion of clay was attained via melt blending, directly in the injection chamber of the injection‐molding machine. The obtained specimens were analyzed by IR spectroscopy, X‐ray diffraction, thermogravimetry, and differential thermal analysis, with the aim of elucidating the effect of clay on the microstructures of the samples. Results clearly show that, depending on the organic modification, the presence of clay can induce strong effects on final crystallinity. This behavior can be attributed mainly to the role played by clay on the kinetics of the crystallization process. Eventually, it was found that the addition of a small percentage of clay (1%) in sPS can substantially widen the processing window of the material. POLYM. ENG. SCI. 46:1768–1777, 2006. © 2006 Society of Plastics Engineers.     

Influence of surface topography,crystallinity, and thermal conductivity on reflectance and color of metallic‐effect high‐density polyethylene parts filled with aluminum pigments

Metallic effect in injection molded parts is created using composites of high‐density polyethylene (HDPE) filled with high‐sparkle aluminum (Al) pigments (HDPE/Al). The mechanism of micro shrinkage induced by the leafing phenomenon influences the surface topography and roughness, and has been studied with SEM and AFM. Reflectance, whiteness index (WI), and luminance (L*) of the surface were assessed in relation to the surface roughness, the particle sizes, the crystallinity and thermal conductivity of composites. The results show that the leafing induces the micro shrinkage and causes micro caverns, which increased surface roughness. Besides, the length of micro caverns and surface roughness increased as the particle size increased. These morphologies were not benefit for improving reflectance, WI, and L* values, therefore the reflectance, WI, and L* values decreased proportionally with the surface roughness and particle sizes increased. High‐sparkle Al pigments improved the crystallinity and thermal conductivity of the composites. A higher reflectance, WI, and L* were associated with a higher crystallinity and a higher thermal conductivity. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Effect of crystallization and interface formation mechanism on mechanical properties of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate

A previous study has shown that the adhesion between the film and substrate of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate was evident with the increases in barrel temperature and injection holding pressure. In this second part of the research work, the crystallinity at the interfacial region (i.e., region between the film and the injected substrate) was extensively studied using FTIR imaging, polarized light microscopy, and DSC in an attempt to determine the level of influence that crystallinity has on the interface and bulk mechanical properties. Consequently, a more thorough and clearer picture of the influence of the inserted film on the interfacial crystallinity and subsequently the substrate mechanical properties, such as peel strength and impact strength, has been revealed. The initial proposition that crystallinity could enhance film–substrate interfacial bonding has been confirmed, judging from the higher peel strength with increasing crystallinity at the interfacial region. Nevertheless, the change in crystallinity was not only confined to the interfacial region. With the film acting as heat‐transfer inhibitor between the injected resin and the mold wall, the total crystal structure of the substrate was substantially altered, which subsequently affected the bulk mechanical properties. The lower impact strength of film‐insert injection‐molded samples compared to that of samples without film inserts provided evidence of how the film could impart inferior properties to the substrate. The difference in cooling rate between the substrate and film might also cause other defects such as warpage and/or residual stress build‐up within the product. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 294–301, 2005     

The role of crystallinity and reinforcement in the mechanical behavior of polyamide‐6/clay nanocomposites

The mechanical behavior of compression‐molded polyamide‐6 (PA6) reinforced with 2 wt% of organo‐nanoclay (montmorillonite intercalated with ω‐amino dodecanoic acid) has been studied and compared to that of PA6. The tensile strength and the Young's modulus of the PA6/clay were 15% higher than those of PA6. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and X‐ray diffraction showed that the crystalline structures of PA6 and PA6/clay differed considerably. A crystallinity of 25% with a dual structure composed of the γ and α forms was obtained in PA6/clay, while a crystallinity of 31% with the α form as the dominant crystalline structure was obtained in PA6. To understand the role of the crystalline structure of PA6, the molding process was modified to obtain PA6 specimens with different levels of crystallinity and different crystalline forms. Quenching molten PA6 at a cooling rate sufficiently high to prevent crystallization gave a material that was predominantly amorphous (crystallinity of 7%) with traces of the mesomorphic β or γ* form. Annealing this material at 80°C considerably increased crystallinity to 21%, which was also of the mesomorphic β or γ* form. PA6 with a predominant crystalline γ form could not be generated. Comparisons with PA6/clay in terms of crystallinity and mechanical behavior lead to the conclusion that the improvements in rigidity and strength observed when montmorillonite is added to PA6 are related to the reinforcing filler and not to a modification of the crystalline structure.     

Effect of flow induced alignment on the thermal conductivity of injection molded carbon nanotube‐filled polystyrene nanocomposites

Carbon nanotube (CNT) nanocomposites with a polystyrene thermoplastic matrix were injection molded and the high shear stress exerted during the injection process partially enabled the alignment of the CNTs in the flow direction. Nanocomposites with different CNT loadings and degrees of alignment were produced, and their thermal conductivities were measured based on ASTM D5470. The results were compared with compression molded samples featuring random alignments of CNTs. The results showed that the injection molded samples possessed anisotropic thermal conductivities, due to the partial alignment of the CNTs in the flow direction. The effective medium approach was used to analytically estimate the thermal conductivity of the molded samples. Good agreement was observed between the experimental and analytically simulated results in lower CNT concentrations (less than 5 wt% of CNT). Using transmission electron microscopy pictures taken of the nanocomposites, the alignment of CNTs in the thermoplastic matrix were modeled; and their thermal conductivities were simulated using the finite element method. Good agreement was observed between the experiments and simulated results. POLYM. ENG. SCI., 55:753–762, 2015. © 2014 Society of Plastics Engineers     

Electrical and morphological properties of microinjection molded polystyrene/multiwalled carbon nanotubes nanocomposites

Masterbatch dilution was utilized to prepare polystyrene/carbon nanotubes (PS/CNT) nanocomposites for microinjection molding (µIM). The effect of processing parameters, such as injection velocity and melt temperature, on the microstructure and electrical conductivity of injection molded microparts was systematically investigated. The electrical conductivity of the microparts was measured in three perpendicular directions to determine anisotropy. Results showed that the measured conductivity is process‐dependent and melt temperature is the main factor that affects the electrical conductivity of the resultant samples. Electrical conductivity increased with an incremental loading fraction of CNT, and the percolation threshold shifted to higher filler loading concentration which was ascribed to the very high shear rate in µIM. In addition, Raman analysis, SEM observations, and simulation results indicated that CNT is preferentially oriented along the flow direction arising from the high shearing effect induced by µIM. POLYM. ENG. SCI., 56:1182–1190, 2016. © 2016 Society of Plastics Engineers     

Improved mechanical properties and structure of PP/nano‐CaCO3 blends prepared by low‐frequency vibration injection molding

BACKGROUD: Melt vibration technology was used to prepare injection samples of polypropylene (PP)/nano‐CaCO₃ blends. It is well known that nano‐CaCO₃ particles are easy to agglomerate owing to their large surface energy. Improving the distribution of nano‐CaCO₃ particles in PP/nano‐CaCO₃ blends is very important for enhancing the mechanical properties. In this work, low‐frequency vibration was imposed on the process of injection molding of PP/nano‐CaCO₃ blends. The aim of importing a vibration field was to change the crystal structure of PP as we studied previously and improve the distribution of nano‐CaCO₃ particles. Furthermore, the mechanical properties were improved. RESULTS: Through melt vibration, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding, the enhancement of the tensile strength and impact strength of the samples molded by vibration injection molding was 17.68 and 175.96%, respectively. According to scanning electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry measurements, it was found that a much better dispersion of nano‐CaCO₃ in samples was achieved by vibration injection molding. Moreover, the crystal structure of PP in PP/CaCO₃ vibration samples changed. The γ crystal form was achieved at the shear layer of vibration samples. Moreover, the degree of crystallinity of PP in vibration samples increased 6% compared with conventional samples. CONCLUSION: Concerning the microstructure, melt vibration could effectively change the crystal structure and increase the degree of crystallinity of PP besides improving the distribution of nano‐CaCO₃ particles. Concerning the macrostructure, melt vibration could enhance the mechanical properties. The improvement of mechanical properties of PP/nano‐CaCO₃ blends prepared by low‐frequency vibration injection molding should be attributed to the even distribution of nano‐CaCO₃ particles and the formation of γ‐PP and the increase of the degree of cystallinity. Copyright © 2007 Society of Chemical Industry     

Moisture absorption by various polyamides and their associated dimensional changes

The dimensional changes associated with moisture absorption were examined for various polyamides (PAs). Plaques of varying thickness were compression‐molded or injection‐molded and then immersed in water. Periodically, the plaques were removed from water and their mass and dimensions were measured. This was continued until they were completely saturated. The more polar PA46 absorbed more water than less polar PA6 and PA66 and therefore, was more susceptible to moisture‐induced dimensional growth. For a given polymer, it was found that the thicker samples took longer to reach saturation, but had the same diffusion coefficient as thinner ones. Changes in dimensions coincided with changes in mass. Sorption and swelling followed slightly different paths, but arrived at their respective equilibrium values at the same time. Within experimental error, dimensional expansion due to water absorption was the same in all directions. Injection‐molded samples absorbed slightly more water than compression‐molded ones, but their absorption rates were equal. Equilibrium water absorption data were used to approximate the dimensional changes associated with the swelling of the PAs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The structure and morphology of syndiotactic polystyrene injection molded coupons

The structure and morphology of syndiotactic polystyrene (sPS) injection molded coupons have been investigated using wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), light microscopy, and laser Raman spectroscopy (LRS). By sectioning the samples at approximately 200 μm increments, profiles across “hot molded” (oil heated to 140°C) and “cold molded” (water heated to 104°C) coupons, could be built up. Using DSC and WAXS, variations in crystallinity and polymorphic phases were observed. The crystallinity was found to remain fairly constant in the “hot molded” samples, whereas the cold molded samples had a pronounced “amorphous” skin, before becoming more uniform towards the center of the specimen. Characterization of the polymers' microstructure, in the molded plaques, was achieved by optical birefringence. The surface of the plaques were successfully etched with an acid/permanganate solution, prior to SEM studies, to reveal their morphology. Overall, the coupons showed very little orientation effects and the structure appeared to be consistent with that of a semicrystalline polymer, crystallized under relaxed conditions.     

Microstructure and crystallography in microcellular injection‐molded polyamide‐6 nanocomposite and neat resin

The effects of adding nanoclay to polyamide‐6 (PA‐6) neat resin, and the effects of processing parameters on cell density and size in microcellular injection‐molded components were investigated. In addition, the crystal sizes, structures, and orientation were analyzed with the use of x‐ray diffraction (XRD) and a polarized optical microscope. The standard ASTM D 638‐02 tensile bars for the analyses were molded according to a fractional four‐factor, three‐level, L9 Taguchi design of experiment (DOE) with varying melt temperature, injection speed, supercritical fluid (SCF) concentration, and shot size. It was found that the presence of montmorillonite (MMT) nanoclay greatly reduced the size of the cells and crystals, but increased their density in comparison with neat resin processed under identical molding conditions. In addition, at the sprue section downstream of the machine nozzle, cell size gradually decreased from the part center toward the skin for both the neat resin and the nanocomposite. It was also found that shot size was the most important processing parameter for both the neat resin and nanocomposite in affecting cell density and size in microcellular injection molding components. Weakly preferred crystal orientations were observed on the surface of microcellular injection‐molded PA‐6/MMT tensile bars. Finally, the addition of nanoclay in PA‐6 neat resin facilitated the formation of γ‐phase crystals in the molded components. Polym. Eng. Sci. 45:52–61, 2005. © 2004 Society of Plastics Engineers.     

Relating scratch resistance to injection molding‐induced morphology of polypropylene

The relationship between the scratch resistance and the injection molding‐induced morphology of polypropylene (PP) was investigated. The crystal structure near the surface was controlled by the mold temperature and the doping of a nucleating agent (NA). Although α‐ and β‐NA were used to improve the scratch resistance of PP that was molded at a mold temperature of 40°C, both of the NAs only slightly affected the scratch resistance due to low crystallinity at the surface. When the mold temperature was increased, the skin layer became thin and a β‐form crystal formed. Plastic deformation under the scratch was limited in the frozen layer. Consequently, the thickness of the frozen layer (which had low crystallinity) had the predominant effect on the scratch resistance in comparison to the polymorphism differences. The crystal morphology was analyzed with synchrotron micro‐beam wide angle X‐ray diffraction and Fourier transform infrared spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011