L. Minkova

Reactive Compatibilizer Precursors for LDPE/PA6 Blends, 1 Ethylene/Acrylic Acid Copolymers

Ethylene/acrylic acid copolymers (EAA) with different acrylic acid (AA) contents have been used as compatibilizer precursors (CPs) for blends of two grades of lowdensity polyethylene (LDPE) with polyamide-6 (PA). In the first part of the work, binary blends of the CPs with LDPE and with PA have been studied in order to get an insight into the interactions of the EAA copolymers with the blends components. It has been shown that the CPs form immiscible, yet highly compatible, blends with LDPE. Investigation of the binary CP/PA blends provided evidence that acidolysis reactions occur between the carboxyl groups of the CPs and the amine and amide groups of PA, with formation of CP/PA graft (CP-g-PA) copolymers, although these reactions need relatively long times to go to completion. In the second part of the work, ternary LDPE/PA/CP blends have been prepared and characterized with a number of techniques. It has been shown that the addition of only 1-2 phr of CP into the LDPE/ PA blends is sufficient to enhance interfacial adhesion, to improve the minor phase droplet dispersion and to hinder coalescence. The effectiveness of the investigated CPs increases with an increase of the AA content from 6 to 11 wt.-%. Partial neutralization of the carboxyl groups of EAA with zinc also seems to improve the CP efficiency and this effect is thought to result from an acceleration of the acidolysis reactions responsible for the formation of CP-g-PA copolymers.

Non-isothermal crystallization kinetics of poly(phenylene sulfide)/Vectra-B blends

Abstract The non-isothermal crystallization behaviour of blends of poly(phenylene sulfide) (PPS) with the thermotropic liquid-crystalline copoly(ester amide) Vectra-B950 (VB) was studied by means of differential scanning calorimetry. The PPS crystallization temperature and the crystallization rate coefficient were found to increase markedly upon addition of 2–50% VB. It was shown that the Ozawa equation is valid not only for neat PPS but also for the blends. The values of the Avrami exponents are in fair agreement with those found previously by isothermal analysis, and do not depend on the presence and the concentration of VB. It has been suggested that the slope of the plots of the cooling crystallization function versus T can be a criterion for the overall non-isothermal crystallization rate. It has been concluded that the non-isothermal crystallization of PPS is strongly accelerated by the presence of the VB phase, whereas the type of nucleation and the geometry of crystal growth do not change, and no reduction of the PPS degree of crystallinity could be noticed.

Microhardness and thermal stability of compatibilized LDPE/PA6 blends

Microhardness tests, water absorption and thermogravimetric measurements have been performed on blends of low density polyethylene (LDPE) with different molar mass and polyamide 6 (PA6) compatibilized with 2 pph poly(ethylene-co-acrylic acid) (Escor 5001 by Exxon). The negative deviation of Vickers microhardness from the additivity has been interpreted by changes in the crystallinity of the blend components. The hardness values of the compatibilized blends that are lower than those of the corresponding uncompatibilized blends have been explained by the decrease of the degree of crystallinity of PA6 phase in the presence of Escor. The molar mass of LDPE almost does not influence on the hardness values. The lower water absorption of the compatibilized blends, caused by the formation of a copolymer between PA6 and the compatibilizer leads to microhardness values of the wet compatibilized blends higher than those of the corresponding uncompatibilized blends. The thermogravimetric measurements demonstrate that the thermal stability of blends increases in the presence of 2 pph Escor 5001. The results confirm the compatibilizing efficiency of Escor 5001 towards LDPE/PA6 blends in a wide composition range.

Blends of normal high density and ultra-high molecular weight polyethylene, γ irradiated at a low dose

The kinetics of a nonisothermal crystallization and melting ofγ irradiated with dose of 6 Mrad blends of an ultra-high molecular-weight polyethylene (UHMWPE) and a high-density polyethylene with normal molecular weight (NMWPE) is investigated by means of DSC. The blends have been prepared at temperature below the flow temperature of UHMWPE: The enthalpies of melting of the polyethylenes increase, while those of their blends decrease after irradiation. The enthalpies of crystallization of the pure polyethylenes are higher, while those of their blends almost do not change or are a bit higher after irradiation. The rates of a nonisothermal crystallization and melting of the polyethylenes increase, while those of the polyethylenes in the blends decrease after irradiation. Thermomechanical measurements under constant load in wide-temperature interval of irradiated polyethylenes and their blends have been made. A high-elastic plateau in viscous-liquid state is established on the thermomechanical curves of UHMWPE, and the blends with high content of UHMWPE. On the basis of results obtained assumptions have been made about the processes taking place in the blends under the action of irradiation, as well as about the character of the mutual influence between the components in the process of irradiation.

Synthesis of PP–LCP graft copolymers and their compatibilizing activity for PP/LCP blends

The aim of this work was the synthesis of new graft copolymers consisting of polypropylene (PP) backbones and liquid crystalline polymer (LCP) branches, to be used as compatibilizing agents for PP/LCP blends. The PP-g-LCP copolymers have been prepared by polycondensation of the monomers of a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2), that is, sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the mole ratio of 1 : 1 : 2, carried out in the presence of appropriate amounts of a commercial acrylic-acid-functionalized polypropylene (PPAA). The polycondensation products, referred to as COPP50 and COPP70, having a calculated PPAA concentration of 50 and 70 wt %, respectively, have been fractionated with boiling toluene and xylene, and the soluble and insoluble fractions have been characterized by Fourier transform infrared and nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry, and X-ray diffraction. All analytical characterizations have concordantly shown that the products are formed by intricate mixtures of unreacted PPAA and SBH together with PP-g-SBH copolymers of different composition. Exploratory experiments carried out by adding small amounts of COPP50 or COPP70 into binary mixtures of isotactic polypropylene (iPP) and SBH while blending have demonstrated that this practice leads to an appreciable improvement of the dispersion of the minor LCP phase, as well as to an increase of the crystallization rate of iPP.

Blends of poly(ethylene 2,6-naphthalate) with liquid-crystalline polymers: crystallization behavior and morphology

The isothermal crystallization behavior and morphology of blends of Poly(ethylene 2,6-naphthalate) (PEN) with two types of liquid-crystalline polymers (LCP) (rigid and semiflexible) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends posses a two-phase morphology due to immiscibility of the two components. The dispersion of the minor LCP phase is favored at a low LCP concentration (7 wt%). The PEN overall crystallization rate is enhanced strongly by the addition of LCPs. The maximum enhancing effect has been found to occur at a LCP concentration of ca. 7 wt%. The POM observations show that PEN spherulite dimensions decrease in the presence of LCPs. These results have been interpreted on the basis of a heterogeneous nucleation played by the crystallized LCP particles on the molten PEN matrix. The nucleation mechanism and the equilibrium melting temperature of PEN are not changed by the presence of a dispersed LCP phase. The relationship between blend morphology and nucleation phenomena has been discussed.

Nonisothermal Crystallization Kinetics and Microhardness of PP/CNT Composites

The nonisothermal crystallization kinetics and microhardness of nanocomposites consisting of a polypropylene matrix (PP) and carbon nanotube filler (CNT) have been investigated. Three types of PP matrixes have been used: two of them are nonfunctionalized PP that differ slightly in their melt flow index, whereas the third is grafted with maleic anhydride (MA). Ozawa formalism has been used to study the nonisothermal crystallization kinetics. The results show that the CNT filler has a nucleation role in the nonisothermal crystallization of PP. For all nanocomposites, the nonisothermal crystallization rate increases up to 4% CNT and then decreases slightly or remains almost constant at the higher filler content. This fact has been interpreted in terms of an aggregation of the particles at high filler concentration, which leads to a decrease of the nucleation ability of the filler because the number of heterogeneous nuclei decreases. The crystallization mechanism of the PP matrixes almost does not change in the presence of the CNT filler. The microhardness of the two nonfunctionalized PP increases when the filler content increases and then remains constant above a certain filler content. The experimental microhardness values of the composites based on the functionalized PP are lower than those of the corresponding calculated additive values. The decrease of the creep constant with the filler addition is not significant, as should be expected when inorganic filler is added to a polymer matrix. This is due to the very fine dispersion of the fillers into the polymer matrix at the nanoscale level.

Clay‐induced Preferred Orientation in Polyethylene/Compatibilized Clay Nanocomposites

Nanocomposites of the organically modified clay Cloisite® 15A (CL15A) dispersed in HDPE‐g‐MA were prepared by melt‐compounding. Microcomposites of the same clay with HDPE were also obtained with similar procedures. The spherulitic morphology of the polymer matrix was evidenced by optical microscopy in thin films, whereas the structure of the up to 2‐mm–thick, compression‐molded samples was investigated by WAXD and SAXS. Preferred orientation of both the clay and the HDPE crystallites were evidenced in the microcomposites and, to a greater extent, in nanocomposites, whereas in HDPE and HDPE‐g‐MA control specimens hardly any anisotropy was detected. The degree of orientation of PE crystals increases with CL15A concentration, but also with clay exfoliation, with lower cooling rates and decreasing sample thickness. The orientation of the clay platelets parallel to the compression‐molded surface appears to be determined by the platelets anisotropy and by shear in the mixing and the compression‐molding procedures. In turn, it determines the preferred uniaxial orientation of HDPE crystals, which have their crystallographic a axis orthogonal, while b and c are coplanar, to the sample surface, as already reported in the literature for melt‐crystallized HDPE films with thickness below 0.3 μm. It is proposed that the HDPE orientation results from confined crystallization between parallel clay platelets which are on average less than 0.1 μm apart. Simple models, qualitatively accounting for the observed orientation of HDPE, are discussed. Organized architectures resulting from confined crystallization of the polymer matrix in nanocomposites with appropriate anisotropic fillers may be a general feature, important in determining key properties of these systems.

Reactive blending of a functionalized polyethylene with a semiflexible liquid crystalline copolyester

Reactive blends (50/50 w/w) of a low molar mass polyethylene containing free carboxylic groups (PEox) and a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2, by Eniricerche) have been prepared at 240°C in a Brabender mixer, in the presence of Ti(OBu) 4 catalyst, for different mixing times (15, 60, and 120 min). In order to prove the formation of a PE-g-SBH copolymer, the blends have been fractionated by successive extractions with boiling toluene and xylene. The soluble fractions and the residues have been analyzed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG and DTG), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). All analytical procedures concordantly show that PE-g-SBH copolymers with different compositions, arising from differences of either the number of PEox carboxylic groups entering the transesterification or the length of grafted SBH branches, are formed as a result of blending. Depending on the relative content of PE and SBH segments, the copolymers dissolve in the solvents, together with any unreacted PEox, or remain in the residues, together with neat SBH. Qualitative IR analyses and quantitative TG measurements have shown that the amount of copolymers increases strongly with the mixing time. Preliminary SEM observations indicate that the unfractionated products of the reactive blending carried out with long (120 min) mixing times lead to improved interfacial adhesion and phase dispersion when added to PE/SBH blends.

Morphology of nanocomposites from ethylene-acrylic acid copolymers

Abstract New nanocomposites have been prepared by melt-compounding from commercial ethylene-acrylic acid copolymers (EAA) of different molar mass, molecular structure (branched or linear) and AA concentration, and a Zn-ionomer, with three commercial clays containing different proportions of the same organic modifier (dimethyldi(hydrogenated tallow)ammonium ion). Their morphology has been preliminarily investigated by X-ray scattering and transmission electron microscopy. The nanocomposites showed disordered intercalated morphology, with an expansion of the average gallery height, which appears to depend quite strongly on the molecular architecture of the EAA, whereas the other investigated variables, including the excess of surfactant used to organically modify the silicate, have negligible effect.