Crystallization behavior of polypropylene/polyamide 6/montmorillonite nanocomposites

Polymer blended materials such as polyamide 6 (PA6)/polypropylene (PP) blends have received considerable attention in recent years. To improve the compatibility of PA6 and PP, compatibilizers like maleic anhydride‐g‐polypropylene (MPP) are often added. In addition, organically modified montmorillonite (MMT) is also used to improve the properties of various materials. In this work, the crystallization behavior of PP/PA6/MMT nanocomposites with MPP compatibilizer was investigated systematically. The annealing process effectively improved the crystallization of α‐PP. The crystallization temperature (T_c) of PA6 was increased by ca 2–3 °C on introducing MPP or MMT alone to the PP/PA6 system, whereas T_c of PP underwent no obvious change. However, when MPP and MMT were added simultaneously, T_c of PP and PA6 increased by 6.6 and 4.2 °C, respectively, and a new crystallization peak corresponding to PP‐g‐PA6 copolymer phase was observed at 162.5 °C. The combined effect of MPP and MMT led to better compatibility of PP with PA6. Moreover, the results of a non‐isothermal crystallization kinetics experiment revealed that the simultaneous introduction of MPP and MMT markedly shortened the crystallization time. Copyright © 2010 Society of Chemical Industry     

Effects of mixing time and blend composition on properties and morphologies of polyamide 6/polycarbonate blends

Summary The role of the mixing time and the composition of polyamide 6/polycarbonate, PA6/PC, mixtures was investigated by torque and thermal measurements as well as by Molau test and morphological analysis.PA6 and PC are clearly incompatible over the whole range of composition showing well segregated phases. However, at high PA6 content and long time of mixing no more phase separation is observed. This has been attributed to chemical reactions between PA6 and PC molecules, that give rise to some block copolymers, which act as interfacial agents between the two polymers.The copolymer extracted from 75/25 PA6/PC blend, mixed for 45 min., shows T_g at about 65°C and two endotherm peaks at 127 and 211°C.Part of this work was presented at the VIII AIM Meeting, Milan 1987     

Isothermal crystallization and melting behaviors of nano TiO2‐modified polypropylene/polyamide 6 blends

Titanium dioxide (TiO₂) nanoparticles were functionalized with toluene‐2,4‐diisocyanate and then polypropylene/polyamide 6/(PP/PA6) blends containing functionalized‐TiO₂ were prepared using a twin screw extruder. Isothermal crystallization and melting behavior of the as‐prepared composites were investigated using differential scanning calorimetry and wide‐angle X‐ray diffraction. Isothermal crystallization analysis shows that the TiO₂ nanoparticles have two effects on PP/PA6 blends, i.e., it can favor the improvement of crystallization ability and decrease the crystallization rate of PP/PA6 blends. The improvement of crystallization ability is superior over decreasement of crystallization rate of PA6 chains caused by TiO₂, therefore PA6 in PP/PA6/TiO₂ nanocomposites have higher crystallization rate than that of PA6 in pure PP/PA6 blends, which indicated TiO₂ nanoparticles favored the crystallization of PA6. The TiO₂ nanoparticles show no effects on the equilibrium melting temperature (T) values of PP phase but decreases the T values of PA6 phase. In addition, the TiO₂ nanoparticles did not change the crystalline polymorph of PP/PA6 blends basically; however, favored the formation of β‐PP. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Interlaboratory Tests on Polymers by Differential Scanning Calorimetry (DSC): Determination of Glass Transition Temperature (Tg)

The present report presents results obtained from an interlaboratory test. 28 participants, mainly from industry and research institutes, measured glass transition temperatures (T_g) by differential scanning calorimetry (DSC) on four different polymers. The materials used were poly(methyl methacrylate) (PMMA), polycarbonate (PC), polysulfone (PSU) and amorphous polyamide (PA 6I/6T). The measured data were collected by EMPA and were evaluated using a robust statistical method. Repeatability and reproducibility data were of special interest. The repeatability limit (r) of glass transition temperatures measured according to DIN 53765 was found in the region of 1–2°C, and the reproducibility limit (R) was around 3–4°C. In addition to the DIN standard, the set of interlaboratory test data was evaluated and considered according to some different approaches and was correlated with data from other EMPA interlaboratory tests performed previously. It was shown that the investigated statistical parameter was always in a similar dimension. The data of the PA sample were found to be an exception. Due to the hygroscopic character of polyamide, the r and R values increase sharply, to an almost three times higher reproducibility limit. Overall, the evaluated data can be used to estimate the results of own and external T_g measurements and their compatibility. The report should therefore support daily work in analytical laboratories where glass transition temperatures are measured by DSC.     

Thermo‐mechanical behavior of polyamide 12—polyamide 66 recycled fiber composites

Postconsumed polyamide 66 (PA66) short fibers derived from carpets were utilized as reinforcement in a commercial polyamide (PA12) matrix at different concentrations, ranging from 10 wt% to 30 wt%, in order to evaluate the effect of PA66 content on the mechanical and dynamic behavior of the resulting materials. DSC tests revealed that both melting and crystallization behavior of PA12 matrix was slightly affected by the presence of the fibers, showing a somewhat nucleation effect of PA66. Quasi‐static tensile tests evidenced that the introduction of PA66 fibers provided a slight stiffening effect on the resulting composites, increasing the elastic modulus with the filler content, especially at testing temperatures above T_g. On the other hand, the presence of agglomerated fibers led to an embrittlement of polyamide composites, showing a significant reduction of the tensile properties at break increasing the PA66 fibers content. Tensile dynamic tests confirmed the stiffening effect provided by the recycled fibers, increasing both dynamic moduli (E′ and E″) with PA66 content over the whole range of considered temperatures. Glass transition temperature of PA12 was substantially increased by the presence of the fibers, while the coefficient of linear thermal expansion above T_g was progressively reduced with the filler content. Interestingly, isothermal creep compliance of the material above T_g was substantially reduced by the presence of PA66 fibers. Morphological analysis on the cryofractured surfaces revealed a quite good fiber‐matrix interfacial adhesion, with the presence of some nucleating phenomena on the pulled out surfaces. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

The effect of pressure and clay on the crystallization behavior and kinetics of polyamide‐6 in nanocomposites

The crystallization kinetics of polyamide‐6 (PA‐6) and its nanocomposite (PNC) with 2% clay were studied, using a pressure dilatometer (50 MPa to 200 MPa) to follow the volume changes associated with the crystallization process. Isobaric experiments were carried out to evaluate the effect of pressure and clay on melting temperature (T_m) and crystallization temperature (T_a) of PA‐6. The melting temperatures of PA‐6 in the PNC were very close to those of PA‐6 alone at comparable pressures, but the crystallization temperatures in the PNC were lower than those of PA‐6 alone. The materials exhibited two crystallization zones in isothermal/isobaric experiments. The initial zone involved both the γ‐form and the α‐form of PA‐6, while in the latter zone the γ‐form was dominant. The Avrami equation was used to fit the isothermal/isobaric crystallization data. The Avrami exponent n was between 1.0 and 3.2 for the γ‐form of unfilled PA‐6, between 0.9 and 2.6 for the γ‐form in PNC and for the γ‐form of PA‐6 alone, n was between 1.0 and 2.1 and in PNC between 1.2 and 2.6. The Avrami rate constants (K) for PA‐6 and PNC depend on the experimental crystallization temperature as well as pressure. The rate of crystallization under similar conditions was higher for PNC. Infrared studies on compression molded PA‐6 and PNC samples, cooled from melt at different rates, confirm the formation of the γ‐form in the initial stages of crystallization, as well as its transformation into the α‐form at later stages. In the case of PNC, the γ‐form stabilized when the sample was quenched from melt.     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

Isothermal crystallization kinetics and melting behavior of in situ compatibilized polyamide 6/Polyethylene-octene blends

We developed in situ compatibilization technology to improve the compatibility between polyamide 6 (PA 6) and polyethylene-octene (POE). In the present work, we investigated the isothermal crystallization and melting behavior of PA 6/POE blends using differential scanning calorimetry (DSC). All specimens exhibited double melting peaks at lower temperature and single melting peaks at higher temperature. The Avrami exponent and equilibrium melting temperature were obtained by analysis of DSC experimental data using the Avrami equation and Hoffman-Weeks theory, respectively. It has demonstrated that the crystallization model of PA 6 for all specimens might be a mixture with two-dimensional, circular, three-dimensional growth with thermal nucleation. We further calculated the nucleation parameter (K _g ) from the obtained crystallization kinetics data using Lauritzen-Hoffmann equation. It was found that the K _g values of the compatibilized PA 6 were lower than that of pure PA 6 whereas increased with the increase of POE content, which was related to the better dispersion of POE and the interaction between PA 6 and the in situ formed POE-g-MAH. Additionally, the spherulite morphology was observed by polarized optical microscopy (POM).     

Thermal and mechanical behavior of polyamide 6/polyamide 6I/6T blends

The thermal and mechanical properties of blends, obtained by mixing polyamide 6 (PA6) and an amorphous aromatic copolyamide G21 (ISO nomenclature PA 6I/6T), were investigated by differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. Quenched blends show a single glass transition temperature; the T_g-composition trend was interpreted by means of the Gordon–Taylor equation. The half-time of crystal-lization decreases by increasing the G21 content and this indicates a depression of the overall crystallization rate. A small decrease in the equilibrium melting temperature of PA6 in the blends was observed; this finding suggests that the interaction parameter in PA6/G21 blends is probably very small. The dynamic mechanical analysis of crystallized blends suggests the presence of a homogeneous amorphous phase even if the crystallization of PA6 occurred. The tensile mechanical properties reveal that G21 acts as stiffener of PA6. The collected experimental data suggest that PA6 and G21 are miscible in the composition range investigated. © 1996 John Wiley & Sons, Inc.     

Blends of polyamide 6, polycarbonate,and poly(propylene oxide). II. Reactive compatibilization–thermal degradation relationships

The thermal degradation of some blends of polyamide 6/polycarbonate (PA6/PC) and polyamide 6/polycarbonate/poly(propylene oxide) (PA6/PC/PPO) were investigated. The copolymer formed during the mixing of polyamide 6 and polycarbonate, at 240°C, for 30 min, increases the thermal stability of PA6/PC and of PA6/PC/PPO blends. This increase in the thermal stability occurs due to the plasticizing effect of PPO, which increases the mobility of the molecules of PA6 and PC, and consequently increases the probability of the reaction between the —NH₂ and —O—CO—O groups of polyamide 6 and polycarbonate, respectively. The ternary blends with PPO (5–10% w/w) have lower thermal stability than PA6/PC blends. This is due to the decrease of miscibility between these polymers and the rise of the diluting effect. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2556–2562, 2001     

Reactive blends of polyamide 6 with polyester elastomer using coupling agents

In situ compatibilized melt blends of polyamide 6 (PA‐6) with polyester elastomer (PEL) were prepared in a corotating twin‐screw extruder using two types of coupling agent (CA): diglycidyl ether of bisphenol A (DGEBA) and 1,4‐phenylene bis(2‐oxazoline) (PBO). The notched impact strength of PA‐6 and PA‐6/PEL blends increased with the addition of coupling agent, especially DGEBA, and the maximum impact toughening of the blend was obtained with 0.6 mol % DGEBA, the composition of minimum domain size observed from SEM. Viscosities of the untreated blends increased over those of the base resins at low frequencies. Viscosities of both the base resins and the blends increased with the addition of CA, and the effect was much more pronounced with DGEBA, especially for PA‐6 and PA‐6–rich blends. The crystallization temperature (T_c) of PEL increased over 10°C, whereas the T_c of PA‐6 decreased by 2–3°C in the blends. With the addition of coupling agents, the crystallization melting temperature (T_m) and T_c of PA‐6 decreased by up to 5°C with DGEBA, implying that the crystallization of PA‐6 is disturbed by the in situ formed PA‐6–CA–PEL or PA‐6–CA–PA‐6 type copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3966–3973, 2004     

Influence of carbon nanotubes with different functional groups on the morphology and properties of PPO/PA6 blends

Carbon nanotubes with different functional groups were prepared and then incorporated into the poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blend via melt blending. The influence of different carbon nanotubes on the morphology and properties of the blend was studied. The results show that addition of pristine CNTs, CNTs‐OH, CNTs‐NH₂ leads to the evolution of the phase structure of PPO/PA6 (mass ratio: 60/40) blend from sea‐island to cocontinuous, whereas incorporation of CNTs‐COOH does not change the blend morphology due to serious aggregation of the carbon nanotubes. Incorporating different CNTs into PPO/PA6 blend increases the tensile modulus and storage modulus of the blends, whereas decreases slightly the tensile strength. At the same time, the glass transition temperatures (T_g) of PA6 and PPO are enhanced. ΔT_g, the gap between the T_g of PA6 and PPO, decreases with the addition of carbon nanotubes due to the stronger interaction of carbon nanotubes with PA6 than PPO. A similar tendency was found in the storage modulus (G′) and complex viscosity (η*) of the composites. The dispersion state of different carbon nanotubes and their interaction with polymer components are different, which causes the different confinement effect to the macromolecular chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of maleated syndiotactic polystyrene on the morphology,mechanical properties,and crystallization behavior of syndiotactic polystyrene/polyamide 6 blends

The compatibilization of syndiotactic polystyrene (sPS)/polyamide 6 (PA‐6) blends with maleic anhydride grafted syndiotactic polystyrene (sPS‐g‐MA) as a reactive compatibilizer was investigated. The sPS/PA‐6 blends were in situ compatibilized by a reaction between the maleic anhydride (MA) of sPS‐g‐MA and the amine end group of PA‐6. The occurrence of the chemical reaction was substantiated by the disappearance of a characteristic MA peak from the Fourier transform infrared spectrum. Morphology observations showed that the size of the dispersed PA‐6 domains was significantly reduced and that the interfacial adhesion was much improved by the addition of sPS‐g‐MA. As a result of reactive compatibilization, the impact strengths of the sPS/PA‐6 blends increased with an increase in the sPS‐g‐MA content. The crystallization behaviors of the blends were affected by the compatibilization effect of sPS‐g‐MA. A single melting peak of sPS in the noncompatibilized blend was gradually split into two peaks as the amount of the compatibilizer increased. A single crystallization peak of PA‐6 in the noncompatibilized blend became two peaks with the addition of 3 wt % sPS‐g‐MA. The new peak was a result of the fractionation crystallization. As the amount of sPS‐g‐MA increased, the intensity of the new peak increased, and the original peak nearly disappeared. Finally, the crystallization peak of PA‐6 disappeared with 20 wt % sPS‐g‐MA in the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2502–2506, 2003     

Influence of the amorphous phase molecular mobility on impact and tensile properties of polyamide 6,6

In this work, the relationship between molecular mobility of polyamide 6,6 amorphous phase and mechanical properties is studied. PA66 formulations having different glass transition temperatures (T_g) obtained by additivation, chemical modification of the polyamide chains, and/or water conditioning at different hygrometry levels, are considered. The main emphasis is put on the impact strength, as measured by instrumented Charpy impact tests over a broad temperature range. It is observed that the brittle‐tough transition temperature T_B/T is closely correlated with the T_g of the samples rather than to the β secondary relaxation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43457.     

Influence of a synthetic ureido nucleating agent on crystallization behavior and mechanical properties of polyamide 6

A synthetic ureido mixture prepared from the reaction of 4,4′‐diphenylmethane disocynanate (MDI) and cyclohexylamine without using any harmful organic solvents, has been used as a nucleating agent (PNA) for polyamide 6 (PA6). The effect of PNA on the crystallization and mechanical properties of PA6 has been studied by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM), tensile test, melt flow index (MFI), and X‐ray diffraction (XRD). The results show that PNA is an effective nucleation agent for PA6. PNA affects the nucleation mechanism of PA6, and substantially accelerates the crystallization rate of PA6 and gives rise to smaller crystal size. In comparison with PA6, the crystallization temperature (T_c) of PA6/PNA (100/0.5) increases 21.3°C and the degree of sub‐cooling (ΔT_c) decreases 23.7°C. Furthermore, because of the heterogeneous nucleation induced by PNA, the spherulites of PA6 become even and tiny based on POM observation. Polymorph transform has been obtained from XRD analysis. The virgin PA6 is free of γ‐phase crystals, presented as α‐phase crystals in this study, but γ‐phase crystal appears after the introduction of PNA. The mechanical and thermal properties of PA6 are obviously improved by the addition of PNA. POLYM. ENG. SCI., 55:2011–2017, 2015. © 2015 Society of Plastics Engineers     

Thermal behavior and morphology of polyamide 6 based multicomponent blends

The thermal behavior and morphology of multicomponent blends based on PA6, polyamide 6 (PA6)/styrene–acrylonitirle copolymer (SAN), PA6/acrylonitrile–butadiene–styrene terpolymer (ABS), and their compatibilized blends with styrene–acrylonitrile–maleic anhydride copolymer (SANMA) were studied using DSC and SEM. The blends were prepared in a twin‐screw extruder under similar processing conditions, keeping the PA6 content fixed at 50 wt %. It was found that, in all the blends, the second component had a nucleating effect and improved the overall degree and rate of crystallization of PA6, whereas addition of a compatibilizer slightly diminished these effects and resulted in significant changes in the blend morphology. The nucleating effect and consequent changes in the crystallization behavior was attributed to the presence of SAN, which is a common component in all the blends. The T_g of PA6 in the blends with a cocontinuous morphology, due to the connectivity between the phases, is higher than in the blends with a disperse‐type morphology. The compatibilized blends have a lower crystallization rate and nucleation ability with a cocontinuous morphology, whereas the uncompatibilized blends have a higher crystallization rate with a higher nucleation ability and a disperse and/or a coarse cocontinuous morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2753–2759, 2002     

Improved processability of PA66-polyimide copolymers with different polyimide contents

Limitations in the properties of polyamide PA66, such as low glass transition temperature and high water absorptivity, limit its applications. Introduction of amorphous polyimide segments into the PA66 main chain lowers the glass transition temperature and melting temperature and also improves its processability. PA66-polyimide (PA-PI) copolymers with different weight ratios of PI are prepared by high temperature and high-pressure solution polymerization. The degree of crystallization of PA-PI copolymers decreases with increasing PI content. The melting point decreases from 261°C for PA66 to 223°C for PA-PI-4. Dynamic mechanical analysis shows that the T_g increases from 70 to 90°C, and the storage modulus can be well maintained. Rheological studies show that the temperature for processing can reach 70°C. Copolymers with different PI contents show different processing viscosities. In addition, water absorptivity (about 1.8%) and dielectric constant values of PA-PI and PA6/6T are similar.     

Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

On Blends of Polyamide 6 and a Hyperbranched Aramid

The hyperbranched (HB) aromatic polyamide synthesised by direct polycondensation of 5‐(4‐aminobenzoylamino)isophthalic acid (ABZAIA) has been solution‐ and melt‐ blended with polyamide 6 (PA6) incorporating different end groups. The concentration of p(ABZAIA) in PA6 has been varied from 5 to 30 wt.‐% in order to evaluate the influence of hyperbranched polymer content on blend properties. Viscosity and glass transition (T_g) data of the solution blends underlined the full miscibility between the components in the explored composition range. The miscibility was not related to any specific type of PA6 end group, thus suggesting a major role for its amide groups in interacting (presumably via hydrogen bonding) with HB functional end groups. Well‐separated powder particles have been obtained by precipitation from diluted solutions both for the neat polymers and for the blends. Also, in the case of blends prepared by melt mixing T_g linearly increased with the HB polymer content, again confirming full miscibility between the blend components. Blend characterisation, solubility tests and melt rheology supported the idea that p(ABZAIA) forms reactive blends with polyamide 6 by melt mixing. As a consequence of these reactions, the hyperbranched aramid strongly modified the rheological behaviour of PA6.

Formation of well dispersed spherical and homogeneous particles after precipitation of a PA6 dilute solution.     

High performance polyamide 6 composites prepared by reactive extrusion

To improve the properties of polyamide 6 (PA6) composites, a series of modified PA6 composites was prepared by reaction extrusion. An amorphous PA6 was first obtained by the complexing reaction of Li⁺ in lithium chloride with amino groups, and then epoxy resins, nano‐SiO₂ as well as POE‐g‐MAH were in turn added into the PA6/LiCl system. The effect of different additives on the crystallization behavior and mechanical properties of PA6 composites was well‐studied by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and mechanical properties tests. The results demonstrated that PA6 was amorphous at 6 phr lithium chloride and a network structure was formed in PA6 matrix in the presence of epoxy resins, thus the mechanical properties of composites greatly were enhanced. However too many nano‐SiO₂ particles might impair the tensile strength of PA6 composites. Additionally, a PA6 composite with excellent properties was obtained in the presence of POE‐g‐MAH due to the crystal form change in PA6 matrix and the strong interaction between PA6 and POE‐g‐MAH. POLYM. COMPOS., 35:985–992, 2014. © 2013 Society of Plastics Engineers