Interactions in blends containing chitosan with functionalized polymers

The phase behavior of blends containing chitosan with poly(vinyl‐alcohol) (PVA) and poly(2‐hidroxyethyl methacrylate) (P2HEM) was analyzed. Blends were obtained by casting from acetic acid solution (HAc) and 1,1,1,3,3,3 hexafluoro‐2‐propanol (HF2P) and studied by DSC, FT‐IR, and TGA. The phase behavior of the blends of chitosan with PVA and P2HEM, studied by DSC, shows that the systems behave as one‐phase systems in HAc as well as in HF2P according to the DSC results. According to the results of FT‐IR analyses of the different absorptions of the blends, relative to the pure components, they show an important shift that is considered evidence of an interaction between the components of the blends. The thermogravimetric analysis of the blends and the pure components shows that the temperature for thermal degradation of the blends is higher that that of the pure components, irrespective of the solvent casting from which the mixture was obtained. These results are interpreted as the formation of a new product that corresponds to a compatible polymer blend. The compatibilization of these systems is attributed to strong interactions, like hydrogen bonds formation between the functionalized polymers and chitosan, due to the presence of interacting functional groups in all the polymers studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1953–1960, 2005     

Physicochemical and morphological evaluation of chitosan/poly(vinyl alcohol)/methylcellulose chemically cross-linked ternary blends

Chitosan/poly(vinyl alcohol)/methylcellulose (CS/PVA/MC) ternary blend was prepared and chemically cross-linked with glutaraldehyde. The prepared ternary blends were characterized by Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The FTIR results showed that the strong intermolecular hydrogen bonds took place between CS and PVA. TGA showed the thermostability of the blend is enhanced by glutaraldehyde as crosslink agent. Results of XRD indicated that the relative crystalline of pure CS film was reduced when the polymeric network was reticulated by glutaraldehyde. Finally, the results of scanning electron microscopy (SEM) indicated that the morphology of the blend is rough and heterogenous, further it confirms the interaction between the functional groups of the blend components.     

Molecular modeling simulations and thermodynamic approaches to investigate compatibility/incompatibility of poly(l-lactide) and poly(vinyl alcohol) blends

This paper investigates the molecular modeling simulation approaches for understanding the blend compatibility/incompatibility of poly(l-lactide), PLL and poly(vinyl alcohol), PVA. Blends of PLL/PVA have been widely used in biotechnology as well as membranes in separation science. Realizing their importance, we thought of investigating to verify experimental observations on their compatibility/incompatibility aspects by calculating thermodynamic interactions between PLL and PVA over the entire range of blend compositions. In doing so, Flory-Huggins interaction parameter, χ, was computed for different blends using atomistic simulations to predict blend miscibility. It was found that at 1:9 blend composition of PLL/PVA, miscibility was observed, but increasing immiscibility was prevalent at higher compositions of PLL component. Computed results confirmed the literature findings on differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and mechanical property studies, suggesting the validity of modeling strategies. Plots of Hildebrand solubility parameter, δ, and cohesive energy density, CED, supported these findings. Miscibility of PLL and PVA polymers is attributed to hydrogen-bonding effect. Literature findings have been validated to understand the nature of interactions between different groups of the polymers by computing radial distribution function, RDF, for groups that are tentatively involved in such interactions, leading to miscibility or immiscibility. RDF plot was constructed to identify the exact contribution of particular atoms of polymers to confirm miscibility/immiscibility of blends. Results of this study are correlated well with the reported data. Kinetics of phase separation was examined using density profiles calculated from the MesoDyn approach to examine miscibility/immiscibility aspects of the blends. Computed free energy from the mesoscopic simulation of blends reached equilibrium, particularly when simulation was performed at higher time step, indicating the stability of the blend at certain compositions. X-ray diffraction profiles have been constructed for individual polymers as well as for their blends, which agreed well with the reported data.     

Miscibility of chitosan/poly(ethylene oxide) blends and effect of doping alkali and alkali earth metal ions on chitosan/PEO interaction

The miscibility of Chitosan (CS) and poly(ethylene oxide) (PEO) in their blends and the effect of K⁺ and Ca²⁺ doping on the CS/PEO interaction have been investigated in this work. CS and PEO appeared to be miscible and the DSC analysis suggested the Flory-Huggins interaction parameter χ_AB to be −0.21. Doping of K⁺ and Ca²⁺ into the CS/PEO blend matrix enhanced the cooperative interaction between CS and PEO and this enhancement was larger for Ca²⁺ than for K⁺. The difference between Ca²⁺ and K⁺ possibly reflects a stronger multi-valence interaction of Ca²⁺ with the amino and hydroxyl groups of CS as well as the ether groups of PEO to form a stable CS/Ca²⁺/PEO complex and a less significant interaction of K⁺, as suggested by DSC, WAXD and FTIR results. MD simulations clearly indicated the correlation between the dynamic behavior and the interaction of K⁺ and Ca²⁺ in the CS/PEO blend matrix.     

Glass transitions and interactions in polymer blends containing poly(4-hydroxystyrene) brominated

The miscibility and interactions of binary blends of poly(4-hydroxystyrene) brominated (P4HSBR) with poly(?-caprolactone) (PCL), poly(vinyl acetate) (PVA) and poly(vinyl methylether) (PVME) are investigated by means of differential scanning calorimetry (DSC). Glass transition temperatures, T_gs, are used to assess the miscibility of these systems. All of them were found to be miscible over the whole composition range. T_gs of the blends are lower than Fox predictions, in contrast to the results previously obtained for systems involving poly(4-hydroxystyrene) (P4HS). The melting of PCL in the blends was studied. From the melting temperature depression of PCL in the blends the polymer-polymer interaction parameter was obtained and compared with the ones obtained for P4HS/PCL and poly(4-hydroxystyrene-co-methoxystyrene) (P4HSM)/PCL systems. The best interactions are achieved in P4HS/PCL and the bromination or methoxylation of the P4HS worsen the interactions with the PCL. The presence of a cusp in the T_g-composition curve was analysed in terms of the Kovacs' theory in systems with P4HS and P4HSBR.     

Influence of the molecular weight of chitosan on the spinnability of chitosan/poly(vinyl alcohol) blend nanofibers

The electrospinning of the biopolymer chitosan (CS) and poly(vinyl alcohol) (PVA) was investigated with 90% acetic acid as the solvent and with different CS/PVA ratios. The long chains of high‐molecular‐weight CS prevented it from forming nanofibers in a high‐voltage field. The treatment of CS under high‐temperature alkali conditions reduced its molecular weight exponentially with the treatment time and caused a reduction of the viscosity consequently. PVA, acting as a plasticizer and accompanied by the alkali‐treated CS of lower viscosity, made the electrospinning of CS/PVA blends possible. The effects of the duration of the alkali treatment on the molecular weight of CS and its viscosity were investigated and optimized. The diameter of the bicomponent nanofiber decreased proportionally with the increase in the CS portion, whereas the surface porosity increased inversely. Fourier transform infrared studies illustrated that the alkali treatment or blending of CS with PVA had no effect on its chemical nature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Processable aromatic polyesters based on bisphenol derived from cashew nut shell liquid: synthesis and characterization

The miscibility of chitosan/poly(ethylene oxide) (CS/PEO) blends was investigated by a combination of experiment and molecular simulation. Results from X-ray diffraction (WAXD) and thermal analysis (DSC) suggest that the maximum miscibility was seen at the PEO weight fraction (w _PEO) =0.2; the optimum stoichiometric ratio for CS and PEO functional groups. The change in vibrational frequencies from infrared spectra was attributed to the specific interaction between PEO ether oxygen with the amino and hydroxyl groups of CS. Radial distribution functions (RDF) from MD simulation suggest that all CS functional groups (NH₂, C3-OH, and C6-OH) can interact with PEO ether groups for which NH₂ has the highest activity. For CS hydroxyl groups, a more significant contribution of C6-OH rather than C3-OH groups that interact with PEO ether oxygen was observed. The interaction parameter (χ) determined from MD simulation was in good agreement with that of the DSC experiment (χ_CS-PEO?=?-0.21). Based on a comparison between χ and χ _critical , CS/PEO blend was predicted to be miscible for w _PEO <0.58 with a maximum at w _PEO =0.2. In addition, the order parameter from the mesoscale simulation was employed to monitor the phase separation in these blends. From MesoDyn simulation, the miscibility was decreased with increasing PEO content, and miscible CS/PEO blends were obtained only with w _PEO <0.58, in good agreement with MD simulation and experiment.     

Study on the Crystallization Kinetic and Characterization of Poly(lactic acid) and Poly(vinyl alcohol) Blends

In this study, poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) blends, with PLA/PVA mass ratios of 100/0, 90/10, 80/20, 70/30, 60/40, 50/50, and 40/60, were prepared by means of the melt blending method. The result of torque measurements and thermal gravimtric analysis tests showed that the addition of PLA can decrease the melt viscosity of PVA and that the second degradation step of PVA nearly disappeared for the PLA₈₀/PVA₂₀ blend. The absorbance peaks of the carbonyl group and the hydroxyl group in the Fourier transform infrared spectra of PLA/PVA blends had significant shifts to lower wave numbers, indicating that there were interactions between these two groups. Combined with the result of the differential scanning calorimetry curves, this interaction would be favorable for improving miscibility. The X-ray diffraction patterns and the polarized light microscope (PLM) micrographs showed that PVA can serve as a nucleating agent to promote the crystallization of PLA in PLA/PVA blends. Moreover, the PLA₈₀/PVA₂₀ blend gave the highest growth rate of PLA spherulite.     

Miscibility, properties and morphology of biodegradable blends of UHMW-PPC/PVA/EVOH

Thermally stable and biodegradable blends of ultrahigh molecular weight poly(propylene carbonate) (UHMW-PPC), poly(vinyl alcohol) (PVA) and poly(ethylene-co-vinyl alcohol) (EVOH) were melt compounded in a batch mixer followed by compression molding. The miscibility, mechanical properties, thermal behavior, and morphologies of the blends were investigated by torque rheometer, Fourier transform infrared spectroscopy, tensile strength test, thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The experimental results showed well interfacial miscibility among phases of PVA, EVOH and PPC. The hydrogen bonding interaction between PPC with PVA and/or EVOH can also be confirmed by Fourier transform infrared spectroscopy spectra. The study on the mechanical properties and thermal behavior demonstrated that PVA/EVOH content can enhance the tensile strength, thermal stability and crystallinity of the blends dramatically. Further, scanning electron microscopic observation revealed a three-phase structure with good interfacial adhesion.     

壳聚糖/聚乙烯醇共混膜的氢键和相容性

采用溶液共混法制备了不同配比的壳聚糖/聚乙烯醇共混膜,通过变温FTIR、TG、DTA、DSC及XRD等对共混膜的结构、氢键相互作用、热行为和结晶性等进行研究。实验结果表明,共混膜中壳聚糖与聚乙烯醇间存在强烈的氢键相互作用。氢键的存在使壳聚糖的热稳定性提高,聚乙烯醇结晶性下降,促进壳聚糖与聚乙烯醇相容。当壳聚糖/聚乙烯醇共混膜的质量比分别为10/0、7/3、5/5、3/7和0/10时,共混膜的初始分解温度分别为244 ℃、257 ℃、260 ℃、262 ℃和285 ℃。聚乙烯醇熔融温度从193 ℃下降到173 ℃,玻璃化转变温度从74.2 ℃上升至80 ℃,结晶度Xc从3.57%下降到1.97%。     

Enhancement of water barrier properties of cassava starch-based biodegradable films using silica particles

Biodegradable films are used in a variety of applications, including packaging. However, their use is limited due to their high moisture and water sensitivity. In this work, cassava starch (CS) was blended with poly(vinyl alcohol) (PVA). Silica particles (SiO₂) were incorporated to increase the hydrophobicity of the blend by intermolecular interaction through hydrogen bonding between the three components. Instead of a plasticizer or crosslinker, a small amount of triethylamine was added to eliminate residual acetate groups in PVA. The miscibility of CS and PVA phases was confirmed by smooth fracture surfaces and a single glass transition temperature. When SiO₂ content was below 5% (wt), the particles were well dispersed in a continuous phase of polymer matrix. At this loading of SiO₂, the increase in tensile strength was as high as 170% and in elongation-at-break, 250%. All loadings of SiO₂ increased thermal stability of the blend films because silanol groups on the surface of SiO₂ particles formed effective interfacial interactions with hydroxyl groups of the polymers. These interactions also prevented the ingress of water molecules, significantly increasing the hydrophobicity of the films. The water contact angle increased as high as 113° and moisture absorbency and water solubility were low. These highly hydrophobic, photodegradable, biodegradable CS/PVA/SiO₂ films show great potential as a low-cost, eco-friendly material.

     

Miscibility of poly(vinyl alcohol)/polyacrylamide blends before and after gamma irradiation

Films of polymer blends having various contents of poly(vinyl alcohol) (PVA) and polyacrylamide (PAM) were prepared by the solution casting technique using water as a common solvent. The thermal, mechanical and morphological properties of these blends before and after exposure to various doses of gamma radiation, up to 100 kGy, have been investigated. The visual observation and reflectance measurements show that PVA/PAM blends are miscible over a wide range of composition. Moreover, the differential scanning calorimetry (DSC) thermograms show only a single glass transition temperature (T_g), but not those of PVA or PAM homopolymers, giving further support to the complete compatibility of such blends. The T_g of PVA/PAM blends decreases with increasing content of PAM but increases after exposure to gamma irradiation, indicating the occurrence of crosslinking. These findings were demonstrated by the scanning electron micrographs of the fracture surfaces and the tensile mechanical properties. The TGA thermograms and percentage mass loss at different decomposition temperatures show that unirradiated PVA homopolymer possesses higher thermal stability than PAM homopolymer and their blends within the heating temperature range investigated, up to 250 °C. An opposite trend is observed within the temperature range 300–500 °C. In general, the thermal stability of homopolymers or their blends improves slighly after exposure to an irradiation dose of 100 kGy. These findings are clearly confirmed by the calculated activation energies of the thermal decomposition reaction of the homopolymers and the blends. © 2003 Society of Chemical Industry     

The phase behavior and the Flory-Huggins interaction parameter of blends containing amorphous poly(resorcinol phthalate-block-carbonate), poly(bisphenol-A carbonate) and poly(ethylene terephthalate)

The phase behavior of the blends of poly(ethylene terephthalate) (PET) and poly(Resorcinol Phthalate-block-Carbonate) (RPC) and the blends of PET and poly(Bisphenol-A Carbonate) (PC) was investigated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Blends of high molecular weight PET and RPC copolymer with 20 mol% resorcinol phthalate (RPC20) showed two glass transition temperatures in DMA and DSC but the cold crystallization rate of PET phase was substantially lowered as compared to neat PET, indicating partial miscibility at all compositions. The RPC20 with M_w = 31,500 g/mol formed miscible blends with PET when PET has weight-average molecular weight <9500 g/mol. The Flory-Huggins interaction parameter between PET and RPC20 was calculated to be 0.029 ± 0.003 by using the Flory-Huggins equation at critical composition and molecular weight. PC with M_w = 30,000 g/mol formed miscible blends with PET only when PET had molecular weight <2800 g/mol, indicating PC/PET blends were much less miscible than RPC20/PET blends. Group contribution methods agreed well with the experimental results obtained both in the present study and a previous study [1], predicting that the addition of a resorcinol phthalate block to a PC backbone should increase the miscibility of PC and PET.     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Thermal properties of poly(vinyl alcohol)–solute blends studied by TMDSC

A thermal analysis study of blends of semicrystalline poly(vinyl alcohol) (PVA) with a pharmaceutical substance, buflomedil pyridoxal phosphate (BPP) is presented. Temperature‐modulated DSC (TMDSC) was used to determine the T_g as well as the crystallinity of blends with various polymer to drug ratios, for different annealing procedures. Positive deviations from a simple expression for the composition dependence of the glass transition of the blend were found. This result, together with the increased thermal stability of PVA–BPP blends, evidenced by TGA analysis, indicates the existence of specific interactions between the polar groups of the two components. The incorporation of dispersed BPP in the PVA matrix results in a composition‐dependent lowering of the polymer's T_m and degree of crystallinity. In addition, we found that, while melting of pure PVA is predominantly reversing, its melting in the blends acquires an increasingly higher nonreversing component with increasing BPP content in the blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1151–1156, 2004     

Preparation method and physical,mechanical, thermal characterization of poly(vinyl alcohol)/poly(acrylic acid) blends

A series of blends of poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) were prepared by solution mixing and casting. Glycerol was used as plasticizer. The blends were characterized for their physicochemical and thermo-mechanical properties. The FTIR results revealed the molecular level interaction between PVA and PAA at all blend ratios. The incorporation of PAA significantly reduced the storage modulus of PVA at a given temperature. PVA gradually lost its crystalline character with the increase of PAA and became fully amorphous when the PAA content in the blend exceeded 50 wt%. The kinetic parameters of the semi-crystalline blends were determined using the Avarami–Erofeev model, which showed excellent fitting with the experimental data from DSC. The loss in crystallinity of PVA also contributed to an increase in swelling of the blend when the PAA content is increased. The morphology study by FE-SEM demonstrated that there is no phase separation among the blend components at all blend ratios.     

Preparation of PAM/PVA blending films by solution-cast technique and its characterization: a spectroscopic study

Polyacrylamide (PAM) and poly(vinyl alcohol) (PVA) were blended with different weight percentages (70/30, 50/50, 30/70) using solution-cast technique. The prepared films were studied by different characterization techniques. The effect of PVA content on PAM blends was investigated by Fourier transform infrared (FTIR), ultra violet visible (UV–vis), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Different mechanical properties of blends were also studied. Significant changes were observed in FTIR, UV–vis, TGA, SEM and mechanical analysis which revealed interactions between the two polymers. FTIR spectra showed the presence of hydrogen bonding between PAM and PVA and hydrophilic nature of the blends. Different optical properties were studied by UV–vis spectroscopy. The weight loss, as a function of temperature of blends, was analyzed by TGA. The results obtained from different experimental techniques were supported by SEM image analysis. FTIR analysis confirmed the conclusion on the specific hydrogen bonding between –CONH₂ groups in PAM and –OH group in PVA. These results showed the change in the thermal stability and mechanical properties. FTIR analysis revealed that a blend ratio of 50/50 wt% had maximum intermolecular interaction between two polymers. It was finally concluded that blend films with the above ratio display higher thermal stability and improved mechanical properties. Due to changes in interactions, the optical parameters were also changed.     

Preparation and characterization of chitosan/poly(vinyl alcohol) blend fibers

Chitosan and poly(vinyl alcohol) blend fibers were prepared by spinning their solution through a viscose‐type spinneret at 25°C into a coagulating bath containing aqueous NaOH and ethanol. The influence of coagulation solution composition on the spinning performance was discussed, and the intermolecular interactions of blend fibers were studied by infrared analysis (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM) and by measurements of mechanical properties and water‐retention properties. The results demonstrated that the water‐retention properties and mechanical properties of the blend fibers increase due to the presence of PVA in the chitosan substract, and the mechanical strength of the blends is also related to PVA content and the degree of deacetylation of chitosan. The best mechanical strength values of the blend fibers, 1.82 cN/d (dry state) and 0.81 cN/d (wet state), were obtained when PVA content was 20 wt % and the degree of deacetylation of chitosan was 90.2%. The strength of the blend fibers, especially wet tenacity could be improved further by crosslinking with glutaraldehyde. The water‐retention values (WRV) of the blend fibers were between 170 and 241%, obviously higher than pure chitosan fiber (120%). The structure analysis indicated that there are strong interaction and good miscibility between chitosan and poly(vinyl alcohol) molecular resulted from intermolecular hydrogen bonds. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2558–2565, 2001     

Blends containing amphiphilic polymers. V. Compatibilization of N‐alkylitaconamic acid‐co‐styrene copolymers with interacting polymers

The phase behavior of blends containing N‐alkylitaconamic acid‐co‐styrene copolymers (NAIA‐co‐S) with poly(N‐vinyl‐2‐pyrrolidone) (PVP) of two different weight average molecular weights (M _w ), poly(2‐vinylpyridine) (P2VPy) and poly(4‐vinylpyridine) (P4VPy), was analyzed by differential scanning calorimetry and Fourier transform infrared spectroscopy. Copolymers containing 80% S are miscible with PVP₁₀, PVP₂₄, and P4VPy over the whole range of composition. In the case of blends with P2VPy, miscibility is observed only for the first three members of the series, i.e., NEIA‐co‐S, NPIA‐co‐S, and NBIA‐co‐S. For copolymers containing hexyl to dodecyl moieties, phase separation is observed in blends with P2VPy. Copolymers containing 50% S are miscible over the whole range of composition irrespective of the homopolymer and the length of the side chain of the itaconamic moiety of the copolymer. This behavior is interpreted in terms of steric hindrance, in the sense that the copolymers with long side chains are not able to interact with the nitrogen of P2VPy because of the position in the aromatic ring. The interactions between copolymers and homopolymers are discussed in terms of specific interactions like hydrogen bonds between the itaconamic moiety and the different functional groups of the homopolymers, together with the hydrophobic interaction, which cannot be disregarded. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2512–2519, 2006     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry