Structures and rheological properties of reactive solutions of block copolymers. Part I. Diblock copolymers in a liquid epoxy monomer

P(S-b-MMA) and P(B-b-MMA) diblock copolymers (BCP) have been solubilized in a liquid epoxy. The obtained solutions have been characterized by rheology and small angle X-ray scattering (SAXS). As in the solid state, BCP can self-organize in solution to form well-ordered micellar structures. The two blocks respective roles have been clearly identified: at room temperature the PS or the PB block microsegregates while the PMMA block for which epoxy constitutes a good solvent, acts as a stabilizer of the microphase separation. The geometries and thermal stabilities of the ordered structures depend strongly on the molar masses and the chemical nature of the BCP blocks. For instance, the total molar mass of the BCP has to be high enough to obtain a periodic structure. On the contrary, if this molar mass is too high, too long relaxation times prevent the system from reaching its equilibrium. For the P(S-b-MMA) copolymer solution, a transition temperature from an order to a disorder state (T_ODT) is observed. The origin of this transition has been attributed to a solubilization of the PS domains around T_ODT. Macroscopically, this transition can be defined as a solid-like to a liquid-like transition. In the case of the P(B-b-MMA) copolymer solution, no order-disorder transition has been observed: it can be explained by the fact that the PB blocks are not soluble in epoxy at any temperature, up to T=200 °C.     

Temperature-dependent interaction parameters of poly(methyl methacrylate)/poly(2-vinyl pyridine) and poly(methyl methacrylate)/poly(4-vinyl pyridine) pairs

Temperature-dependent interaction parameters (α) of poly(methyl methacrylate)/poly(2-vinyl pyridine) (PMMA/P2VP) pair and PMMA/poly(4-vinyl pyridine) (PMMA/P4VP) pair were obtained from the SAXS profiles at various temperatures, and curve fitting to the random phase approximation theory. For this purpose, symmetric P2VP-block-PMMA and P4VP-block-PMMA copolymers were synthesized anionically. The molecular weights of both block copolymers were controlled to exhibit the disordered state over the entire experimental temperatures. We found that the value of α for PMMA/P4VP was larger than PMMA/P2VP, similar to polystyrene (PS)/poly(vinyl pyridine) pairs. However, the difference between in α between PMMA/P2VP and PMMA/P4VP was much smaller than that between PS/P2VP and PS/P4VP. This might be attributed to the hydrophilic PMMA block compared with hydrophobic PS block. Finally, the order-to-disorder transition temperature for symmetric P2VP-block-PMMA copolymers was determined by small angle X-ray scattering and birefringence methods.     

Sequence distribution affect the phase behavior and hydrogen bonding strength in blends of poly(vinylphenol-co-methyl methacrylate) with poly(ethylene oxide)

Experimental results indicate that the PEO was miscible with PVPh-r-PMMA copolymers as shown by the existence of single composition-dependent glass transition temperature over the entire compositions. However, the PVPh-b-PMMA copolymer with PEO shows a like closed loop phase-separated region in this copolymer/homopolymer blend system. Furthermore, FTIR reveals that at least three competing equilibrium are present in these blends; self-association (hydroxyl-hydroxyl), interassociation (hydroxyl-carbonyl) of PVPh-co-PMMA, and hydroxyl-ether interassociation between PVPh and PEO. Based on the Painter-Coleman Association Model (PCAM), a value for inter-association, K_C=300 is obtained in PVPh-b-PMMA/PEO blend system at room temperature. Although the relative ratio of interassociation equilibrium constant of PEO to PMMA is larger in PVPh-b-PMMA/PEO blend system, the PVPh-r-PMMA/PEO blend system has greater Δν and greater homogeneity at the molecular scale than the PVPh-b-PMMA/PEO blend system because of the ΔK effect.     

Exfoliation of organoclay nanocomposites based on polystyrene-block-polyisoprene-block-poly(2-vinylpyridine) copolymer: Solution blending versus melt blending

Exfoliated nanocomposites based on polystyrene-block-polyisoprene-block-poly(2-vinylpyridine) (SI2VP triblock) copolymer were prepared by solution blending and melt blending. Their dispersion characteristics were investigated using transmission electron microscopy, X-ray diffraction, and small-angle X-ray scattering (SAXS). For the study, SI2VP triblock copolymers with varying amounts of poly(2-vinylpyridine) (P2VP) block (3, 5, and 13 wt%) and different molecular weights were synthesized by sequential anionic polymerization. In the preparation of nanocomposites, four different commercial organoclays, treated with a surfactant having quaternary ammonium salt, were employed. It was found from SAXS that the microdomain structure of an SI2VP triblock copolymer having 13 wt% P2VP block (SI2VP-13) transformed from core-shell cylinders into lamellae when it was mixed with an organoclay. It was found further that the solution-blended nanocomposites based on a homogeneous SI2VP triblock copolymer having 5 wt% P2VP block (SI2VP-5) gave rise to an exfoliated morphology, irrespective of the differences in chemical structure of the surfactant residing at the surface of the organoclays, which is attributable to the presence of ion-dipole interactions between the positively charged N⁺ ion in the surfactant residing at the surface of the organoclay and the pyridine rings in the P2VP block of SI2VP-5 and SI2VP-13, respectively. Both solution- and melt-blended nanocomposites based on microphase-separated SI2VP-13 having an order-disorder transition temperature (T_ODT) of approximately 210 °C also gave rise to exfoliated morphology. However, melt-blended nanocomposite based on a high-molecular-weight SI2VP triblock copolymer having a very high T_ODT (estimated to be about 360 °C), which was much higher than the melt blending temperature employed (200 °C), gave rise to very poor dispersion of the aggregates of organoclay. It is concluded that the T_ODT of a block copolymer plays a significant role in determining the dispersion characteristics of organoclay nanocomposites prepared by melt blending.     

Transition behavior and ionic conductivity of lithium perchlorate-doped polystyrene-b-poly(2-vinylpyridine)

We report the transition behavior and the ionic conductivity of ion-doped amorphous block copolymer, based on two compositionally different polystyrene-block-poly(2-vinylpyridine) copolymers (PS-b-P2VPs) that can self-assemble into nanostructures, where P2VP block is ionophilic to lithium perchlorate (LiClO₄). The transition temperatures of LiClO₄-doped PS-b-P2VP, like the order-to-disorder transition (T_ODT), were measured by small-angle X-ray scattering (SAXS) and depolarized light scattering (DPLS). The selective ionic coordination to the nitrogen units of P2VP block leads to the increase of the repulsive interactions between two block components from weak- to strong-segregation regime with increasing amount of LiClO₄, which results subsequently in the increased T_ODT. However, for a compositionally asymmetric PS-b-P2VP under lamellar morphology, the ionic conductivity by the addition of LiClO₄ was remarkably increased at higher temperatures, representing that the effective ionic coordination at the greater volume fraction of P2VP block component improves the ionic conductivity as the temperature approaches to a rubbery phase.     

Morphology of polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) composite particles

Polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) (PS/PS-b-PMMA/PMMA) composite particles were prepared by releasing toluene from PS/PS-b-PMMA/PMMA/toluene droplets dispersed in a sodium dodecyl sulfate aqueous solution. The morphology of the composite particles was affected by release rate of toluene, the molecular weight of PS-b-PMMA, droplet size, and polymer composition. ‘Onion-like’ multilayered composite particles were prepared from toluene droplets of PS-b-PMMA and of PS/PS-b-PMMA/PMMA, in which the weights of PS and PMMA were the same. The layer thicknesses of the latter multilayered composite particles increased with an increase in the amount of the homopolymers. PS-b-PMMA/PS composite particles had a sea-islands structure, in which PMMA domains were dispersed in a PS matrix. On the other hand, PS-b-PMMA/PMMA composite particles had a cylinder-like structure consisting of a PMMA matrix and PS domains.     

Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers

The dispersion of magnetic nanoparticles (NPs) in homopolymer poly(methyl methacrylate) (PMMA) and block copolymer poly(styrene-b-methyl methacrylate) (PS-b-PMMA) films is investigated by TEM and AFM. The magnetite (Fe₃O₄) NPs are grafted with PMMA brushes with molecular weights from M = 2.7 to 35.7 kg/mol. Whereas a uniform dispersion of NPs with the longest brush is obtained in a PMMA matrix (P = 37 and 77 kg/mol), NPs with shorter brushes are found to aggregate. This behavior is attributed to wet and dry brush theory, respectively. Upon mixing NPs with the shortest brush in PS-b-PMMA, as-cast and annealed films show a uniform dispersion at 1 wt%. However, at 10 wt%, PS-b-PMMA remains disordered upon annealing and the NPs aggregate into 22 nm domains, which is greater than the domain size of the PMMA lamellae, 18 nm. For the longest brush length, the NPs aggregate into domains that are much larger than the lamellae and are encapsulated by PS-b-PMMA which form an onion-ring morphology. Using a multi-component Flory-Huggins theory, the concentrations at which the NPs are expected to phase separate in solution are calculated and found to be in good agreement with experimental observations of aggregation.     

Effect of atom transfer radical polymerization macroinitiator on properties of poly(meth)acrylate-based pentablock type of thermoplastic elastomers

We report well controlled synthesis of novel tri-component [polyisobutylene (PIB), poly(n-butyl acrylate) (PnBA) and poly(methyl methacrylate) (PMMA)] pentablock copolymers (PMMA-b-PnBA-b-PIB-b-PnBA-b-PMMA) by Atom Transfer Radical Polymerization (ATRP) using PIB as a macroinitiator. The surface properties (hydrophobicity, in vitro oxidative stability and cellular interaction) and the bulk properties (phase separation and mechanical properties) of the PIB-containing pentablock copolymers were compared with PMMA-b-PnBA-b-PDMS-b-PnBA-b-PMMA (where PDMS = polydimethylsiloxane) and conventional PMMA-b-PnBA-b-PMMA copolymers synthesized by PDMS and PnBA macroinitiators respectively. It is revealed that type of ATRP macroinitiator (with low glass transition temperature) influences the properties of resultant pentablock copolymers in terms of phase separation, mechanical properties in vitro oxidative stability, cytocompatibility and cell proliferation. Pentablock copolymers synthesized by PIB macroinitiator exhibited superior overall properties compared to pentablock copolymers synthesized by PDMS macroinitiator and neat triblock copolymer synthesized by PnBA macroinitiator. Among the copolymers tested, one with composition PIB:PnBA:PMMA = 10:64:26 (w/w) exhibited best mechanical property, oxidative stability and cytocompatibility. The newly designed PIB-containing pentablock copolymer may be useful where softness, flexibility, processability and biostability/cytocompatibility are desired.     

Lamella reorientation in thin films of a symmetric poly(l-lactic acid)-block-polystyrene upon crystallization at different temperatures

The thin films of a symmetric crystalline-coil diblock copolymer of poly(l-lactic acid) and polystyrene (PLLA-b-PS) formed lamellae parallel to the substrate surface in melt. When annealed at temperatures well above the glass transition temperature of PLLA block (T_g^PLLA), the PLLA chains started to crystallize, leading to reorientation of lamellae. Such reorientation behavior exhibited dependence on the correlation between the crystallization temperature (T_c), the glass transition temperature of PS (T_g^PS), the peak melting point of PLLA crystals (T_m^PLLA), and the end melting point of PLLA crystals (T_m,end^PLLA). When annealed at (T_c=) 80 °C (T_c < T_g^PS < T_ODT, order-disorder transition temperature), 123 °C (T_g^PS < T_c < T_m^PLLA < T_ODT), 165 °C (T_g^PS < T_m^PLLA < T_c < T_m,end^PLLA < T_ODT), the parallel lamellae became perpendicular to the substrate surface, exclusively starting at the edge of surface relief patterns. Meanwhile, the corresponding lamellar spacing was significantly enhanced. The PLLA crystallization between PS layers was hypothesized to account for the lamella reorientation during annealing. The crystallization, chain conformation, and possible chain folding mechanisms were discussed, based on detailed analysis of the lamellar structure before and after crystallization.     

Complicated phase behavior and ionic conductivities of PVP-co-PMMA-based polymer electrolytes

We have used DSC, FTIR spectroscopy, and ac impedance techniques to investigate the interactions that occur within complexes of poly(vinylpyrrolidone-co-methyl methacrylate) (PVP-co-PMMA) and lithium perchlorate (LiClO₄) as well as these systems' phase behavior and ionic conductivities. The presence of MMA moieties in the PVP-co-PMMA random copolymer has an inert diluent effect that reduces the degree of self-association of the PVP molecules and causes a negative deviation in the glass transition temperature (T_g). In the binary LiClO₄/PVP blends, the presence of a small amount of LiClO₄ reduces the strong dipole-dipole interactions within PVP and leads to a lower T_g. Further addition of LiClO₄ increases T_g as a result of ion-dipole interactions between LiClO₄ and PVP. In LiClO₄/PVP-co-PMMA blend systems, for which the three individual systems—the PVP-co-PMMA copolymer and the LiClO₄/PVP and LiClO₄/PMMA blends—are miscible at all compositional ratios, a phase-separated loop exists at certain compositions due to a complicated series of interactions among the LiClO₄, PVP and PMMA units. The PMMA-rich component in the PVP-co-PMMA copolymer tends to be excluded, and this phenomenon results in phase separation. At a LiClO₄ content of 20 wt% salt, the maximum ionic conductivity occurred for a LiClO₄/VP57 blend (i.e., 57 mol% VP units in the PVP-co-PMMA copolymer).     

Effect of tacticity of poly(methyl methacrylate) on interfacial region with silica in polymer nanocomposite

The effect of tacticity on the interfacial region between poly(methyl methacrylate) (PMMA) and silica in a PMMA/silica nanocomposite was investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The glass transition temperature (T_g) values of the syndiotactic (st-) and atactic (at-) PMMA/silica nanocomposites are higher than those of the neat PMMA. Conversely, the T_g of the isotactic (it-) PMMA/silica nanocomposite is slightly higher than that of the neat it-PMMA. DSC and XRD results suggest that the restriction of the PMMA chain mobility in the silica nanoparticle interfacial region heightens as the syndiotactic content increases. FT-IR results show that this phenomenon is caused by the interaction between the carbonyl group of PMMA and the silanol group on the silicon dioxide surface. Therefore, it can be concluded that the syndiotactic-rich PMMA has a significantly different molecular mobility from that of the neat PMMA in the interfacial region with silica nanoparticle surface than isotactic-rich PMMA.     

Thermal analysis of FeCl3-doped poly(3-butylthiophene) and poly(3-dodecylthiophene)

Summary For neutral and FeCl₃-doped poly(3-butylthiophene) (P3BT) and poly(3-dodecylthiophene) (P3DDT), conductivity measurement and thermal analysis are performed. Before doping, the glass transition temperatures (T_g) of the P3BT and P3DDT are 75.4°C and 5.6°C respectively. No melting transition of an ordered phase for P3BT is observed. But for P3DDT, the melting temperatures of ordered side chains and main chains are 56.1°C and 116.3°C respectively. Upon doping, the T_g 's shift upward to 150.5°C and 51.2°C for P3BT and P3DDT respectively and the two melting peaks of the ordered phases of P3DDT disappear. The dopant anions decompose in the range of about 150 to 230°C. The conductivities increase with increasing temperature and reach maxima at 135°C and 28°C and drop sharply in the range of 160–200°C and 130–170°C for P3BT and P3DDT respectively. This indicates that the thermal motion of the main chains would lead to a drop of conductivity due to thermal undoping, while the dopant decomposition would lead to a rapid loss of conductivity and an occurrence of crosslinking reaction.     

Synthesis of rod-coil diblock copolymers by ATRP and their honeycomb morphologies formed by the ‘breath figures’ method

We have synthesized rod-coil diblock PPQ-b-PMMA copolymers by using the versatile atom-transfer radical polymerization method and have characterized them by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The methyl ketone-terminated rod-coil diblock PMMA copolymer has a higher value of T_g, because of its syndiotactic-like structure, and a higher decomposition temperature than does the PMMA homopolymer. The presence of the PPQ block tends to retard the early decomposition of the PMMA chain. A regularly porous, honeycomb-structured film was prepared from the dichloromethane solution of the diblock copolymers under a flow of moist air. The diameters of the spherical pores can be controlled in the range from 0.8 to 3 μm by modifying both the rod-coil copolymers' relative molecular weights and the casting conditions. The wall thickness of the film is varied linearly with the relative molecular mass (M_r).     

Poly(vinylidene fluoride) ultrafiltration membranes containing hybrid silica nanoparticles: Preparation,characterization and performance

Poly(vinylidene fluoride) (PVDF) ultrafiltration membranes were prepared by immersion precipitation method using poly(hydroxyethyl methacrylate)-block-poly(methyl methacrylate) grafted silica (PHEMA-b-PMMA@SiO₂) nanoparticles as additives. The hybrid nanoparticles were synthesized by the surface initiated atom transfer radical polymerization (SI-ATRP), and they were characterized in detail by FT-IR, TEM, DLS and GPC. Results confirm that core–shell structure is formed after grafting PHEMA-b-PMMA brushes on the silica nanoparticles. Their average hydrodynamic diameter also increases with the prolongation of grafting time. After blending PVDF with the hybrid silica nanoparticles, the composite PVDF membranes exhibit high porosity and improved water permeation. Especially, when the molecular weight is 1.73 × 10⁵ g/mol for PHEMA-b-PMMA on the hybrid nanoparticles, the water flux of the PVDF composite membrane is 2.5 times than that of the control PVDF membrane, while the rejection to bovine serum albumin (BSA) remains at a high level (>90%). In addition, all the composite PVDF membranes show lower BSA adsorption and larger water flux recovery ratio than the control PVDF membrane. The improvement of membrane performance is attributed to the good hydrophilicity of PHEMA-b-PMMA@SiO₂ nanoparticles. Our results suggest that PHEMA-b-PMMA@SiO₂ nanoparticles with moderate molecular weight of PHEMA-b-PMMA are suitable for the property optimization of PVDF-based composite membranes.     

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature. The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF₆) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a “jelly-like” consistency. The composite ionic conductivity measured over the range −30 °C to 60 °C was always lower than that of the neat BMITFSI/BMIPF₆ and LiTFSI-BMITFSI/LiTFSI-BMIPF₆ electrolytes but still very high (>1 mS/cm at 25 °C up to 50 wt% PMMA). While addition of LiTFSI to IL does not influence the glass T_g and T_m melting temperature significantly, dispersion of PMMA (especially at higher contents) resulted in increase in T_g and disappearance of T_m. In general, the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport. However, for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other. Because of the beneficial physico-chemical properties and interesting ion transport mechanism, we envisage the present soft matter electrolytes to be promising for application in electrochromic devices.     

Macroscopically oriented lamellar microdomains created by “cold zone-heating” method involving OOT

The zone-heating method, which involves ordering of materials under moving temperature gradient ∇T, has been widely used as a technique to create macroscopically oriented ordered structures of various kinds of materials. We applied this method to a large molecular weight symmetric polystyrene-block-polyisoprene diblock copolymer (dibcp) at a temperature where the ∇T field exists below its order-disorder transition temperature T_ODT of the dibcp. In this method we first prepared the solvent-cast bulk films of the dibcp having a nonequilibrium morphology of hexagonally packed cylindrical microdomains (hex-cyl) by using a solvent selectively good for polyisoprene blocks. Then the zone-heating method was applied to the order-order transition process from the nonequilibrium hex-cyl to equilibrium lamellae. The “cold zone-heating” method, “cold” in the sense of the ∇T field existing below T_ODT, successfully created macroscopically oriented lamellae with their normals preferentially oriented parallel to the ∇T axis and their edges preferentially standing with respect to the bulk film surfaces. It was also found that the initial orientation of the (100) plane of hex-cyl normal to the ∇T axis prefers to that parallel to the ∇T axis for a better macroscopic alignment of lamellae. A possible model for the cold zone-heating-induced lamellar orientation will be discussed in the text.     

Influence of Se and Te substitutions at Tl-site of Tl(Ba,Sr)CaCu2O7 superconductor on the AC susceptibility and electrical properties

The Sr and Ba bearing Tl-1212 phase, Tl(Ba,Sr)CaCu₂O₇ is an interesting superconductor. The Sr only bearing TlSr₂CaCu₂O₇ is not easily prepared in the superconducting form. The Ba only bearing TlBa₂CaCu₂O₇ on the other hand does not show improvement in the transition temperature with elemental substitution. In this work the influence of multivalent Se (non-metal) and Te (metalloid) substitutions at the Tl-site of Tl_1-xM_x(Ba,Sr)CaCu₂O₇ (M = Se or Te) superconductors for x = 0–0.6 was studied. The samples were prepared via the conventional solid-state reaction method. XRD patterns showed a single Tl-1212 phase for x = 0 and 0.1 Se substituted samples. The critical current density at the peak temperature, T_p of the imaginary (χ”) part of the AC susceptibility (χ = χ’ +χ”), J_c-inter(T_p) for all samples was between 15 and 21 A cm⁻². The highest superconducting transition temperature was shown by the x = 0.3 Se-substituted sample (T_c-onset = 104 K, T_c-zero = 89 K, T_cχ’ = 104 K and T_p = 80 K). Te suppressed the superconductivity of Tl-1212 phase. The order of highest transition temperatures are as follows: Tl_1-xTe_x(Ba,Sr)CaCu₂O₇<Tl(Ba,Sr)CaCu₂O₇<Tl_1-xSe_x(Ba,Sr)CaCu₂O₇. This work showed that Se was better than Te in improving the transition temperature and flux pinning of the Tl-1212 phase. The roles of ionic radius of Se and Te on the superconductivity of Tl(Ba,Sr)CaCu₂O₇ are discussed in this paper.     

The kinetics of dithiocarbamate-mediated polyurethane-block-poly(methyl methacrylate) polymers

One important advantage offered by polymeric iniferters is the possibility that polycondensation polymers could be further reacted with vinyl monomers to produce novel block copolymers with interesting properties. The objective of this work was the kinetic investigation of polyurethane-block-poly(methyl methacrylate) (PU-b-PMMA) using dithiocarbamate (DC)-based polyurethane macroiniferter (PUMI) at different concentrations. It is shown that the copolymerization reactions followed the first order dependency. A linear increase of molecular weight with monomer conversion demonstrated that the copolymerization followed the mechanism of controlled radical polymerization. The rate of polymerization (R_p) at specific reaction time increased as the PUMI concentration increased from 0.34 × 10⁻³ mol/L to 2.74 × 10⁻³ mol/L, pass through a maxima, and decreased as PUMI concentration was increased beyond 2.74 × 10⁻³ mol/L. The thermogravimetric analysis showed that both PUMI and PU-b-PMMA degraded in three distinctive stages but the PU-b-PMMA is thermally more stable than the PUMI especially at lower temperatures. Thus, a combination of polycondensation and free radical photopolymerization methods, as demonstrated in this study, could be used to synthesize polyurethane-based block copolymers with tailored chain lengths of different blocks suitable for biomedical applications.     

Structure and properties of highly stereoregular isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) blends treated with supercritical CO2

The structure and properties of highly stereoregular isotactic poly(methyl methacrylate) (it-PMMA) and syndiotactic poly(methyl methacrylate) (st-PMMA) blends with crystalline stereocomplex formed by supercritical CO₂ treatment at temperatures ranging from 35 to 130 °C were investigated by means of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and dynamic mechanical analysis (DMA) measurements. The melting temperature, T_m, and the heat of fusion, ΔH_m, had maximum values at about 200 °C and 25 J/g, respectively. The degree of crystallinity evaluated by WAXD ranged in value from 32 to 38%. The fringed-micellar stereocomplex crystallites were formed in case of treatment temperatures below 90 °C, and the orderliness perpendicular to the helix axis of the fringed-micellar crystallites was considered to be increased with increasing treatment temperature. In case of treatment temperature of 130 °C, the fringed-micellar crystallites and the lamellar crystallites with high orderliness parallel to the helix axis coupled with the perpendicular orderliness were formed, and the respective double endothermic peaks, T_m¹ and T_m³, were observed in DSC due to the melting of the two kinds of stereocomplex crystallites. The it-PMMA/st-PMMA blends containing the fringed-micellar crystallites maintained high values of storage modulus, E′, up to higher temperature compared with the amorphous blends. The E′ of the blend treated with CO₂ at 130 °C decreased twice at temperatures corresponding to T_m¹ and T_m³.