Phase Diagrams of Semicrystalline Polymer–Crystalline Substances: Polyolefins–1,2,4,5-Tetrachlorobenzene

The full phase diagrams of low-density polyethylene (LDPE), high-density polyethylene (HDPE), and isotactic polypropylene (i-PP) mixtures with 1,2,4,5-tetrachlorobenzene (TeCB), including the solubility curve of TeCB in a solid polymer, were constructed by an optical method. The diagrams contain a eutectic point that corresponds to the situation when the crystallization of TeCB out of its solution in a polyolefin is accompanied by the crystallization of monomer units of the macromolecules. As a result, the polymer acquires a gel structure with crystallites as crosslinks and amorphous regions saturated with TeCB. It is demonstrated that the eutectic point position on the phase diagram can be used for ranking polymers with respect to their thermodynamic affinity to a solvent. For the studied systems, the affinity to TeCB was decreased in the order i-PP, HDPE, and LDPE. Direct experimental evidence was obtained that TeCB crystals can be dissolved in a solid polymer via a vapor phase mechanism, which leads to the polymer amorphization.     

State diagrams of partially crystalline polymer-good solvent systems: The isotactic polypropylene-m-xylene system

In the development of concepts according to which partially crystalline polymers are, in terms of phase state, microheterogeneous metastable liquids, a state diagram of the isotactic polypropylene-m-xylene system is obtained and discussed. It is shown that, in the absence of the limiting line in the diagram that reflects the temperature dependence of the liquid solubility in the partially crystalline polymer, no correct interpretation for the thermodynamic meaning of the temperature dependence of complete amorphization of such a polymer on the initial composition of a binary system (the liquidus curve) is possible.     

A semicrystalline polymer as a metastable microheterogeneous liquid

A concept according to which semicrystalline polymers, in terms of their phase state, are treated as specific (metastable and microheterogeneous) liquids is proposed. Literature evidence and experimental data obtained by the authors serve as the basis for the discussion of structural and thermodynamic features of these liquids, which manifest themselves during contact with low-molecular-mass compounds.     

The Effect of Severe Plastic Deformation on the Structure and Mechanical Properties of Al–Mg–Li Alloys

The structural-phase state and mechanical properties of commercial aluminum alloys produced by severe plastic deformation are studied and compared to the initial polycrystalline state. This kind of treatment is found to give rise to the formation of a homogeneous ultrafine-grained structure with second-phase particles occurring predominantly along grain boundaries. With this structure, the strain-temperature and strain-rate intervals wherein the superplastic properties of the alloys under study are observed are shifted to lower temperatures and higher rates.     

Poly[3,3-bis(azidomethyl)oxetane]–2,4-dinitro-2,4-diazapentane

Constructing phase diagrams for the mixtures of semicrystalline polymers and low molecular mass substances by DSC can meet with difficulties in the case of slow polymer crystallization. A problem of this kind is encountered for high-energy compositions poly[3,3-bis(azidomethyl)oxetane] (PBAMO)–2,4-dinitro-2,4-diazapentane (DNAP). In this study, the experimental phase diagram PBAMO–DNAP is constructed by an optical method, which makes it possible to visualize structural transformations. The kinetic studies by DSC and XRD reveal that 30–50 days of storing a homogenized PBAMO–DNAP mixture at room temperature are needed to attain stationary values of the crystallinity degree and heat of fusion. Even after that, the DSC method cannot deliver a solubility curve of DNAP in PBAMO, which is naturally generated by the optical method. This curve separates a domain of physical gels, effectively crosslinked by polymer crystallites and swollen with the plasticizer molecules, from a two-phase domain, in which the above gel reaches osmotic equilibrium with the pure plasticizer. It is also shown that the melting temperature of DNAP drops with growing the PBAMO content in the mixture, which is consistent with a decrease in the mean size of plasticizer crystals formed in polymer pores during the previous cooling.     

Phase equilibria and transformations in low-density polyethylene–<Emphasis Type="Italic">p</Emphasis>-xylene system

The state diagram of the low-density polyethylene–p-xylene system that contains the solubility curve of p-xylene in the polymer is first built using the optical method with the involvement of the DSC data. It has been shown that, at 72°C, in a blend with a polymer mass fraction of 0.28, the full amorphization of the polymer proceeds simultaneously with the dissolution of p-xylene in it. Blends with a lower polymer content are also homogenized at the same temperature, although the duration of this process can take several days. In blends with a high polymer content, homogenization occurs at a higher temperature. This process is preceded by the formation of microheterogeneous single-phase gel with network junctions as polymer crystallites and amorphous regions saturated by p-xylene. Cooling of the homogeneous blends to–20°С is not accompanied by the full separation of low- and high-molecular-mass phases; in this case p-xylene not only forms an individual crystalline phase, but also partially crystallizes in amorphous regions of the polymer.     

Melting of polyolefins in presence of liquids

The existence of a section with a constant melting point in the curve of melting polyolefins in presence of a liquid was confirmed experimentally by the method of differential scanning calorimetry.     

Effect of structural states in near-surface layers of commercial titanium on its fatigue life and fatigue fracture mechanisms

Changes of structural states in near-surface layers of α-titanium strongly affect its fatigue life and fatigue fracture mechanisms. In α-titanium subjected to alternate bending a sliding mode crack develops, resulting in slight delamination of the material. Hydrogenation of α-titanium surface layers preserves their sliding mode cracking but greatly enhances their delamination. Nanostructuring of α-titanium surface layers increases their nanohardness and elastic modulus and causes opening mode cracking. The fatigue life of the material after surface hydrogenation decreases three times, and after surface nanostructuring, it increases four times.     

Scale invariance of structural transformations in plastically deformed nanostructured solids

The scale-invariant mechanical behavior of a nanostructured solid is associated with plastic distortion as a major mechanism of nano- and microscale structural transformations. Active grain boundary sliding in a deformed material (microscale) within its highly developed planar subsystem (nanograin boundaries) causes a progressive increase in lattice curvature and plastic distortion of atoms which produces nonequilibrium vacant sites in the nanostructure. The motion of nonequilibrium point defects in nanostructure curvature zones provides conditions for noncrystallographic plastic flow, dissolution or dispersion of initial phases, and formation of nonequilibrium phases in a deformed material. The possibility of reversible structural phase transformations in the presence of high lattice curvature opens the way to greatly increase the fatigue life of surface nanostructured polycrystalline materials.