Location of functionalized-TiO<Subscript>2</Subscript> nanoparticle in an immiscible PP/PA6 blends and its effect on the compatibility of the components

Nanocomposites based on 70/30 (w/w) polypropylene (PP)/polyamide 6 (PA6) immiscible blends and functionalized-TiO₂ nanoparticles were prepared via melt compounding. The influences of TiO₂ on the morphology of nanocomposites were investigated. Scanning electron microscopy results revealed the domain size of the dispersed PA6 phase decreased in presence of functionalized-TiO₂ and the TiO₂ nanoparticles were preferentially located at the PA6 phase and at the interfacial region between PP and PA6, which were ascertained by differential scanning calorimetry. The functionalized-TiO₂ nanoparticles played the compatibilizer for the immiscible PP/PA6 blends, increasing the interaction of the two phases in certain extent. Therefore, a clear compatibiliting effect was induced by the TiO₂ in the immiscible PP/PA6 blends.     

Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Polyethylene terephthalate/low density polyethylene/titanium dioxide blend nanocomposites: Morphology,crystallinity, rheology,and transport properties

Physical features of polyethylene terephthalate (PET)/low density polyethylene (LDPE) immiscible blends, rich in PET, with and without titanium dioxide (TiO₂) nanoparticles are studied. These materials are of industrial interest, because they can be obtained by recycling PET bottles containing TiO₂ with their corresponding polyethylene made caps. Their potential application in packaging is investigated. Droplet-matrix morphology is observed by scanning electron microscopy; coalescence occurs during compression molding. Transmission electron microscopy results show that TiO₂ nanoparticles are located at the interface between PET and LDPE, forming a physical barrier that favors development of smaller droplets. Thermal analysis results are compatible with the morphology of the blends and the location of the TiO₂ nanoparticles. Viscosity obtained by extrusion continuous flow and oscillatory flow measurements in the linear regime show that some of the blends have viscoplastic behavior. Permeability results reveal that 80PET/20LDPE/TiO₂ blend nanocomposite shows a balanced barrier character to both oxygen and water vapor. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46986.     

Confined crystallization phenomena in immiscible polymer blends with dispersed micro- and nanometer sized PA6 droplets, part 2: reactively compatibilized PS/PA6 and (PPE/PS)/PA6 blends

In this paper the relation between the blend phase morphology and the fractionated crystallization behavior of PA6 in reactively compatibilized immiscible PS/PA6 and (PPE/PS)/PA6 immiscible blends is studied. Reactive compatibilization is used as an effective tool for controlling the blend phase morphology, and to reduce the PA6 dispersed droplet size. As reactive compatibilizers, SMA2 and SMA17 are used, which differ in their level of miscibility with the amorphous PS and (PPE/PS) components. With SMA2 a strong shift of PA6 crystallization to much higher supercoolings than before is found after compatibilization resulting in crystallization at temperatures as low as 85 °C. This is ascribed to the strong decrease of the droplet sizes down to 100-150 nm. Nucleation experiments show that heterogeneous bulk nucleation can be reintroduced in the submicron-sized PA6 droplets by adding enough nucleating agents of sufficient small size. The degree of fractionated crystallization is found to depend on the interface between PA6 droplets and surrounding medium, as it is influenced by vitrification of the matrix polymer and by the location of the compatibilizers SMA2 and SMA17. The method used for mixing the reactive compatibilizer with the blend components also affects the fractionated crystallization process.     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Carbon black self-networking induced co-continuity of immiscible polymer blends

This work aims to clarify the mechanism of nanoparticle-induced co-continuity in immiscible polymer blends. An industrially relevant system, carbon black (CB)-filled acrylonitrile-butadiene-styrene (ABS)/polyamide 6 (PA6) blends, is investigated via scanning electron microscopy, selective extraction tests, dynamic mechanical analysis, and electrical conductivity measurements. The CB particles are found to be preferentially localized in the PA6 phase, and with an increase in CB loading (Φ_CB), the critical volume fraction of PA6 (Φ_PA6) that is essential for building the co-continuous structure decreases. The product of Φ_PA6 and Φ_CB, n, remains constant for the given system, suggesting that there exists an intrinsic cooperative effect between the CB and the CB-localized polymer phase. A further decrease in Φ_PA6 is achieved either by loading CB with a higher self-networking capability or by isothermal post-treatments for sufficient self-agglomeration of the CB clusters. It is demonstrated that, under the direction of CB self-networking, the CB-localized polymer domains tend to fuse together into co-continuous organization with little phase coarsening. Therefore, CB self-assembly not only plays a key role in extending phase co-continuity over a much larger composition range but also acts on stabilizing the co-continuous polymer domains during the melt processing.     

Nanoparticle-induced co-continuity in immiscible polymer blends – A comparative study on bio-based PLA-PA11 blends filled with organoclay,sepiolite, and carbon nanotubes

Different amounts of organoclay, sepiolite, and carbon nanotubes are added to an immiscible blend of poly(lactic acid) (PLA) and polyamide 11 (PA11) with drop-matrix morphology aiming at elucidating the mechanisms through which unevenly distributed nanoparticles may induce co-continuity. Morphological and dynamic-mechanical analyses show that the three fillers, preferentially located inside the minor PA11 phase, are all able to convert the drop-matrix morphology of the blend into a stable, highly co-continuous one provided a critical nanoparticle loading is exceeded. The cross-checking of the experimental results reveals that co-continuity occurs when the strength of the particle network encapsulated inside the PA11 is sufficient to balance the inclination of the stretched polymer domains to retract back towards lower aspect ratio shapes driven by interfacial tension. A single dimensionless group that combines the yield stress of the filled PA11, the bending resistance of the nanoparticles, and the PLA-PA11 interfacial tension, seems able to rationalize our data, providing a general criterion for the optimal selection of fillers suitable to induce co-continuity in immiscible polymer blends.     

Morphology and mechanical property changes in compatibilized high density polyethylene/polyamide 6 nanocomposites induced by carbon nanotubes

Addition of carbon nanotubes to immiscible polymer blends with co‐continuous morphology features to improve the electrical conductivity has attracted much attention in recent years; however, less attention has been paid to the effect of carbon nanotubes on the morphology and corresponding physical properties of immiscible polymer blends with typical sea‐island morphology. In this work, therefore, functionalized multiwalled carbon nanotubes (FMWCNTs) were introduced into an immiscible high density polyethylene/polyamide 6 (HDPE/PA6) blend which was compatibilized by maleic anhydride grafted HDPE (HDPE‐MA). The distribution of FMWCNTs and the phase morphologies of the nanocomposites were characterized using scanning electron microscopy and transmission electron microscopy. The crystallization and melting behaviors of the components were analyzed by differential scanning calorimetry, which is thought to be favorable for an understanding of the distribution of FMWCNTs. It is interesting to observe that the morphology of PA6 particles is very dependent on the method of preparation of the nanocomposites. Correspondingly, FMWCNTs exhibit an apparent reinforcement effect and/or an excellent toughening effect for the compatibilized HDPE/PA6 blend, depending upon their distribution state and the variation of PA6 morphology. This work proves that FMWCNTs have a potential application in further improving the mechanical properties of compatibilized immiscible polymer blends. Copyright © 2012 Society of Chemical Industry     

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     

Incorporation of modified Stöber silica nanoparticles in polystyrene/polyamide-6 blends: Coalescence inhibition and modification of the thermal degradation via controlled dispersion at the interface

The controlled dispersion of Stöber silica nanoparticles (SiNPs) at the interface of a PS/PA6 (80/20 wt%) blend was achieved by means of surface modifications using 3-methacryloxypropyltrimethoxysilane (MPS). The final localization of SiNPs in the blend was predicted using wetting parameter calculation and confirmed by scanning electronic microscopy (SEM) observations. Stability of blends during annealing was evaluated qualitatively by laser diffraction particle size analyzer. Morphologies of the blends in the molten state were observed using optical microscopy. Flammability of blends was investigated using pyrolysis-combustion flow calorimeter (PCFC). Results showed that both microstructure stability during annealing and thermal degradation of the blend, were improved when MPS-modified SiNPs are located at the interface. SEM pictures revealed that the MPS-modified SiNPs form a solid barrier between PS and PA6 phases which inhibits coalescence process and modifies the thermal degradation mechanisms.     

A dissipative particle dynamics study on the compatibilizing process of immiscible polymer blends with graft copolymers

The dissipative particle dynamics (DPD) is used to study the compatibilizing process of an immiscible polymer blend using a graft copolymer as a compatibilizer. Polystyrene (PS) and polyamide 6 (PA6) are chosen as the polymer components of the blend. The graft copolymer is composed of PS as the backbone and PA6 as the grafts. Mesoscale morphology, density distribution, end-to-end distance of PA6 and interfacial tension are investigated. Simulations show that the presence of a graft copolymer contributes to the formation of finer and more uniform dispersed domains by preventing them from collision and coalescence. In the presence of a graft copolymer, the density distribution is more uniform and the dynamic equilibrium of the blend morphology is reached more rapidly. For a given backbone and number of grafts per backbone, the compatibilizing efficiency of the graft copolymer first increases with increasing graft length. However, when the graft length exceeds a certain value, it starts decreasing.     

Formation and stability of string phase in polyamide 6/polystyrene blends in confined flow: Effects of nanoparticles and blend ratio

Influences of silica nanoparticles on the microstructural evolution of polyamide 6 (PA6)/polystyrene (PS) blends with varying blend ratios were investigated in confined shear flow. Hydrophilic silica nanoparticles were found to promote the formation of PA6 strings with excellent shape stability during shearing. It was ascribed to the promoted coalescence of PA6 droplets induced both by the significantly increased droplet viscoelasticity and confinement, and the reduced interfacial tension by adding silica nanoparticles. Additionally, the width and aspect ratio of droplets obtained by experiments were compared with the predictions of Maffettone–Minale, Minale, Shapira‐Haber, MMSH, and modified M models. Good agreements were found in the droplet width in blends with low nanoparticle concentrations, whereas the experimental aspect ratio showed a negative deviation to model predictions, which was attributed to the enhanced droplet viscoelasticity and the omitted droplet orientation angle in these models. © 2015 American Institute of Chemical Engineers AIChE J, 62: 564–573, 2016     

Polyamide/Polystyrene Blend Compatibilisation by Montmorillonite Nanoclay and its Effect on Macroporosity of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells

This work deals with a new route to modify polymer blend morphology in order to improve the porosity of gas diffusion layers (GDLs) for proton exchange membrane fuel cells (PEMFCs). First, electrically conductive polymer‐based blends were carefully formulated using a twin‐screw extrusion process. Blend electrical conductivity was ensured by the addition of high specific surface area carbon black and synthetic graphite flakes. Final GDL porosity, in particular its macroporosity, was generated by melt blending polyamide 11 (PA11) matrix with polystyrene (PS) followed by PS extraction with tetrahydrofuran (THF) solvent at room temperature. In order to improve GDL porosity by the optimisation of PS dispersion in the PA11 matrix, PA11/PS blends were compatibilised by the addition of 2 wt.‐% of clay. It was observed that both macroporosity and pore size distribution were beneficially modified after blend compatibilisation. Final GDL conductivity of about 1.25 S cm^–1, a porosity of 53% and a specific pore surface area of 75 m² g^–1 were achieved.     

Blend composition dependence of the compatibilizing efficiency of graft copolymers for immiscible polymer blends

This work is concerned with the dependence of the compatibilizing efficiency of graft copolymers on the composition of immiscible polymer blends. A series of graft copolymers of polystyrene (PS) and polyamide 6 (PA6), denoted as PS‐g‐PA6, with different molecular structures were used as compatibilizers. The PS‐g‐PA6 was more efficient for the PS/PA6 (80/20) blend than for the PS/PA6 (20/80) one, indicating that a graft copolymer whose backbone and grafts match the matrix and the disperse phase polymers, respectively, has higher compatibilizing efficiency. This is in disagreement with the literature. Moreover, whatever the blend composition, for PS‐g‐PA6 graft copolymers with the same backbone and the same number of grafts per backbone, the longer the grafts, the higher their compatibilizing and stabilizing efficiency; for a given backbone/graft mass ratio, the longer the grafts and concomitantly the smaller the number of grafts per backbone, the higher the compatibilizing and stabilizing efficiency of the graft copolymer. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Morphological effects on glass transition behavior in selected immiscible blends of amorphous and semicrystalline polymers

The effects uncompatibilized immiscible polymer blend compositions on the T_g of the amorphous polymer were studied in the systems polystyrene/polypropylene (PS/PP), polystyrene/high density polyethylene (PS/PE) and polycarbonate/high density polyethylene (PC/PE). In the two similar systems of PS/PP and PS/PE, the T_g of PS increased with decreasing PS percentage in the blends. This variation in glass transition is attributed to the polymer domain interactions resulting from the different morphologies of various blend compositions. Experiments were conducted to study these effects by preparing blends with various polymers that varied the relationship between the T_g of the amorphous polymer and the crystallization behavior of the semicrystalline polymer. Results show that the variation in amorphous component T_g with composition depends strongly on the physical state of the semicrystalline domains. Whereas the T_g of PS in PS/PE blends changed with composition, the T_g of PC in the PC/PE blend did not change with composition.     

Morphology and rheology of immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology and the rheological properties of an immiscible polymer blend (polypropylene/polystyrene, PP/PS 70/30) was investigated. Two types of pyrogenic nanosilica were used: a hydrophilic silica with a specific surface area of 200 m²/g and a hydrophobic silica having a specific surface area of 150 m²/g. First, a significant reduction in the PS droplet volume radius, from 3.25 to nearly 1 μm for filled blends with 3 wt% silica, was observed. More interestingly, image analysis of the micrographs proved that the hydrophilic silica tends to confine in the PS phase whereas hydrophobic one was located in the PP phase and at the PP/PS interface (interphase thickness ≈ 100-200 nm). Furthermore, a migration of hydrophilic silica from PP phase toward PS domains was observed.An analysis of the rheological experimental data was based on the framework of the Palierne model, extended to filled immiscible blends. Due to the partition of silica particles in the two phases and its influence on the viscosity ratio, limited cases have been investigated. The rheological data obtained with the hydrophobic silica were more difficult to model since the existence of a thick interphase cannot be taken into account by the model. Finally, the hypothesis that hydrophilic silica is homogeneously dispersed in PS droplets and that hydrophobic silica is dispersed in PP matrix was much closer to the actual situation. It can be then concluded that stabilization mechanism of PP/PS blend by hydrophilic silica is the reduction in the interfacial tension whereas hydrophobic silica acts as a rigid layer preventing the coalescence of PS droplets.     

Reactive blending of poly (dimethylsiloxane) with nylon 6 and poly (styrene):Effect of reactivity on morphology

Reactive compatibilization was used to control and stabilize 20–30wt% poly(dimethylsioxane) (PDMS) dispersions in nylon 6 (PA) and poly(styrene) (PS), respectively. The effect of the type of reation (amine (NH₂)/anhydride (An), NH₂/ epoxy(E) and carboxylic acid (COOH)/E) on the morphology was studied with electron microscopy. PS and PDMS have mutual solvents thus it was possible to use gel permeation chromatography (GPC) to determine the concentration of block copolymer in PS/PDMS blends. Reactive blending of PA6 with difunctional PDMS‐(AN)₂ did not decrease the PDMS particle size compared to the non‐reactive blend (～10μm). Particle size decreaeased significantly to about 0.5 μm when PA6 was blended with a PDMS containing about 4 random An groups along the chain. For the PS/PDMS blends, GPC revealed that the NH₂/An reaction formed about 3% block copolymer and produced stable PDMS particles ～ 0.4 μm. No reaction was detected for the PS‐NH₂/PDMS‐E blend and the morphology was coarse and unstable. Also, PS‐NH₂/PDMS‐An reactivity was lower compared to other systems such as PS/ poly (isoprene) and PS/poly(methaacrylte) using the same reaction. This was attributed to the relatively thinner PS/PDMS interface dueto the high PS/PDMs immiscibility.     

Kinetics-controlled compatibilization of immiscible polypropylene/polystyrene blends using nano-SiO2 particles

Rigid inorganic filler has been long time used as a reinforcement agent for polymer materials. Recently, more work is focused on the possibility that using filler as a compatibilizer for immiscible polymer blends. In this article, we reported our efforts on the change of phase morphology and properties of immiscible polypropylene(PP)/polystyrene(PS) blends compatibilized with nano-SiO₂ particles. The effects of filler content and mixing time on the phase morphology, crystallization behavior, rheology, and mechanical properties were investigated by SEM, DSC, ARES and mechanical test. A drastic reduction of PS phase size and a very homogeneous size distribution were observed by introducing nano-SiO₂ particles in the blends at short mixing time. However, at longer mixing time an increase of PS size was seen again, indicating a kinetics-controlled compatibilization. This conclusion was further supported by the unchanged glass transition temperature of PS and by increased viscosity in the blends after adding nano-SiO₂ particles. The compatibilization mechanism of nano-SiO₂ particles in PP/PS blends was proposed based on kinetics consideration.     

Confined crystallization phenomena in immiscible polymer blends with dispersed micro- and nanometer sized PA6 droplets, part 3: crystallization kinetics and crystallinity of micro- and nanometer sized PA6 droplets crystallizing at high supercoolings

Crystallization kinetics and crystallinity development of PA6 droplets having sizes from 0.1 to 20 μm dispersed in immiscible uncompatibilized PS/PA6 and reactively compatibilized (PS/Styrene-maleic anhydride copolymer=SMA2)/PA6 blends are reported. These blend systems show fractionated crystallization, leading to several separate crystallization events at different lowered temperatures. Isothermal DSC experiments show that micrometer-sized PA6 droplets crystallizing in an intermediate temperature range (T_c∼175 °C) below the bulk crystallization show a different dependency on cooling rate compared to bulk crystallization, and an athermal crystallization mechanism is suggested for PA6 in this crystallization temperature region. The crystallinity in these blends decreases with PA6 droplet size. Random nucleation, characteristic for a homogeneous nucleation process, is found for sub-micrometer sized PA6 droplets crystallizing between T_c 85 and 110 °C using isothermal DSC experiments. However, crystallization in the PA6 droplets is most likely initiated at the PA6-PS interface due to vitrification of the PS matrix during crystallization. Very imperfect PA6 crystals are formed in this low temperature crystallization region, leading to a strongly reduced crystallinity. These crystals show strong reorganization effects upon heating.     

Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006