Non‐Ionic,Poly(ethylene oxide)‐Based Surfactants as Intercalants/Dispersants/Exfoliants for Poly(propylene)‐Clay Nanocomposites

Summary: Poly(propylene) (PP)‐clay nanocomposites were prepared from unmodified montmorillonite clays (NaMMT), with poly(ethylene oxide)‐based nonionic surfactants as dispersants/intercalants/exfoliants. The primary objective of this research was to find dispersants that (a) allow PP nanocomposites to be formed by direct melt mixing; (b) are effective with unmodified clays and (c) comprise of only a minor component with respect to both the clay and the overall composition. Linear, branched, gemini and sugar‐based surfactants and structures containing poly(dimethyl siloxane) and poly(methyl methacrylate) blocks were examined. These additives were found to be effective in breaking down the clay agglomerates to tactoids, giving some expansion of the clay structure and partial exfoliation and providing substantially improved clay dispersion. The properties of the derived nanocomposites depend on the level of additive and its structure. Tensile and impact properties show significant improvement over the precursor PP. Also notable are the significantly better thermal and thermo‐oxidative stabilities, as compared to both PP and “clay alone” composites. For optimal properties, it is both necessary and desirable that the surfactant should only be a minor constituent (20–50%) of the composition, with respect to the clay. A preferred surfactant is linear PE‐block‐PEO, with a short PEO block and an alkyl chain with approximately 30 carbon atoms (C₃₀).

     

In‐Situ Fiberized Poly(ethylene terephthalate) as a Reinforcement to Poly(propylene) Matrix

The reinforced poly(propylene) (PP)/poly(ethylene terephthalate) (PET) in‐situ fiberized composites were prepared by extrusion‐drawing‐injection molding. The influences of PET weight fraction (f_w) on the PET fiberization, phase morphology, and mechanical properties of the composites, together with their functional mechanisms were studied by contrast to the normal‐blended materials without drawing. The results show that as the f_w rises from 0 to 20%, the number of PET fibers increases, whereas their diameter and dispersity decrease till f_w = 15% and then increase, and the number of remained PET particles tends to rise. These changes of PET fiberization and phase morphology with f_w were attributed to the consequence of the combined actions of breakup, coalescence, and deformation of the PET dispersed phase in the PP matrix during the extrusion drawing. Correspondingly, the tensile strength (σ_t) and Young's modulus (E) of the in‐situ composites increase till f_w = 15% and then decrease, with maximum gains of σ_t and E of about 20 and 70% relative to the neat PP, respectively. This σ_t/f_w relation was ascribed to the counterbalanced result between the reinforcing effect of the dispersed phase on matrix and the interfacial flaw effect of two immiscible phases, while the E/f_w relation was considered as a representation of the rigidizing effect of the fibers on the matrix being controlled by both their number and diameter.

In‐situ PET fibres (PET/PP = 85/15) in an as‐drawn filament.     

A Reactive Flame Retardant as a Poly(propylene)‐Sized Glass Adhesion Promoter

Summary: Contact‐mode AFM adhesion strength measurements were employed in order to investigate the capability of PBBMA FR as an adhesion promoter in PP composites. The reactive FR exhibited superior coupling properties in comparison to conventional coupling agents such as PP‐g‐ma introduced in reinforced PP composites.

AFM image showing the recess carved out by the AFM tip in a PBBMA layer deposited on glass treated with APS.     

热致相分离法平片式聚(乙烯-乙烯醇)微孔膜的制备和表征

以丙三醇为稀释剂,用热致相分离方法(TIPS)制备了无纺布支撑的平片式聚(乙烯-乙烯醇)(EVOH)微孔膜。实验研究了冷却速率及EVOH初始浓度对膜结构及性能的影响,测定了EVOH／丙三醇体系的相图．用扫描电子显微镜(SEM)及泡点法表征了微孔膜的微观结构及表面孔径,同时测试了膜的纯水通量。结果表明,随着冷却速率的加快,结晶曲线向低温移动。EVOH初始浓度决定了体系的相分离方式．由液-液相分离及固-液相分离机理形成的膜分别具有花边结构与球间缝隙结构;冷却速率影响膜的孔径大小和形态。随着冷却速率及EVOH初始浓度的降低,膜的孔径及纯水通量均逐渐增大。     

Time‐Temperature Creep Behaviour of Poly(propylene) and Polar Ethylene Copolymer Blends

Polymers commonly undergo deformation under an applied stress over their lifetime; some deformations are irrecoverable once the source of stress is removed. Therefore an understanding of the response of a polymer can be achieved by investigating the viscoelastic properties using creep experiments, where the behaviour can be monitored under small deformational loads. Poly(propylene) (PP) was blended with a polar elastic, thermoplastic, poly[ethylene‐co‐(methyl acrylate)] (EMA), to toughen the matrix. EMA formed a dispersed phase in PP that maintained its strength through its crystallinity rather than crosslinking. EMA can form a compatible interface with PP through inclusion of maleated‐PP as a compatibiliser. The viscoelasticity of the PP–EMA blends, particularly the creep behaviour is an important factor if the properties of PP are to be maintained. The creep and recovery of PP–EMA blends with varying compositions were investigated under different loads and number of cycles. High EMA content provided an alternative deformation pathway due to its elastomeric properties. The experimental creep behaviour has been evaluated using the 4‐element model with some limitations evident in the viscoelastic transitional region.

     

Long‐Term Properties of Butt‐Welded Poly(propylene)

It is still not clear why the long‐term properties of plastic weld seams can only be differentiated by the very expensive medium tensile creep tests. One hypothesis for justifying this is based on the change in the structure of the weld seam surroundings, another cites the consumption of antioxidants and the following ageing in the weld seam area to be responsible for this. Butt‐welded weld seams made of poly(propylene) were systematically produced under different process parameters. Corresponding to the particular hypothesis, these weld seams were then analyzed in various ways to find correlations or to prove one of the hypotheses. Regarding their short‐term weld seam quality, the analyzed weld seams could not be differentiated through short‐term tensile or short‐term bend test. However, the medium tensile creep tests showed significant differences in both time until failure and long‐term weld seam quality. Under long‐term loading, the start of the brittle crack could be detected in most weld seams in the fine spherulite‐zone or between this zone and the area of the flow lines. This demonstrated again that only long‐term tests are suitable for examining different weld seam qualities. Depending on the welding parameters, times until failure decline with increasing heated‐tool temperature and heating time. Though these parameters lead to a higher consumption of antioxidants in the weld seam, a degradation was not detected in the breaking area. In fact, increasing heated‐tool temperatures and heating times, as well as higher joining pressures lead to a change in the internal structure of the material. This can be seen in morphological structure analyses in the larger bend of the entire weld seam area. A larger bend, however, correlates with higher residual stresses in the weld seam. In the medium tensile creep tests, these residual stresses as well as the tensile stress in the border region and the compressive stress in the middle are superimposed by the tensile stress resulting from the test stress. Thus a greater bend of the weld seam area and higher residual stresses in the weld seam itself lead to shorter times until failure in medium tensile creep tests.

Schematic representation of the formation of residual stresses in a weld seam and residual stresses in the different bended weld seam areas.     

Dwarf Cavendish as a Source of Natural Fibers in Poly(propylene)‐Based Composites

Summary: Composite materials were prepared by compounding and hot‐pressing PP or MAPP and lignocellulosic fibers extracted from the rachis of Musa acuminate Colla var. Dwarf Cavendish banana tree. The fibers were used as raw filler or after a chemical treatment expected to remove most of the extractible compounds. The resulting materials were characterized using SEM, DSC, DMA, tensile tests and water sorption experiments. All results show that the main aspect involved in the interfacial adhesion between the polar filler and the non‐polar matrix is the extraction of lignin and fatty substances. This results in higher values of the degree of crystallinity and crystallization temperature of the matrix, higher mechanical properties and lower water sensitivity.

Scanning electron micrograph showing the cross section of the lignocellulosic filler obtained from rachis of banana tree: (a) raw, and (b) extracted fibers.     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Thermal Behavior of Isotactic Poly(propylene)/Maleated Poly(propylene) Blends

This paper analyzes the thermal and thermo‐oxidative degradation behavior, phase separation, melting, and crystallization of blends consisting of isotactic poly(propylene) (IPP) and poly(propylene) grafted with maleic anhydride (PP‐g‐MA). It has been established that, depending on the blend composition and crystallization/preparation procedure, the blends of IPP and PP‐g‐MA can either co‐crystallize or evidence phase separation. This conclusion has been attained by comparing the DSC results of crystallization under dynamic and isothermal conditions with X‐ray diffraction results. On the basis of the obtained results, the optimum mixing ratios have been established as 95–85 wt.‐% IPP/5–15 wt.‐% PP‐g‐MA. Thermo‐oxidative behavior has been studied by thermogravimetry and differential thermal analysis.

     

Flow Instabilities in Linear and Branched Syndiotactic Poly(propylene)s

Extrusion flow experiments of linear and branched syndiotactic poly(propylene)s were carried out. The work was focused on flow instabilities. Ionized radiation was employed to induce long chain branching in linear samples. Sharkskin and melt fracture were postponed in the case of slightly long branched samples, which possess an enhanced melt elasticity compared to linear samples. For the most elastic samples the nature of the flow instability changed: sharkskin disappeared and melt fracture was observed instead. The correlation between sharkskin and melt strength results is discussed.

     

Quantifying Structural and Solid‐State Viscoelastic Properties of Poly(propylene) (PP)/Poly(oxymethylene) (POM) Blend Films

In this study, isotactic poly(propylene) (PP)/poly(oxymethylene) (POM) blend films, including of POM as minor phase in the range of 10–30 wt%, are prepared in a twin screw extruder equipped with a slit‐die and cast film haul‐off unit. It is found that the blend films show characteristic immiscible matrix‐droplet morphology. Short‐term uniaxial tensile creep behaviors of films imply that the introducing of POM significantly improves the elastic modulus and decreases the total creep strain of PP/POM blends. Creep tests are also performed at various temperatures and long‐term deformations of samples are predicted by applying of time‐temperature superposition principle and the Findley model. It is found that the presence of POM domains into PP matrix enhances the creep resistance of PP especially at high temperatures. It is concluded that the PP‐rich PP/POM blend films show much lower short and long‐term creep strains compared to PP.

     

Dynamic Mechanical Properties of Poly(propylene) Blends with Poly[ethylene‐co‐(methyl acrylate)]

Summary: Blends of poly(propylene) (PP) were prepared with poly[ethylene‐co‐(methyl acrylate)] (EMA) having 9.0 and 21.5% methyl acrylate comonomer. A similar series of blends were compatibilized by using maleic anhydride grafted PP. The morphology and mechanical properties of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) in tensile mode. The DMA method and conditions were optimized for polymer film specimens and are discussed in the experimental section. The DSC results showed separate melting that is indicative of phase‐separated blends, analogous to other PP‐polyethylene blends but with the added polarity of methyl acrylate pendant side groups that may be beneficial for chemical resistance. Heterogeneous nucleation of PP was decreased in the blends because of migration of nuclei into the more polar EMA phase. The crystallinity and peak‐melting temperature did not vary significantly, although the width of the melting endotherm increased in the blends indicating a change had occurred to the crystals. DMA analysis showed the crystal‐crystal slip transition and glass transition (T_g) for PP as well as a T_g of the EMA copolymer occurring chronologically toward lower temperatures. The storage modulus of PP and the blends was generally greater with annealing at 150 °C compared with isothermal crystallization at 130 °C. The storage modulus of the blends for isothermally crystallized PP increased with 5% EMA, then decreased for higher amounts of EMA. Annealing caused a decrease with increasing copolymer content. The extent of the trend was greater for the compatibilized blends. The T_g of the blends varied over a small range, although this change was less for the compatibilized blends.

Storage modulus for PP and EMA9.0 blends annealed at 150 °C.     

Temperature Sensitive Behavior of Poly(N‐isopropylacrylamide) Grafted Onto Electron Beam‐Irradiated Poly(propylene)

Summary: N‐Isopropylacrylamide (NIPAAm) was graft‐polymerized from its acetone solution onto poly(propylene) (PP) films, after electron‐beam irradiation in the presence of air oxygen. The effects of pre‐irradiation dose as well as monomer concentration, reaction temperature and reaction time on the grafting efficiency were investigated. Typical conditions for achieving maximum grafting yield were observed for 1 M monomer concentration, after PP pre‐irradiation with a 300 kGy dose and a reaction temperature of 50 °C. The location of the graft polymerization was examined by different methods including measurements of dimensional variations, calorimetry, SEM and AFM. The temperature‐responsive behavior of grafted copolymer was studied by swelling and contact angle measurements at different temperatures.

Temperature dependence of the swelling ratio in water as a function of temperature.     

Functionalization of Poly(propylene) Fabric with 4‐Vinylpyridine,N,N‐Dimethylacrylamide and Styrene by γ‐Radiation‐Induced Grafting in an Aqueous Environment

Summary: VP and co‐monomers DMAAm and ST were successfully grafted onto a PP fabric in an emulsion copolymerization process initiated by γ‐radiation. The radiation dose, concentration of VP, the ratio of VP/DMAAm and VP/ST in the reaction solution, and the reaction temperature dependent graft copolymerization were investigated. The order of dependence of the initial rate of grafting on the radiation dose was found to be in the range of 1.2 to 0.93 for VP; 0.84 to 0.70 for VP/DMAAm and for VP/ST was in the range of 0.59 to 0.41. The activation energy of the graft copolymer reaction was determined to be 40.18 J · mol^?1 for 0.464 mol · L^?1 VP. In the case of co‐monomer mixtures (VP/DMAAm: 0.464/0.5) the energy of activation was noticeably higher at 49.71 J · mol^?1 while for VP/ST (0.464/0.436) the activation energy was same as that of VP. XRD results showed that overall crystallinity significantly decreased with the increase of graft weight with a noticeable change in the chemical structure of the PP, indicating that the graft copolymer reaction was taking place both in the amorphous and crystalline regions of PP. A similar characteristic behavior was also obtained by DSC, which revealed the presence of an endotherm process in the range of 25 to 130 °C depending on the degree of grafting, attributed to the grafted chains of the monomer/co‐monomers. In order to determine the graft copolymer reaction of VP, DMAAm and ST onto the backbone of PP, the reaction products were characterized by FTIR spectroscopy. A good correlation was found between changes of crystallinity and level of graft copolymerization as determined by WAXRD and DSC.

Typical XRD traces of as‐received PP fabric (PPF) and grafted with VP (PPF‐g‐VP).     

Poly(propylene)/poly(ethylene terephthalate‐co‐isophthalate) blends and glass bead filled composites: Microstructure and thermomechanical properties

Blends of poly(propylene) (PP) and poly(ethylene terephthalate‐co‐isophthalate) (co‐PET) (95/5) with and without compatibilizing agent (maleic anhydride PP), as well as composites of these blends with glass beads (50 wt%) with and without silane coupling agent surface‐treatment, were prepared and studied on a basis of the material microstructure and thermomechanical properties. Infrared and Raman spectroscopy, as well as transmission electron microscopy, displayed evidence of MAPP compatibilizing action for the blend. Differential scanning calorimetry showed a remarkable effect of nucleation rate increase exerted by co‐PET on the PP crystallization. Moreover, glass beads were found to increase the PP nucleation rate slightly. PP crystallinity hardly varied with the composition. Wide angle X‐ray diffraction allowed determination of differences in the orientation of the poly(propylene) b‐axis, with more homogeneous orientations in the presence of both co‐PET and glass beads. MAPP promoted the PP b‐axis orientation. Differences in PP α′ relaxation could be analyzed through dynamic‐mechanical thermal analysis (DMTA). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1841–1852, 2004     

Mechanical,rheological, thermal,and morphological properties of blends based on poly(propylene)/poly(propylene‐co‐1‐octene)/poly(ethylene‐co‐1‐octene)

The effect of addition of propylene copolymer, produced by metallocene catalysts, on the mechanical, rheological, and morphological properties of blends based on poly(propylene) (PP) and ethylene–1‐octene copolymer (EOC) was evaluated. It was observed that the addition of 2 wt % propylene–1‐octene copolymer (POC) improved the impact strength of the EOC/PP blends. The rheological analysis indicated that the addition of propylene copolymer produced materials with improved processability. Thermal and morphological analysis showed that the POC acts as a compatibilizer on the EOC/PP blends. © 2003 Wiley Periodicals, J Appl Polym Sci 89: 1690–1695, 2003     

Grafting of Hindered Amine Stabilizer in Poly(propylene) Films under γ‐Irradiation

Summary: In this paper, the grafting of a hindered amine stabilizer (HAS) is studied in isotactic poly(propylene) (PP) films under γ‐irradiation. The HAS used has a definite structure that combines a hindered amine functionality and a UV‐absorbing unit (benzylidene malonate ester group) detectable at 308 nm in the UV spectrum of PP film and 314 nm in chloroform. The stabilizer is added to the polymer at various concentration ratios: 0.1, 0.2, and 0.3 wt.‐%. The percentage of HAS grafting in the PP film at various additive concentrations is determined as a function of γ‐radiation dose in the range of 0–100 kGy by direct spectroscopic measurements through the absorption band of the stabilizer in the UV spectra of the PP film. The percentage of free HAS extracted with chloroform from the PP film versus the radiation dose is determined by UV spectroscopy for all the additive concentrations used. This study reveals that only 80% of the HAS is grafted on the 100 kGy irradiated PP matrix independent of the additive concentration used. However, the percentage of HAS grafted on PP films displays an exponential dependence on γ‐radiation dose. These results are consistent with the data obtained on the free HAS content. γ‐Irradiation grafting of HAS in the PP is accompanied by the oxidative degradation of the polymer substrate that is evaluated by increasing the carbonyl index and reducing significantly the oxidation induction time of the PP films.

The percentage of hindered amine stabilizer grafted to the PP film as a function of γ‐radiation dose.     

Effect of Organoclay on the Morphology and Properties of Poly(propylene)/Poly[(butylene succinate)‐co‐adipate] Blends

The effect of organically modified clay on the morphology and properties of poly(propylene) (PP) and poly[(butylene succinate)‐co‐adipate] (PBSA) blends is studied. Virgin and organoclay modified blends were prepared by melt‐mixing of PP, PBSA and organoclay in a batch‐mixer at 190 °C. Scanning electron microscopy studies revealed a significant change in morphology of PP/PBSA blend in the presence of organoclay. The state of dispersion of silicate layers in the blend matrix was characterized by X‐ray diffraction and transmission electron microscopic observations. Dynamic mechanical analysis showed substantial improvement in flexural storage modulus of organoclay‐modified blends with respect to the neat polymer matrices or unmodified blends. Tensile properties of virgin blends also improved in the presence of organoclay. Thermal stability of virgin blends in air atmosphere dramatically improved after modification with organoclay. The effect of organoclay on the melt‐state liner viscoelastic properties of virgin blends was also studied. The non‐isothermal crystallization behavior of homopolymers, virgin, and organoclay‐modified blends were studied by differential scanning calorimeter. The effect of incorporation of organoclay on the cold crystallization behavior of PP/PBSA blends is also reported.

     

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and Poly(propylene carbonate) Blends: an Efficient Method to Finely Adjust Properties of Functional Materials

Polyhydroxyalkanoate (PHA) and poly(propylene carbonate) (PPC) are blended in order to investigate their mutual contributions in terms of functional properties. A wide range of blend composition is processed through extrusion from dry blends. Droplet‐matrix morphology is observed for all samples. Thermal investigations reveal the PPC effect on the PHA crystallization process with a decrease and broadening of the crystallization temperature window and on the depression of its glass transition temperature. This investigation also confirms the as yet un‐reported non‐miscibility of this kind of blend. However, a slight phase interaction is expected since thermal behavior of PHA is impacted. The fragile behavior of PHA is balanced by the high ductility of PPC. The weak strain at break of PHA can thus be increased by up to 200% although a significant amount of PPC is needed to start modifying this property. Stress at break and modulus are linearly decreased from pure PHA to pure PPC values. PPC also acts as an impact modifier for PHA. In terms of barrier properties, PHA brings a large contribution even at low content to the initially high oxygen and water vapor permeability of PPC.

     

Flexural Creep Behavior of Unidirectional and Cross‐Ply All‐Poly(propylene) (PURE®) Composites

The long‐term viscoelastic behavior of reinforced all‐poly(propylene) composites was studied by flexural creep tests. Both unidirectional and cross‐ply laminates were prepared from PURE® coextruded tapes by vacuum bag molding in an autoclave. The specimens were subjected to isothermal creep tests at different temperatures ranging from 20 to 80 °C under an applied load. The time‐temperature superposition principle was verified for the creep data. An Arrhenius type relationship was found to better describe the shift data obtained from the creep tests. The activation energies relating to the different reinforcement architecture and different relaxation process were calculated.