Amplification effect of platelet type nanoparticles on the orientation behavior of injection molded nylon 6 composites

The effect of platelet type nanoparticles and processing conditions; mold temperature and injection speed, on the development of local microstructure in injection molded nylon 6 parts was investigated. The molded parts exhibit two crystal forms (α and γ) of nylon 6 in varying proportions from skin to core. The γ crystals preferentially grow near the surface regions and α crystal fraction increases with distance from the surface in all molded parts. However, the spatial variation of crystal phases across the thickness in nanocomposites differs from that of unfilled nylon 6. Nanoplatelets induce high levels of orientation of the polymer matrix throughout the thickness of the molded part even at high mold temperatures where nonisothermal effects are highly suppressed and confined to very close proximity of surfaces. These high chain orientation levels observed in nanoparticle filled systems is a result of the shear amplification effect that occurs in small spaces between adjacent nanoparticles of differing velocity. The local preferential crystalline orientation of nylon 6 resin and nanoparticles across the thickness of the molded parts are investigated using a series of structure characterization techniques including microbeam wide angle X-ray, SAXS and TEM.     

Structure and property study of nylon‐6/clay nanocomposite fiber

The crystal structures of nylon‐6 and nylon‐6/clay fibers were investigated on annealing and drawing. Annealing increased the γ‐crystalline form of both fibers, as indicated by the DSC curves, and its effect was dominant in nylon‐6/clay fiber. On drawing, the γ‐crystalline form was easily converted into the α form in nylon‐6, whereas it was still observed at a relatively high spin‐draw ratio in nylon‐6/clay fiber. However, although the α‐crystal form was dominant in nylon‐6, the γ‐crystal form was dominant in nylon‐6/clay with annealing and drawing, on the basis of the XRD data. The fast crystallization rate of nylon‐6/clay compared with pure nylon‐6 was confirmed, on the basis of the Avrami exponent. The initial modulus of nylon‐6/clay fiber was 30 % higher than the neat nylon‐6 fiber. The reinforcing effect of clay on the dynamic storage modulus was observed. Copyright © 2004 Society of Chemical Industry     

Unique clay orientation in the injection-molded bar of isotactic polypropylene/clay nanocomposite

In this article, the injection-molded bars of isotactic polypropylene/organoclay nanocomposite with different clay contents have been obtained via dynamic packing injection molding (DPIM). The oriented microstructure including layered nanoparticles and PP lamellae has been inspected through 2D-WAXS analyses along the sample thickness of the molded bars. Depending on the clay content and sample thickness, various oriented clay structures with nanoparticles uniplanar-axially oriented parallel to the surface of molded bar, or partially tumbled around the flow axis of the molded bar, or even a random orientation, could be observed. The observed orientation behavior of nanoparticles could be temporarily elucidated as the results of the sensitive response of layered nanoparticles to shear deformation and the structural recovery of clay network assisted by the electrostatic attraction existing between adjacent nanoplatelets.     

Polymorphic behavior of nylon 6/saponite and nylon 6/montmorillonite nanocomposites

X‐ray diffraction methods and DSC thermal analysis have been used to investigate the structural change of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliaton of the layered saponite or montmorillonite by subsequent polymerization. Both X‐ray diffraction data and DSC results indicate the presence of polymorphism in nylon 6 and in nylon 6/clay nanocomposites. This polymorphic behavior is dependent on the cooling rate of nylon 6/clay nanocomposites from melt and the content of saponite or montmorillonite in nylon 6/clay nanocomposites. The quenching from the melt induces the crystallization into the γ crystalline form. The addition of clay increases the crystallization rate of the α crystalline form at lower saponite content and promotes the heterophase nucleation of γ crystalline form at higher saponite or montmorillonite content. The effect of thermal treatment on the crystalline structure of nylon 6/clay nanocomposites in the range between Tg and Tm is also discussed.     

Preparation and characterization of polyamide‐6 with three‐branched chains

With trimesinic acid as a molecular weight regulator, the hydrolytic polymerization of ?‐caprolactam was carried out, and nylon‐6 or polyamide‐6 with three‐branched chains was obtained. Through a systematic study of the effects of conditions such as the reaction time and concentration of trimesinic acid on the polymerization, we found that the conversion of caprolactam was almost insensitive to the initial concentrations of the regulators, but the relative viscosity of the polymer decreased with increasing trimesinic acid. Characterization investigations showed that differential scanning calorimetry curves changed from a single peak for normal nylon‐6 to one main peak and one shoulder or one small peak for the branched polymer; the melting point of the star‐shaped nylon‐6 decreased with an increasing amount of trimesinic acid, whereas its crystallization temperature was higher than that of linear‐chain nylon‐6. A wide‐angle X‐ray diffraction study indicated that the crystal structure of the star‐shaped nylon‐6 still belonged to the α form, and the crystallizability of the branched polymer with an elevated amount of trimesinic acid during polymerization did not seem to be weakened; the characteristic absorption of infrared spectra provided indirect evidence for the existence of branched chains in the polymer. Moreover, the mechanical properties of star‐shaped nylon‐6 and linear‐chain nylon‐6 were compared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3184–3193, 2001     

Crystallization behavior of nylon 6 nanocomposites

The crystallization behavior of nylon 6 nanocomposites formed by melt processing was investigated. Nanocomposites were produced by extruding mixtures of organically modified montmorillonite and molten nylon 6 using a twin screw extruder. Isothermal and non-isothermal crystallization studies involving differential scanning calorimetry (DSC) were conducted on samples to understand how organoclay concentration and degree of clay platelet exfoliation influence the kinetics of polyamide crystallization. Very low levels of clay result in dramatic increases in crystallization kinetics relative to extruded pure polyamide. However, increasing the concentration of clay beyond these levels retards the rate of crystallization. For the pure nylon 6, the rate of crystallization decreases with increasing the molecular weight as expected; however, the largest enhancement in crystallization rate was observed for nanocomposites based on high molecular weight polyamides; this is believed to stem from a higher degree of platelet exfoliation in these nanocomposites. Wide angle X-ray diffraction (WAXD) and DSC were further used to characterize the polymer crystalline morphology of injection molded nanocomposites. The outer or skin layer of molded specimens was found to contain only γ-crystals; whereas, the central or core region contains both the α and γ-forms. The presence of clay enhanced the γ-structure in the skin; however, the clay has little effect on crystal structure in the core. Interestingly, higher levels of crystallinity were observed in the skin than in the core for the nanocomposites, while the opposite was true for the pure polyamides. In general, increasing the polymer matrix molecular weight resulted in a lower degree of crystallinity in molded samples as might be expected.     

Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

尼龙6/粘土纳米复合材料的性能

对尼龙6/粘土纳米复合材料(PA6CN)的力学性能、结晶性能、流变性能、热稳定性、阻隔性能、阻燃性能、各向异性和可纺性进行了综述。加入粘土后,基体尼龙6的晶型变为γ型,改善了尼龙6的力学性能,提高了热变形温度,降低了吸水率,改善了气体阻隔性和材料的阻燃性,拓宽了复合材料的应用范围。     

Molecular origins of toughening mechanism in uniaxially stretched nylon 6 films with clay nanoparticles

Introduction of nanoplatelets into the nylon matrix preorients the polymer chains in the film plane during melt casting leading to uniplanar (001) texture in nylon 6 crystalline as well as clay phase. This behavior enhances the uniformity of films during cold deformation well above the glass transition temperature by suppressing the localized necking behavior. The clay platelets reduce the polymer interchain hydrogen bonding and entanglements leading to decrease of long range “connectivity”. As a result, a delay in strain hardening during deformation occurs allowing much larger deformations to be attained without fracture. This in turn leads to increase in toughness.     

Abrasion studies of nylon 6/montmorillonite nanocomposites using scanning electron microscopy,fourier transform infrared spectroscopy,and X‐ray photoelectron spectroscopy

In this article, abrasion performance of commercial nylon 6 and nylon 6/montmorillonite (MMT) nanocomposites was studied. The polymer nanocomposites showed poor abrasion resistance compared to the neat polymer. The wear loss increased linearly with clay concentration. Changes in surface morphology, composition, and structure were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR)‐attenuated total reflection spectroscopy, and X‐ray photoelectron spectroscopy (XPS). SEM images showed that all the abraded surfaces contained fractured particles. However, the abraded nanocomposite surfaces had much deeper grooves compared to the homopolymer. FTIR results showed an increase in the amount of α crystals and a decrease in the amount of γ crystals on all the surfaces after abrasion. This was attributed to the strain‐induced γ to α crystal transformation. The largest amount of α crystals was formed in the abraded surface of pure nylon 6, and the amount of α crystals formed decreased with increasing MMT content. XPS results showed an increase in the [Si]/[N] elemental ratio for all nanocomposites after abrasion, indicating an increase in the clay content of the surface. Abrasive wear mechanism is as follows: (1) tensile tearing is the dominant wear mechanism for all the samples; (2) the cutting mechanism becomes more important when MMT content increases; (3) the polymer matrix is easier to be removed than clay during the abrasion process; (4) in nylon 6/MMT systems, the poor abrasion resistance is attributed to defects at the clay‐polymer interface, resulting in greater wear of the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shear amplification of orientation in Nylon 11/clay nanocomposites during melt casting and resulting electrical properties

In this study, the effect of organically modified clay on the orientation enhancement in Nylon 11 in melt casting was investigated. Nylon 11 was mixed with 1 and 3 wt% Cloisite 20A using twin screw extrusion and they were cast into films with varying take-up speeds. The addition of clay in Nylon 11 helped increase orientation levels substantially in melt cast films, both as a function of clay concentration as well as take-up speeds. This was primarily due to shear amplification effect caused by the movement of adjacent clay nanoparticles due to the shear flow gradient within the die. At low clay concentrations, the sub-T_m stretchability, and electrical breakdown strength improve as the presence of clay reduces inter/intrachain hydrogen bonding. At higher clay concentrations, both orientation and electrical breakdown levels decrease. The latter is primarily caused by increased percolation path of charge carriers. Nevertheless, clay nanoplatelets were very effective in their role as melt processing aids, as they enhance orientation levels of Nylon 11 thin films by shear amplification effect where they increase local chain orientation of chains trapped between clay platelets while their orientation relaxation is suppressed.     

Barrier and mechanical properties of injection molded montmorillonite/polyesteramide nanocomposites

Properties of injection‐molded biodegradable polyesteramide composites containing 5 and 13 wt% octadecylammonium‐treated montmorillonite clay have been studied. Oxygen transmission rates and mechanical properties were measured. X‐ray diffraction was used to assess the degree of intercalation of the clay layer stacks, and transmission electron microscopy (TEM) was used to assess the morphology and degree of layer delamination. A substantial reduction in oxygen permeability was observed when clay was added to the composites. The oxygen permeability of the 13 wt% clay sample was only 20% of that of the pure polymer. The in‐plane stiffness and in‐plane strength of the sheets were greatly improved without any embrittlement. These beneficial effects were probably due to the high degree of clay layer exfoliation and orientation observed by TEM. Heat shrinkage, toughness analysis, and cutting operations suggested that the polymer chains and the clay layers were oriented parallel to the plane of the sheet. TEM and X‐ray showed that stacked layers were still present but that these were significantly intercalated. The clay‐layer periodic spacing increased from 25 Å to approximately 35 Å during processing. POLYM. ENG. SCI. 45:135–141, 2005. © 2004 Society of Plastics Engineers     

Advances in Epoxy/Graphene Nanoplatelet Composite with Enhanced Physical Properties: A Review

In this review, development from graphene nanoplatelet, that is, comprised of short bulk of single layer graphene, into modified-polymer/graphene nanoplatelet composite is presented. Preparation methods of graphite, graphene, and graphene nanoplatelets have also been discussed. Graphene nanoplatelet and modified graphene nanoplatelet commend unique properties to composites such as excellent thermal and electrical conductivity as well as mechanical and barrier properties. Graphene nanoplatelet fabrication techniques by solution mixing, melt blending, and in situ polymerization are also discussed. Excellent dispersion of nanoplatelets in polymer/graphene nanoplatelet depends upon the selection of suitable fabrication technique. Moreover, the corresponding significance, exploitation, challenges, and future aspect of polymer/graphene nanoplatelet-based material is overviewed.     

Structure and thermal behaviour of nylon 6 nanocomposites

In this article, nylon 6/clay nanocomposites with 5 wt % clay (NCN5) were prepared by a twin screw extruder. The effects of annealing including solid‐state annealing (170 and 190°C) and melt‐state annealing (240°C) on the polymorphic behavior and thermal property of NCN5 and nylon 6 have been comparatively studied as a function of annealing time using modified differential scanning calorimetry (MDSC) and wide‐angle X‐ray diffraction. It was demonstrated that NCN5 and nylon 6 exhibit a similar polymorphic behavior when they were annealed at 190°C for different time durations. As the annealing temperature was elevated to 240°C, significant differences in thermal behavior and polymorphism between NCN5 and nylon 6 could be found. For example, the α crystal became the absolutely dominating crystalline phase for NCN5 sample independent on the annealing durations, whereas the formation of γ crystal is greatly enhanced in neat nylon 6 with increasing annealing time. Moreover, a small endothermic peak is observed around 180°C in both nylon 6 and NCN5 samples annealed at 170 and 190°C, which might be related to the melting of microcrystals formed in the amorphous regions during annealing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3116–3122, 2006     

High temperature behaviour of the crystalline phases in unfilled and clay-filled nylon 6 fibers

Temperature-induced crystalline phase transitions in neat nylon 6 fibers as well as nylon 6/montmorillonite nanocomposite fibers have been studied by means of wide-angle X-ray scattering. Both types of melt spun fibers only consist of the γ crystalline phase that does not display any transition during heating up to the melt. In contrast, fibers drawn up to the maximum draw ratio at 140 °C display the single α phase with a high degree of chain orientation. During the temperature increase, the α phase undergoes a gradual structural disordering but preserves its monoclinic character up to melting. The structural evolution of the α form turned out sensitive to the thermal and mechanical treatment of the fibers. Annealing the unfilled drawn fibers at 150 °C prior to the WAXS experiment improves the thermal stability of the α form due to healing of the processing-induced crystalline defects. The montmorillonite-filled fibers display both the α and the γ crystals, which readily turn into α crystal form only upon drawing. Due to the matrix shearing between the MMT platelets, the H-bonded sheets display a higher thermal stability as compared with unfilled drawn fibers. Upon cooling from the melt, the first signs of crystallization are of γ form in the MMT-PA6 fibers, but the α form rapidly turns predominant. Crystallization kinetics considerations are put forward to account for this finding.     

The electrorheological properties of polyaniline nanofiber/kaolinite hybrid nanocomposite

A novel polyaniline nanofiber/kaolinite nanoplatelet hybrid nanocomposite was synthesized by means of rapidly mixed in situ polymerization. The resultant polyaniline/kaolinite hybrid nanocomposite was characterized via different techniques, such as X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results show that 2D clay nanoplatelets are coated by the 1D polyaniline nanofibers. The nanoclay platelets can improve the thermal stability of polyaniline nanofibers. An electrorheological effect is found with the suspension of polyaniline nanofiber/kaolinite nanoplatelet hybrid nanocomposite dispersed in silicone oil. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1104‐1113, 2013     

Ferroelectric switching in spin-coated nylons 11 and 12

Here, we investigate the correlation between the crystal structures and the ferroelectric switching by a sinusoidal alternative electric field for spin-coated nylon 11 films as an odd nylon and for nylon 12 as an even nylon. These spin-coated nylons afforded thin films with thicknesses ranging from 101 to 125 nm. The obtained thin films were subjected to melt-quenching, melt-cooling down, annealing-quenching, or annealing-cooling down. These processes were notably related to the resulting crystal structures. In particular, the crystal structures involving twisted bonds in the molecular chains were significantly related to ferroelectricity in both nylon 11 and nylon 12. Namely, the vector component of the amide dipole moments is transverse to the direction of the molecular chains, which is induced by the presence of more twisted bonds and is significantly related to the remanent polarization P_r for both nylons. In nylon 11, the hydrogen bonding interaction between the intermolecular amide dipole moments in the α and δ crystal forms was weakened by the existence of more twisted bonds. In nylon 12, the nonpolar γ crystal form was transformed to a polarizable γ’ crystal form because of the existence of more twisted bonds. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48438.     

Morphology and crystallization behavior of nylon 6‐clay/neat nylon 6 bicomponent nanocomposite fibers

Nylon 6‐clay hybrid/neat nylon 6, sheath/core bicomponent nanocomposite fibers containing 4 wt % of clay in sheath section, were melt spun at different take‐up speeds. Their molecular orientation and crystalline structure were compared to those of neat nylon 6 fibers. Moreover, the morphology of the bicomponent fibers and dispersion of clay within the fibers were analyzed using scanning electron microscopy and transmission electron microscopy (TEM), respectively. Birefringence measurements showed that the orientation development in sheath part was reasonably high while core part showed negligibly low birefringence. Results of differential scanning calorimetry showed that crystallinity of bicomponent fibers was lower than that of neat nylon 6 fibers. The peaks of γ‐crystalline form were observed in the wide‐angle X‐ray diffraction of bicomponent and neat nylon 6 fibers in the whole take‐up speed, while α‐crystalline form started to appear at high speeds in bicomponent fibers. TEM micrographs revealed that the clay platelets were individually and evenly dispersed in the nylon 6 matrix. The neat nylon 6 fibers had a smooth surface while striped pattern was observed on the surface of bicomponent fibers containing clay. This was speculated to be due to thermal shrinkage of the core part after solidification of the sheath part in the spin‐line. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39996.     

Injection molding: The effect of fill time on properties

The effect of fill time on the mechanical properties, surface appearance, and part dimensions of several polymers was determined. Two crystalline materials, polypropylene and nylon 6,6, and an amorphous material, acrylonitrile-butadiene-styrene (ABS), were used. In addition, the effect of the presence of glass fibers was examined using glass fiber reinforced nylon 6,6. The fill time was varied from 0.8 to 20 sec which included both the viscous flow controlled region (short fill times) where laboratory samples are ordinarily molded and the heat transfer controlled region (long fill times) where production parts arc commonly molded. No large variations in tensile properties were observed for polypropylene or nylon, but a 10 percent increase in peak tensile stress and strain for ABS did indicate that molecular orientation increased with increasing fill time. However, significant differences did occur in the properties of glass reinforced nylon. Peak tensile stress increased 15 percent and flexural strength decreased 10 percent as the fill time was increased. Although no change in the flexural modulus was observed, the scatter in the modulus decreased with increasing fill time. These property variations can be attributed to differences in the glass fiber orientation of the skin and core regions of the part. The measurement of molded tensile bar dimensions indicated there was little effect of fill time on the shrinkage of the various polymers except for shrinkage in the length direction for polypropylene. The shrinkage increased from 13 to 15.4 mm/m over the fill time range, a great enough difference to affect the fit of large parts. The most dramatic change with fill time was the surface appearance of the glass reinforced nylon. The surface of samples molded at short fill times had a dark uniform color and smooth appearance while samples molded at long fill times had a lighter color and a porous surface. This surface porosity is due to crystallization prior to complete pressurization of the mold. Therefore, in addition to affecting surface appearance, other surface related properties such as aging and the ability to plate plastic parts could also be affected.     

Puncture deformation and fracture mechanism of oriented polymers

In this study, we investigated the effect of orientation by solid‐state cross‐rolling on the morphology, puncture deformation, and fracture mechanism of an amorphous TROGAMID material and three semicrystalline polymers: high‐density polyethylene (HDPE), polypropylene (PP), and nylon 6/6. In amorphous TROGAMID, it was found that orientation preferentially aligned polymer chains along the rolling deformation direction and reduced the plastic deformation of TROGAMID in a low‐temperature puncture test. The decrease of ductility with orientation changed the fracture mechanism of TROGAMID from ductile hole enlargement failure in the unoriented control to a more brittle delamination failure in TROGAMID cross‐rolled to a 75% thickness reduction. For semicrystalline polymers HDPE, PP, and nylon 6/6, the randomly oriented crystalline lamellae in the controls were first oriented into an oblique angle to the rolling direction (RD) before the lamellae became fragmented and preferentially oriented with the chain axis parallel to the RD. The morphological change resulted in the decrease of ductility in HDPE in the low‐temperature puncture test. In PP and nylon 6/6, the brittle fracture of unoriented controls was changed into ductile failure when they were cross‐rolled to a 50% thickness reduction. This was attributed to the tilted crystal lamellae morphology, which permitted chain slip deformation of crystals with the chain axis parallel to the maximum shear stress direction. With further orientation of PP and nylon 6/6 to a 75% thickness reduction, the failure mechanism changed back to brittle fracture as the morphology transformed into a layered discoid structure with the chain axis of the fragmented crystal blocks parallel to the RD; this prevented chain slip deformation of the crystals. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012