Alejandro J. Müller

Applications of Successive Self-Nucleation and Annealing (SSA) to Polymer Characterization

A new technique to thermally fractionate polymers using DSC has been recently developed in our laboratory. The applications of the novel successive self-nucleation and annealing (SSA) technique to characterize polyolefins with very dissimilar molecular structures are presented as well as the optimum conditions to thermally fractionate any suitable polymer sample with SSA. For ethylene/α-olefin copolymers, the SSA technique can give information on the distribution of short chain branching and lamellar thickness. In the case of functionalized polyolefins, detailed examinations of SSA results can help to establish possible insertion sites of grafted molecules. The application of the technique to characterize crosslinked polyethylene and crystallizable blocks within ABC triblock copolymers is also presented.

Homogeneous nucleation of the dispersed crystallisable component of immiscible polymer blends

SummaryImmiscible melt mixed blends of a crystallisable polyolefin (isotactic polypropylene, PP) and atactic polystyrene (PS) were prepared in a wide composition range. It was found that when PP is the major component in the blend its crystallisation behaviour is not affected by blending it with PS. However if PP is the minor component, it will be dispersed in the immiscible PS matrix, hence the nucleation mechanism changes from predominantly heterogeneous to predominantly homogeneous as long as the size of the dispersed PP droplets is below a critical value (of the order of 1–2 μm).

Nucleation and crystallization of isotactic poly(propylene) droplets in an immiscible polystyrene matrix

In this work, isotactic poly(propylene) (iPP) was finely dispersed in immiscible atactic polystyrene (PS) matrices. When the dispersion obtained is fine enough (droplet size of approximately 1-2 μm), the iPP crystallizes in a fractionated fashion as temperatures between 104 and 42°C. By applying a self-nucleation procedure, we were able to corroborate that what causes the fractionated crystallization in most droplets is the lack of highly active heterogeneous nuclei (i.e. those normally active at low supercoolings in the bulk polymer) in every droplet. When a sulficient amount of a compatibilizer is used to obtain very small particle sizes and more homogenerous dispersions, the iPP crystallizes exclusively at a low temperature exotherm that exbibits an onset at 51°C and peaks at 46°C. Wide-angle X-ray diffraction measurements indicated that both the iPP in the bulk and in dispersed droplets crystallized in the monoclinic α-phase, this evidence may rule out the possibility that the crystallization observed at 46°C is due to the formation of another crystal modification or a mesomorphic phase as previously suggested in literature. The results presented in this work indicate that this low temperature exotherm may represent the dynamic crystallization during cooling of heterogeneity-free droplets that nucleate homogeneously at temperatures close to 51°C.

Miscibility of linear and branched polyethylene blends by thermal fractionation : use of the successive self-nucleation and annealing (SSA) technique

Abstract In the present work, the recently developed thermal fractionation technique successive self-nucleation and annealing (SSA) was applied to blends of branched and linear polyethylenes (PEs), as a method to evaluate the phenomena of miscibility and segregation in PE blends. The melting behavior of the systems, after a controlled cooling and after the application of SSA was compared. The DSC scans corresponding to cooling of blend samples from the melt or subsequent heating displayed an overlap of the exotherms and endotherms, respectively, of the blend components that could lead to interpretations of partial miscibility. These effects were interpreted as arising from: a nucleation effect of the crystals formed by the more linear PE on the crystals of branched PE, a dilution effect of the molten branched chains on the crystals formed by the more linear PE and finally possible partial miscibility effects. However, after SSA, even when the nucleation and dilution effects are still present for some of the fractions produced, the thermal fractionation procedure helps to distinguish them from co-crystallization effects. This is mainly achieved by observing how the number of thermal fractions generated by SSA in the blends varies with composition and by comparing the relative amounts of the thermal fractions produced by SSA. The results indicate that only those PE fractions that are similar in chemical structure, as regards to content and distribution of short chain branches, are probably miscible in the melt and can oppose molecular segregation during SSA and therefore produce stable co-crystals in the solid state. The application of SSA to the study of PE blends can be a quick and convenient tool for making comparisons and ascertain miscibility of different types of PE blends.

Fractionated crystallisation of polyethylene and ethylene/α-olefin copolymers dispersed in immiscible polystyrene matrices

In this work, several PS/HDPE (high density polyethylene), PS/LLDPE (linear low density polyethylene) and PS/ULDPE (ultra low density polyethylene) blends were prepared in a composition range were atactic polystyrene (PS) was always the matrix component. All the types of polyethylenes employed, when dispersed into droplets, exhibited fractionated crystallisation exotherms in the temperature range between 67 and 70 °C. These low crystallisation temperatures are probably closer to the homogeneous nucleation temperature of linear polyethylene than any previously reported value, since they occur at higher supercoolings. The higher values of crystallisation temperatures previously reported could be explained by the crystallisation from heterogeneous nuclei of relatively low nucleation efficiency or by a weak nucleation capacity of the droplets interface. By applying a self-nucleation procedure we were able to corroborate that what causes the fractionated crystallisation is the lack of highly active heterogeneous nuclei (i. e., those normally active at low supercoolings in the bulk polymer) in every droplet. When polyethylene/α-olefin copolymers are finely dispersed in a PS matrix, a molecular segregation process can be induced during mixing facilitated by the heterogeneous distribution of short chain branches in the copolymers. The crystallisation of droplets that contained mostly these highly branched chains occurs at temperatures lower than 50 °C, thereby producing another low temperature exotherm which may be the lowest present in the blend and could be mistaken by the crystallisation of homogeneously nucleated crystals. We have shown that the self-nucleation technique can help to distinguish these low temperature exotherms from those originated by differences in nucleation behaviour; therefore, a plausible interpretation of all the possible fractionated crystallisation exotherms of ethylene/α-olefin copolymer droplets was made possible.

Shear rheology and porous media flow of wormlike micelle solutions formed by mixtures of surfactants of opposite charge

The rheology of solutions of wormlike micelles formed by oppositely charged surfactant mixtures (cationic cetyl trimethylammonium p-toluene sulfonate, CTAT, and anionic sodium dodecyl sulfate, SDS), in the dilute and semi-dilute regimes, were studied under simple shear and porous media flows. Aqueous mixtures of CTAT and SDS formed homogeneous solutions for SDS/CTAT molar ratios below 0.12. Solutions of mixtures exhibited a strong synergistic effect in shear viscosity, especially in the semi-dilute regime with respect to wormlike micelles, reaching a four order of magnitude increase in the zero-shear rate viscosity for solutions with 20 mM CTAT. Oscillatory shear results demonstrated that the microstructure of CTAT wormlike micelles is sensitive to SDS addition. The cross-over relaxation times of wormlike micelles of 20 mM CTAT solutions increased by three orders of magnitude with the addition of up to 2 mM of SDS, and the solutions became increasingly elastic. The shear thickening process observed in shear rheology became more pronounced in porous media flow due to the formation of stronger cooperative structures induced by the extensional component of the flow.

Heterogeneous nucleation and self-nucleation of poly(p-dioxanone)

The changes in nucleation behaviour upon addition of Boron Nitride (BN), Talc and Hydroxyapatite (HA) to poly(p-dioxanone) (PPDX) were monitored by DSC and Polarised Optical Microscopy (PM). Self-nucleation DSC studies evidenced the existence of the usual three self-nucleation domains depending on the self-nucleation temperature (Ts) employed. By far the best nucleation agents for PPDX were its own self-nuclei and this result was independent of the presence or absence of any of the other nucleating agents employed; once Domain II was reached, self-nucleation dominated the nucleation process. BN and Talc were able to nucleate PPDX, thereby increasing its nucleation density, its dynamic crystallisation temperature upon cooling from the melt (Tc) and its enthalpy of crystallisation (ΔHc). BN was a better nucleating agent than talc. HA on the other hand caused an “antinucleation” effect on PPDX characterised by a decrease in its nucleation density, a decrease in its Tc and in ΔHc. Isothermally crystallised PPDX exhibited large banded spherulites whose morphology changed as a function of crystallisation temperature from single banded structures with a very clear Maltese cross to double banded spherulites. PPDX also shows a change in growth regime upon increasing crystallisation temperature (from Regime III to Regime II) according to the kinetic interpretation of growth rate data. BN did not cause any significant modification of the spherulitic growth kinetics (in Regime II) except for a small decrease in surface free energy of PPDX crystals (σe). On the other hand HA was found to increase the spherulitic growth rate and the overall crystallisation rate of PPDX, this increase was caused by a degradation process experienced by the polymer during the treatments involved in isothermal crystallisation that was only present in the samples with HA. It is postulated that the interaction between the phosphate groups on the surface of HA and the ester groups of PPDX are responsible for both the antinucleation effect and the catalysis of the hydrolytic degradation of PPDX.

The evaluation of the state of dispersion in immiscible blends where the minor phase exhibits fractionated crystallization

SummaryDifferential Scanning Calorimetry (DSC) can provide a qualitative measure of the state of dispersion of an immiscible blend if the minor phase exhibits fractionated crystallization when dispersed into fine particles. The technique is only sensitive to the volume of the dispersed particle and not to its shape and can only be used when the exotherms of interest do not overlap with other thermal transitions present in the multicomponent system. Selfnucleation is a valuable tool to ascertain the presence of fractionated crystallization. The morphology induced by fractionated crystallization in immiscible blends could lead to enhanced plastic deformation during yielding of the matrix.

Crystallization in Block Copolymers with More than One Crystallizable Block

Recent results on the crystallization of block copolymers with more than one crystallizable block are reviewed. The effect that each block has on the nucle- ation, crystallization kinetics and location of thermal transitions of the other blocks has been considered in detail. Depending on the thermodynamic repulsion between the blocks, the initial melt morphology in weakly segregated double crystalline di- block copolymers can be sequentially transformed by the crystallization of the dif- ferent blocks. The crystallization kinetics of each block can be dramatically affected by the presence of the other, and by the crystallization temperature; the magni- tude of the effect is a function of thermodynamic repulsion. Also the morphology has been investigated and peculiar double crystalline spherulites with intercalated semi-crystalline lamellae of each component have been observed in weakly segre- gated diblock copolymers. In the case of ABC triblock copolymers with more than one crystallizable block, many interesting effects have been found; among them, self-nucleation, sequential or coincident crystallization, and fractionated crystalliza- tion can be mentioned. Additionally, the effect of the topological constrains due to the number of free ends has been studied. Factors like chemical structure, molec- ular weight, molecular architecture and number of crystallizable blocks provide a very large number of possibilities to tailor the morphology and properties of these interesting novel materials.

Stereocomplexation of polylactide enhanced by poly(methyl methacrylate): improved processability and thermomechanical properties of stereocomplexable polylactide-based materials.

Stereocomplexable polylactides (PLAs) with improved processability and thermomechanical properties have been prepared by one-step melt blending of high-molecular-weight poly(l-lactide) (PLLA), poly(d-lactide) (PDLA), and poly(methyl methacrylate) (PMMA). Crystallization of PLA stereocomplexes occurred during cooling from the melt, and, surprisingly, PMMA enhanced the amount of stereocomplex formation, especially with the addition of 30-40 % PMMA. The prepared ternary blends were found to be miscible, and such miscibility is likely a key factor to the role of PMMA in enhancing stereocomplexation. In addition, the incorporation of PMMA during compounding substantially raised the melt viscosity at 230 °C. Therefore, to some extent, the use of PMMA could also overcome processing difficulties associated with low viscosities of stereocomplexable PLA-based materials. Semicrystalline miscible blends with good transparency were recovered after injection molding, and in a first approach, the thermomechanical properties could be tuned by the PMMA content. Superior storage modulus and thermal resistance to deformation were thereby found for semicrystalline ternary blends compared to binary PLLA/PMMA blends. The amount of PLA stereocomplexes could be significantly increased with an additional thermal treatment, without compromising transparency. This could result in a remarkable thermal resistance to deformation at much higher temperatures than with conventional PLA. Consequently, stereocomplex crystallization into miscible PLLA/PDLA/PMMA blends represents a relevant approach to developing transparent, heat-resistant, and partly biobased polymers using conventional injection-molding processes.