Strain amplitude response and the microstructure of PA/clay nanocomposites

Polyamide 6/clay nanocomposites (PAn, where n is the mass fraction of clay) with various clay loading were prepared by melt compounding in a twin screw extruder. Exfoliation of clay in a PA matrix was confirmed by X-ray diffraction. Strain amplitude response of PAn in both melt and solution states has been investigated. In the melt state, critical strain amplitude of PAn is sensitive to strain amplitude response and decrease logarithmically with increasing clay loading. The elastic moduli (G′) of PAn are reversible under frequency loop sweeps. Comparisons of strain amplitude response in both melt and solution states have been conducted. Two different responses have been observed: strain thinning in the melt state and weak strain overshoot in the solution state. FTIR studies show that amide II band of PAn shifts toward high wavenumbers, but amide I band and N-H stretching vibration are independent of clay loading. We suggest that two types of strain amplitude response of PAn can be explained: strain thinning which is dominant in PAn caused by physical adsorption and entanglement of PA chains on nanoclays and weak strain overshoot caused by weak bonds between PA chains and nanoclays.     

PA6/粘土纳米复合材料的流变性能

采用毛细管流变仪测定了原位聚合的 PA6/粘土纳米复合材料及 PA6的流变性能。结果表明 :在实验条件下 ,纳米 PA6属于假塑性流体 ,其非牛顿指数小于 PA6。在 2 40℃时 ,当剪切速率大于660 s-1时 ,纳米 PA 6的表观粘度小于 PA6,且随粘土含量的增加而逐渐降低。当剪切速率小于 932 s-1时 ,纳米 PA6的粘流活化能大于 PA6,说明纳米 PA6对温度更敏感     

Glass fiber reinforced polyamide‐6 nanocomposites

Polyamide 6 nanocomposites (PA6/NC) are novel type of composite materials comprising extremely thin, “nanometer scale” dispersions of smectitic silicate platelets. We prepared such PA6/NC materials via a melt compounding technique using suitably organomodified montmorillonite or hectorite type clays. The high surface to volume ratio of such thin silicate dispersions in PA6/NC leads to a high reinforcement efficiency even at 2 to 5 wt% of clay, achieving high specific modulus, strength and heat distortion temperature under load (DTUL). In addition, the platelet orientation and their surface nucleation effects seem to promote a faster crystallization and higher crystallinity in PA‐6/NC (particularly at the surface and in thin‐wall injection moldings), as compared to the standard PA‐6. Such morphological features in PA‐6/NC also result in improved moisture resistance. Recognizing these benefits, we investigated the use of PA‐6/NC as a matrix for making both short and long glass fiber (GF) reinforced composites. Significant improvements in modulus were achievable in both the dry and the moisture conditioned state for PA‐6/NC compared to standard PA‐6, at any given level of glass fiber reinforcement. In general a small amount (3‐4 wt%) of the nanometer scale dispersed clay is capable of replacing up to 40 wt% of a standard mineral filler or 10‐15 wt% of glass fiber in PA‐6 composites to give equivalent stiffness at a lower density or a lower part weight advantage. In addition, improved moisture resistance, permeation barrier and fast crystallization/mold cycle time contribute to the usefulness of such composites.     

Free volume sizes in intercalated polyamide 6/clay nanocomposites

The effect of incorporating modified clay into a polyamide 6 (PA6) matrix, on the free volume cavity sizes and the thermal and viscoelastic properties of the resulting nanocomposite, was studied with positron annihilation lifetime spectroscopy, differential scanning calorimetry and dynamic mechanical analysis. At low concentrations of clay the fraction of PA6 crystals melting close to 212 °C was increased, while the fraction of the α-form PA6 crystals, melting close to 222 °C, was reduced. At higher concentrations of clay, a crystal phase with increased thermal stability emerged. Addition of more than 19 wt% clay caused a reduction of the heat of fusion of PA6. An unexpected reduction of the ΔC_p at the glass transition, contradicting the measured reduction of the heat of fusion, was detected, indicating an altered mobility in the non-crystalline regions. The viscoelastic response of PA6/clay nanocomposites, as compared to unfilled PA6, pointed towards a changed mobility in the non-crystalline regions. At high concentrations of clay (>19 wt%) an increase of the free volume cavity diameter was observed, indicating a lower chain packing efficiency in the PA6/clay nanocomposites. The increased free volume sizes were present both above and below the glass transition temperature of PA6.     

Preparation of nanocomposites by melt compounding polylactic acid/polyamide 12/organoclay at different screw rotating speeds using a twin screw extruder

This study analyzes the effect of different screw rotating speeds on the clay dispersion and mechanical properties of nanocomposites prepared by melt compounding polylactic acid (PLA) with an organoclay in a co‐rotating twin screw extruder. Polyamide 12 (PA12) was used as an additive. Two different screw rotating speeds, 65 rpm and 150 rpm, were used in this study. According to the tensile strength data, the Young's modulus of the PLA/clay nanocomposites showed improvement at a screw rotating speed of 150 rpm. The Young's modulus improved with the addition of the organoclay to PLA matrix, but decreased when PA12 was added to the PLA matrix. The tensile strengths and elongations become small by adding organoclay to PLA matrix. The tensile strengths of the PLA/organoclay nanocomposites increased for the higher screw rotating speed (150 rpm). The d‐spacing of PLA/PA12/Clay nanocomposites was independent of the addition of PA12. The size of the clay aggregates in the PLA/PA12/Clay nanocomposites is smaller than that of PLA/Clay. Furthermore, the thermal stability of the PLA/Clay nanocomposite increases with addition of PA12, while on the whole, it had little influence on the tensile properties. POLYM. COMPOS., 29:1–8, 2008. © 2007 Society of Plastics Engineers     

Manipulating the phase morphology in PPS/PA66 blends using clay

By adding a small amount of clay into poly(p‐phenylene sulfide) (PPS)/polyamide 66 blends, the morphology was found to change gradually from sea–island into cocontinuity and lamellar supramolecular structure, as increasing of clay content. Clay was selectively located in the PA66 phase, and the exfoliated clay layers formed an edge‐contacted network. The change of morphology is not caused by the change of volume ratio and viscosity ratio but can be well explained by the dynamic interplay of phase separation between PPS and PA66 through preferential adsorption of PA66 onto the clay layers and through layer–layer repulsion. This provides a means of manipulating the phase morphology for the immiscible polymer blends. The mechanical and tribological properties of PPS/PA66 blends with different phase morphologies (different clay contents) were studied. Both tensile and impact strength of the blends were found obviously increased by the addition of clay. The antiwear property was greatly improved for the blends with cocontinuous phase form. Our work indicates that the phase‐separating behavior of polymer blends contained interacting clay can be exploited to create a rich diversity of new structures and useful nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of clay on phase morphology and mechanical properties in polyamide 6/EPDM-g-MA/organoclay ternary nanocomposites

In this study, both organoclay and EPDM-g-MA rubber were used to simultaneously improve the toughness and stiffness of polyamide 6 (PA6). We first prepared PA6/EPDM-g-MA/organoclay ternary nanocomposites using melt blending. Then the composites were subjected to traditional injection molding and so-called dynamic packing injection molding. The dispersion of clay, phase morphology, crystallinity and orientation of PA6 as well the mechanical properties were characterized by WAXD, SEM, DSC, 2D-WAXS and mechanical testing, respectively. The effects of clay on phase morphology and mechanical properties of PA6/EPDM-g-MA blends could be summarized as follows: (1) weakening interphase adhesion between PA6 and EPDM-g-MA rubber particles, resulted in increasing of rubber particle size, as the clay and rubber contents are low; (2) preventing coalescence of rubber domains, arisen in decreasing of rubber particle size, as the clay and rubber contents are high; (3) the blocking effect on the overlap of stress volume around rubber particles caused broadening of the brittle-ductile transition region and decrease of toughness, and (4) the effective stress transfer leading a better reinforcement when the interparticle distance is smaller than the critical value.     

FT-IR spectroscopic study of hydrogen bonding in PA6/clay nanocomposites

Fourier transform infrared spectroscopy was used to investigate PA6/clay nanocomposites (PA6CN) with various cooling histories from the melt, including rapid cooling (water-quenched), middle-rate cooling (air-cooling) and slow cooling (mold-cooling). In contrast to pure PA6 dominated by the α-phase, the addition of clay silicate layers favor the formation of the γ-crystalline phase in PA6CN.We focus on the reason why silicate layers favor the formation of γ-phase in PA6. Vaia et al. suggested that the addition of clay layers forces the amide groups of PA6 out of the plane formed by the chains. This results in conformational changes of the chains, which limits the formation of H-bonded sheets so that the γ-phase is favored. If this assumption is correct, PA6CN is expected to show some differences as compared with PA6 with respect to hydrogen bonding.The silicate layers were indeed found to weaken the hydrogen bonding both in the α- and γ-phases. This was also confirmed by X-ray diffraction studies. The γ-phase is most likely concentrated in regions close to the silicate layers, whereas the α-phase is favored in the bulk matrix.     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of nanofiller on fibril formation in melt‐drawn HDPE/PA6 microfibrillar composite

Effect of layered silicates on structure of microfibrillar composites (MFCs) with reinforcing PA6 fibrils formed in situ by melt drawing was studied. Clay was added to HDPE/PA6 MFC using different mixing protocols including simultaneous addition, application of pre‐made masterbatches with both constituents and their combinations. In all cases, majority of nanofiller (NF) was contained inside PA6 fibrils. On the other hand, fibrils dimensions were significantly affected by the clay addition protocol; their marked increase in the case of simultaneous addition of all components and application of HDPE/C30 nanocomposite indicate important effect of NF migration to the PA6 phase in the course of mixing and melt drawing. The effect of properties of PA6 and HDPE phases and NF migration on the morphology evolution is discussed. It is shown that the fiber shape and volume after sample drawing are controlled by the interplay between the dispersed fibril extension and coalescence. POLYM. ENG. SCI., 55:2133–2139, 2015. © 2015 Society of Plastics Engineers     

Polyamide 6/clay nanocomposites using a cointercalation organophilic clay via melt compounding

Polyamide 6/clay nanocomposites (PA6CN) were prepared via the melt compounding method by using a new kind of organophilic clay, which was obtained through cointercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of this kind of organophilic clay in the matrix was studied by means of X‐ray diffraction (XRD) and transmission electron microscopy (TEM); the silicate layers were dispersed homogeneously and nearly exfoliated in the matrix. This was probably the result of the strong interaction between epoxy groups and amide end groups of PA6. The mechanical properties and heat distortion temperature (HDT) of PA6CN increased dramatically. The notched Izod impact strength of PA6CN was 80% higher than that of PA6 when the clay loading was 5 wt %. Even at 10 wt % clay content, the impact strength was still higher than that of PA6. The finely dispersed silicate layers and the strong interaction between silicate layers and matrix decreased the water absorption. At 10 wt % clay content, PA6CN only absorbs half the amount of water compared with PA6. The dynamic mechanical properties of PA6CN were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 953–958, 2003     

Microstructure,crystallization and dynamic mechanical properties of polyamide/clay nanocomposites after melt‐state annealing

Polyamide 6/clay (PA/clay) nanocomposites produced by melt‐compounding were treated under various melt‐state annealing processes. The effect of melt‐state annealing on the microstructure, crystallization, and dynamic mechanical properties was characterized by transmission electron microscope (TEM), modulated differential scanning calorimetry (MDSC), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and dynamic mechanical analysis (DMA). Clay layers were exfoliated in PA matrix. The crystalline transformation between α and γ‐crystalline phase was virtually dependent on the annealing process and clay loading. After melt‐state annealing between 230 and 250°C, clay induced the appearance of a new endothermic peak in PA/clay. PA/clay after melt‐state annealing exhibited a higher elastic modulus above T_g and a lower β relaxation below T_g as compared with the non‐annealed sample. FTIR analysis demonstrated that the melt‐state annealing caused strong hydrogen bonding interaction of amide groups with clay layers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Morphology and melt rheology of nylon 11/clay nanocomposites

Nylon 11 (PA11)/clay nanocomposites have been prepared by melt‐blending, followed by melt‐extrusion through a capillary. Transmission electron microscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (G′) and loss modulus (G″) values than neat PA11. The values of G′ and G″ increase steadily with clay loading at low concentrations, while the G′ and G″ for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of G′ and G″. Finally, a comparison has been made between the complex and steady viscosities to verify the applicability of the empirical Cox‐Merz rule. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 542–549, 2006     

Thermal and mechanical properties of PA12/C30B nanocomposites in relationship with nanostructure

This work focuses on the effect of nanoclay mass fraction on the properties of polyamide 12 matrix. Relationships between mechanical, thermal, and structural properties of polyamide 12/Cloisite^® 30B nanocomposites were studied. The material structure, previously described from XRD and TEM experiments, was more thoroughly characterized in the present work using SEM and FTIR techniques. The FTIR results clearly showed that clay galleries are intercalated by PA chains, which leads to a partially exfoliated nanostructure, confirming the TEM observations and the XRD analysis. However, a few micrometric aggregates are evidenced by SEM analysis, particularly at high clay fractions. TGA and DTA measurements showed that the thermal stability of PA12 matrix is slightly modified by the Cloisite^® 30B content. Viscoelastic properties of the nanocomposites in solid‐state were analyzed as functions of strain, frequency, and temperature. The extent of the linear response regime of the material is shown to be sensitive to the amount of clay: nonlinearities appear at lower strain values as the clay mass fraction increases. Both relative dynamical moduli also increase with increasing clay mass fraction, with frequency dependence for the viscous modulus and without frequency dependence for the elastic modulus. Finally, similarities have been pointed out between viscoelastic properties of the nanocomposites in solid and melt states. For example, the percolation threshold is highlighted at the same clay mass fraction, ～2%, in both states. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41938.     

Thermal and viscoelastic property of epoxy–clay and hybrid inorganic–organic epoxy nanocomposites

The properties of nanostructured plastics are determined by complex relationships between the type and size of the nanoreinforcement, the interface and chemical interaction between the nanoreinforcement and the polymeric chain, along with macroscopic processing and microstructural effects. In this article, we investigated the thermal and viscoelastic property enhancement on crosslinked epoxy using two types of nanoreinforcement, namely, organoion exchange clay and polymerizable polyhedral oligomeric silsesquioxane (POSS) macromers. Glass transitions of these nanocomposites were studied using differential scanning calorimetry (DSC). Small-strain stress relaxation under uniaxial deformation was examined to provide insights into the time-dependent viscoelastic behavior of these nanocomposites. Since the size of the POSS macromer is comparable to the distance between molecular junctions, as we increase the amount of POSS macromers, the glass transition temperature T_g as observed by DSC, increases. However, for an epoxy network reinforced with clay, we did not observe any effect on the T_g due to the presence of clay reinforcements. In small-strain stress relaxation experiments, both types of reinforcement provided some enhancement in creep resistance, namely, the characteristic relaxation time, as determined using a stretched exponential relaxation function increased with the addition of reinforcements. However, due to different reinforcement mechanisms, enhancement in the instantaneous modulus was observed for clay-reinforced epoxies, while the instantaneous modulus was not effected in POSS–epoxy nanocomposites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1993–2001, 1999     

Multifunctional high density polyethylene nanocomposites produced by incorporation of exfoliated graphite nanoplatelets 1: Morphology and mechanical properties

This research explores the potential of using exfoliated graphite nanoplatelets, xGnP, as the reinforcement in high density polyethylene (HDPE). Two kinds of xGnP nanoparticles were used; xGnP‐1 has the thickness of 10 nm and a platelet diameter of 1 μm, whereas xGnP‐15 has the same thickness but the diameter is around 15 μm. HDPE/xGnP nanocomposite were fabricated first by melt blending and then followed by injection molding. The HDPE/xGnP nanocomposite's flexural strength, modulus and impact strength were evaluated and compared with composites filled with commercial reinforcements such as carbon fibers (CF), carbon black (CB) and glass fibers (GF). Polymer nanocomposites from HDPE/xGnP are equivalent in flexural stiffness and strength to HDPE composites reinforced with glass fibers and carbon black but slightly less than that of HDPE/carbon fiber composites at the same volume fraction. However, the Izod impact strength of HDPE/xGnP nanocomposites is significantly greater (∼250%) than all other reinforcements at the same volume fractions. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

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.     

High-temperature X-ray diffraction studies on polyamide6/clay nanocomposites upon annealing

Summary The influence of nanodispersed clay on the α crystalline structure of polyamide 6 (PA6) was examined in-situ with X-ray diffraction (XRD) between room temperature and melting. In pure PA6 upon annealing the α crystalline phase was substituted by an unstable pseudohexagonal phase at 150°C, then it transformed into a new stable crystalline structure - high temperature α′ phase above the transition temperature. However, in PA6/clay nanocomposite (PA6CN), the α phase did not present crystalline phase transition on heating. The increase in the annealing temperature only led to continuous intensity variation. The different behaviors were caused by the confined spaces formed by silicate layers, which constrained the mobility of the polymer chains in-between. Received: 4 April 2002 / Revised version: 12 May 2002 / Accepted: 12 May 2002     

Crystal structures and their effects on the properties of polyamide 12/clay and polyamide 6–polyamide 66/clay nanocomposites

Both polyamide 12 (PA 12)/clay and polyamide 6–polyamide 66 copolymer (PA 6/6,6)/clay nanocomposites were prepared by melt intercalation. The incorporation of 4–5 wt % modified clay largely increased the strength, modulus, heat distortion temperature (HDT), and permeation resistance to methanol of the polyamides but decreased the notched impact strength. Incorporation of the clay decreased the melt viscosities of both the PA 12 and PA 6/6,6 nanocomposites. Incorporation of the clay increased the crystallinity of PA 6/6,6 but had little effect on that of PA 12, which explained why the clay obviously increased the glass‐transition temperature of PA 6/6,6 but hardly had any effect on that of PA 12. The dispersion and orientation of both the clay and the polyamide crystals were studied with transmission electron microscopy, scanning electronic microscopy, and X‐ray diffraction. The clay was exfoliated into single layers in the nanocomposites, and the exfoliated clay layers had a preferred orientation parallel to the melt flow direction. Lamellar crystals but not spherulites were initiated on the exfoliated clay surfaces, which were much more compact and orderly than spherulites, and had the same orientation with that of the clay layers. The increase in the mechanical properties, HDT, and permeation resistance was attributed to the orientated exfoliated clay layers and the lamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4782–4794, 2006