Multiparameter solution model and evaluation of polymer–polymer miscibility using inverse gas chromatography data

Inverse gas chromatography (IGC) has been widely used to determine the Flory–Huggins parameters, χ, between solutes (probes) and polymers. This study correlated the Flory–Huggins parameter data using a multiparameter model, which included dispersion, polarity, acidity, and basicity components. The parameters of poly(ε‐caprolactone) (PCL) and polyepichlorohydrin (PECH) were calculated from IGC data using a series of probes. The parameters of the polymers were used to evaluate mutual miscibility between PCL and PECH. The results predicted miscibility in agreement with the conclusion of an IGC study using blends of PCL and PECH. A method to estimate the confidence interval of polymer parameters was proposed. The anomalous solubility parameter of polymer mixtures previously reported was also explained using this model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility enhancement on the poly(vinylchloride)/poly(methylmethacrylate) blend and characterization by inverse gas chromatography: The corrected polymer–polymer interaction parameters from the probes dependency

The miscibility of poly(vinyl chloride)/poly(methylmethacrylate) (PVC/PMMA) system was improved by introducing some pyrrolidone units into the main chains of PMMA. For that purpose, we have synthesized two copolymers of poly(methylmethacrylate‐co‐vinylpyrrolidone) (MMVP) through a radical polymerization and carried out a comparative study of PVC/MMVP blends by inverse gas chromatography (IGC) and differential scanning calorimetry (DSC) methods. The adequacy of seven n‐alkane probes has been tested to determine the thermodynamic parameters. The miscibility of the two systems has been proved by a single T_g for each blend. This observation was also confirmed by DSC analysis. To highlight the presence of interaction and its intensity between PVC and MMVP in the blends, the polymer–polymer interaction parameters have been evaluated by IGC trough which the influence of the solute has been resolved. The Schneider approach confirmed the miscibility of these systems as the K deviates positively from unity. The miscibility has been appeared highlighted from the positive difference in surface energy between the pure polymers and their blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization of biodegradable polymers by inverse gas chromatography. II. Blends of amylopectin and poly(ε‐caprolactone)

Amylopectin (AP), a potato‐starch‐based polymer with a molecular weight of 6,000,000 g/mol, was blended with poly(ε‐caprolactone) (PCL) and characterized with inverse gas chromatography (IGC), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). Five different compositions of AP–PCL blends ranging from 0 to 100% AP were studied over a wide range of temperatures (80–260°C). Nineteen solutes (solvents) were injected onto five chromatographic columns containing the AP–PCL blends. These solutes probed the dispersive, dipole–dipole, and hydrogen‐bonding interactions, acid–base characteristics, wettability, and water uptake of the AP–PCL blends. Retention diagrams of these solutes in a temperature range of 80–260°C revealed two zones: crystalline and amorphous. The glass‐transition temperature (T_g) and melting temperature (T_m) of the blends were measured with these zones. The two zones were used to calculate the degree of crystallinity of pure AP and its blends below T_m, which ranged from 85% at 104°C to 0% at T_m. IGC complemented the DSC method for obtaining the T_g and T_m values of the pure AP and AP–PCL blends. These values were unexpectedly elevated for the blends over that of pure AP and ranged from 105 to 152°C for T_g and from 166 to 210°C for T_m. The T_m values agreed well with the XRD analysis data. This elevation in the T_g and T_m values may have been due to the change in the heat capacity at T_g and the dependence of T_g on various variables, including the molecular weight and the blend composition. Polymer blend/solvent interaction parameters were measured with a variety of solutes over a wide range of temperatures and determined the solubility of the blends in the solutes. We were also able to determine the blend compatibility over a wide range of temperatures and weight fractions. The polymer–polymer interaction coefficient and interaction energy parameter agreed well on the partial miscibility of the two polymers. The dispersive component of the surface energy of the AP–PCL blends was measured with alkanes and ranged from 16.09 mJ/m² for pure AP to 38.26 mJ/m² when AP was mixed with PCL in a 50/50% ratio. This revealed an increase in the surface energy of AP when PCL was added. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3076–3089, 2006     

Probe dependency of polymer‐plasticizer and polymer‐polymer interaction parameters in inverse gas chromatography

Inverse gas chromatography has been widely used to determine the Flory–Huggins parameter, χ, between a plasticizer and a polymer, or between two polymers. Many studies showed that interaction parameters may be probe dependent. In a recent study it was proposed that, when a specific interaction occurred between two polymers, the probes had less interaction with the polymers, leading to a lower solubility parameter for polymer blends than the volume average of the components. An equation was derived to relate the probe dependency to the deviation of solubility parameter of polymer mixtures. Here this approach is applied to plasticized poly(vinyl chloride) (PVC) and a copolymer, and to poly(vinylidene fluoride)–poly(ethyl methacrylate) blends. For a PVC and epoxidized oil system the relative deviation of specific retention volume showed two trends, with saturated hydrocarbons as one group, and polar and aromatic probes as another group. For the poly(vinylidene fluoride)/poly(ethyl methacrylate) system the plot of retention volume deviation versus solubility parameter of probes also showed separate trends for n‐alkanes, esters, and alcohols. But the plot of ?₂?₃RT(χ₂₃/V₂) versus solubility parameter had better linearity for the systems studied. The slope of this plot was used as an indicator for miscibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Glass‐transition temperature of poly(vinylidene fluoride)‐poly(methyl acrylate) blends: Influence of aging and chain structure

The glass‐transition temperature (T_g) of the poly(vinylidene fluoride) (PVF₂)‐poly(methyl acrylate) (PMA) blends increase with aging time. The T_g versus log(time) plots are straight lines whose slope values depend on the head to head (H–H) defect content of PVF₂ samples and on the composition of the blends. The values of polymer–polymer interaction parameters (χ) increase with an increase in the H–H defect of PVF₂ for a fixed composition of the blend. Consequently, the T_g of the blend decreases with an increase in the H–H defect of the PVF₂ sample. However, after aging for longer times this decrease of the T_g with H–H defects is lower than those of the unaged blends. The possible reasons are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1541–1548, 2001     

Compatibility studies of sulfonated poly(ether ether ketone)–poly(ether imide)–polycarbonate ternary blends

Binary blends of the sulfonated poly(ether ether ketone) (SPEEK)–poly(ether imide) (PEI) and SPEEK–polycarbonate (PC), and ternary blends of the SPEEK–PEI–PC, were investigated by differential scanning calorimetry. SPEEK was obtained by sulfonation of poly(ether ether ketone) using 95% sulfuric acid. From the thermal analysis of the SPEEK–PEI blends, single glass transition temperature (T_g) was observed at all the blend composition. For the SPEEK–PC blends, double T_gs were observed. From the results of thermal analysis, it is suggested that the SPEEK–PEI blends are miscible and the SPEEK–PC blends are immiscible. Polymer–polymer interaction parameter (χ₁₂) of the SPEEK–PEI blends was calculated from the modified Lu and Weiss equation, and found to range from −0.011 to −0.825 with the blend composition. For the SPEEK–PC blends, the χ₁₂ values were calculated from the modified Flory–Huggins equation, and found to range from 0.191 to 0.272 with the blend composition. For the SPEEK–PEI–PC ternary blends, phase separation regions that showed two T_gs were found to be consistent with the spinodal curves calculated from the χ₁₂ values of the three binary blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2488–2494, 2000     

Thermal properties of melt‐blended poly(ether ether ketone) and poly(ether imide)

The thermal properties of blends of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) prepared by screw extrusion were investigated by differential scanning calorimetry. From the thermal analysis of amorphous PEEK–PEI blends which were obtained by quenching in liquid nitrogen, a single glass transition temperature (T_g) and negative excess heat capacities of mixing were observed with the blend composition. These results indicate that there is a favorable interaction between the PEEK and PEI in the blends and that there is miscibility between the two components. From the Lu and Weiss equation and a modified equation from this work, the polymer–polymer interaction parameter (χ₁₂) of the amorphous PEEK–PEI blends was calculated and found to range from −0.058 to −0.196 for the extruded blends with the compositions. The χ₁₂ values calculated from this work appear to be lower than the χ₁₂ values calculated from the Lu and Weiss equation. The χ₁₂ values calculated from the T_g method both ways decreased with increase of the PEI weight fraction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 733–739, 1999     

Part 7. Effects of poly(L‐lactide‐co‐ϵ‐caprolactone) on morphology,structure, crystallization,and physical properties of blends of poly(L‐lactide) and poly(ϵ‐caprolactone)

Blended films of poly(L ‐lactide) [ie poly(L ‐lactic acid)] (PLLA) and poly(?‐caprolactone) (PCL) without or mixed with 10 wt% poly(L ‐lactide‐co‐?‐caprolactone) (PLLA‐CL) were prepared by solution‐casting. The effects of PLLA‐CL on the morphology, phase structure, crystallization, and mechanical properties of films have been investigated using polarization optical microscopy, scanning electron microscopy, differential scanning calorimetry and tensile testing. Addition of PLLA‐CL decreased number densities of spherulites in PLLA and PCL films, and improved the observability of spherulites and the smoothness of cross‐section of the PLLA/PCL blend film. The melting temperatures (T_m) of PLLA and PCL in the films remained unchanged upon addition of PLLA‐CL, while the crystallinities of PLLA and PCL increased at PLLA contents [X_PLLA = weight of PLLA/(weight of PLLA and PCL)] of 0.4–0.7 and at most of the X_PLLA values, respectively. The addition of PLLA‐CL improved the tensile strength and the Young modulus of the films at X_PLLA of 0.5–0.8 and of 0–0.1 and 0.5–0.8, respectively, and the elongation at break of the films at all the X_PLLA values. These findings strongly suggest that PLLA‐CL was miscible with PLLA and PCL, and that the dissolved PLLA‐CL in PLLA‐rich and PCL‐rich phases increased the compatibility between these two phases. © 2003 Society of Chemical Industry     

Enzymatic degradation of blends of poly(ε‐caprolactone) and poly(styrene‐co‐acrylonitrile) by Pseudomonas lipase

In polymer blends, the composition and microcrystalline structure of the blend near surfaces can be markedly different from the bulk properties. In this study, the enzymatic degradation of poly(ε‐caprolactone) (PCL) and its blends with poly(styrene‐co‐acrylonitrile) (SAN) was conducted in a phosphate buffer solution containing Pseudomonas lipase, and the degradation behavior was correlated with the surface properties and crystalline microstructure of the blends. The enzymatic degradation preferentially took place at the amorphous part of PCL film. The melt‐quenched PCL film with low crystallinity and small lamellar thickness showed a higher degradation rate compared with isothermally crystallized (at 36, 40, and 44°C) PCL films. Also, there was a vast difference in the enzymatic degradation behavior of pure PCL and PCL/SAN blends. The pure PCL showed 100% weight loss in a very short time (i.e., 72 h), whereas the PCL/SAN blend containing just 1% SAN showed ～50% weight loss and the degradation ceased, and the blend containing 40% SAN showed almost no weight loss. These results suggest that as degradation proceeds, the nondegradable SAN content increases at the surface of PCL/SAN films and prevents the lipase from attacking the biodegradable PCL chains. This phenomenon was observed even for a very high PCL content in the blend samples. In the blend with low PCL content, the inaccessibility of the amorphous interphase with high SAN content prevented the attack of lipase on the lamellae of PCL. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 868–879, 2002     

Porous biodegradable polyesters. II. Physical properties,morphology, and enzymatic and alkaline hydrolysis of porous poly(ϵ‐caprolactone) films

Porous poly(?‐caprolactone) (PCL) films were prepared by water extraction of poly(ethylene oxide) (PEO) from their solution‐cast phase‐separated blend films and the dependence of their blend ratio [X_PCL = PCL/(PEO + PCL)] and molecular weight of PEO on the porosity, pore size, crystallinity, crystalline thickness, mechanical properties, morphology, and enzymatic and alkaline hydrolysis of the porous PCL films were investigated. The film porosity or extracted weight ratio was in good agreement with the expected values, irrespective of X_PCL and molecular weight of PEO. The maximum pore size was larger for the porous films prepared using PEO having a lower molecular weight, compared with films prepared using PEO having a higher molecular weight at the same X_PCL. Differential scanning calorimetry of the porous PCL films revealed that their crystallinity and crystalline thickness were almost constant, regardless of X_PCL and molecular weight of PEO. The Young's modulus and tensile strength of the porous films decreased, whereas the elongation‐at‐break increased with decreasing X_PCL. The enzymatic and alkaline hydrolysis rates of the porous films increased with a decrease in X_PCL and an increase in the molecular weight of PEO. The porous PCL films having Young's modulus in the range of 2–24 kg/mm² and enzymatic hydrolysis rate in the range of one‐ to 20‐fold that of the nonporous PCL film could be prepared by altering X_PCL and the molecular weight of PEO. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2281–2291, 2001     

Phase behavior of poly(ε-caprolactone)/ poly (vinylidene fluoride) blends

The miscibility of blends of poly (ε-caprolactone) (PCL)/poly(vinylidene fluoride) (PVDF) was studied by measuring the cloud point, melting point depression and crystallization kinetics. Lower critical solution temperature (LCST) behavior was observed at PCL-rich compositions, whilst it was not observed at high compositions of PVDF. However it is possible that an LCST could exist below the melting point of PVDF. From analysis of the melting point depression, the Flory interaction parameter x₁₂, was calculated from the Nishi-Wang equation and the value was found to be-1.5. The crystallization rate of PCL increased with increasing amount of PVDF in the blend. The spinodal curve for PCL/PVDF blends was simulated by using the lattice-fluid theory.     

Miscibility of block copolymers of poly(ε‐caprolactone) and poly(ethylene glycol) with poly(3‐hydroxybutyrate) as well as the compatibilizing effect of these copolymers in blends of poly(ε‐caprolactone) and poly(3‐hydroxybutyrate)

Atactic poly(3‐hydroxybutyrate) (a‐PHB) and block copolymers of poly(ethylene glycol) (PEG) with poly(ε‐caprolactone) (PCL‐b‐PEG) were synthesized through anionic polymerization and coordination polymerization, respectively. As demonstrated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) measurements, both chemosynthesized a‐PHB and biosynthesized isotactic PHB (i‐PHB) are miscible with the PEG segment phase of PCL‐b‐PEGs. However, there is no evidence showing miscibility between both PHBs and the PCL segment phase of the copolymer even though PCL has been block‐copolymerized with PEG. Based on these results, PCL‐b‐PEG was added, as a compatibilizer, to both the PCL/a‐PHB blends and the PCL i‐PHB blends. The blend films were obtained through the evaporation of chloroform solutions of mixed components. Excitingly, the improvement in mechanical properties of PCL/PHB blends was achieved as anticipated initially upon the addition of PCL‐b‐PEG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2600–2608, 2001     

Polymorphic and miscibility behavior in crystalline/crystalline blends of poly(pentamethylene terephthalate) with poly(heptamethylene terephthalate)

BACKGROUND: The phase behavior of blends of semicrystalline aryl polyesters with long methylene segments (? (CH₂)_n? with n = 5 or 7) in the repeat units has not been much studied. Thus, crystalline/crystalline blends comprising monomorphic poly(pentamethylene terephthalate) (PPT) and polymorphic poly(heptamethylene terephthalate) (PHepT) were prepared and the crystal growth kinetics, polymorphism behavior and miscibility in this blend system were probed using polarized‐light optical microscopy, differential scanning calorimetry and wide‐angle X‐ray diffraction. RESULTS: The PPT/PHepT blends of all compositions were first proven to be miscible in the melt state or quenched amorphous phase, whose interaction strength was determined (χ₁₂ = ? 0.35), showing favorable interactions and phase homogeneity. Although the spherulites of neat PPT and PHepT could exhibit ring bands at different crystallization temperature (T_c) ranges (100–110 and 50–65 °C, respectively), the spherulites of PPT/PHepT (50/50) blend became ringless in the range 50–110 °C. Growth analysis and polymorphic behavior in the crystalline phases of the blends provided extra evidence for the miscibility between these two crystalline polymers. Spherulitic growth rates of PPT in the PPT/PHepT blends were significantly reduced in comparison with those of neat PPT. In addition, miscible blending of a small fraction of monomorphic PPT (20 wt%) with polymorphic PHepT altered the crystal stability and led to the originally polymorphic PHepT exhibiting only the β‐crystal form when melt‐crystallized at all values of T_c. CONCLUSION: The highly intimate mixing in polymer chains of crystalline PPT and PHepT causes significant disruption in ring‐band patterns and reduction in crystallization rates of PPT as well as alteration in the polymorphic behavior of PHepT. Copyright © 2009 Society of Chemical Industry     

Surface energy parameters of polymers from directly measured interfacial tension with probe polymers

The surface energy parameters of polycaprolactone (PCL) were determined at 160 and 180^°C from its interfacial tensions with probe polymers. The probe polymers were polystyrene (PS) and poly(methyl methacrylate) (PMMA). This method is based on the well-known relationship between blend interfacial tension and polymer surface energy parameters, and requires the use of at least two probe polymers, whose surface energy parameters at the temperature of interest have been independently determined. It also requires direct measurement of blend interfacial tension at the high temperatures of interest. The interfacial tensions were obtained from direct measurements by the imbedded fiber retraction method. The following results were obtained: (a) γ ^P (polar component) values for PCL was within the range reported using other methods, (b) γ ^D (dispersion component) values for PCL decreased with increasing temperature, consistent with expectations and (c) γ ^D values for PCL were on the high end, but still within the rather broad range of reported values.     

Thermal Property and Hydrogen Bonding in Blends of Poly(vinylphenol) and Poly(hydroxylether of Bisphenol A)

The thermal property and hydrogen bonding in polymer blends of poly(vinylphenol) (PVPh) and poly(hydroxylether of bisphenol A) (phenoxy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (NMR). This PVPh/phenoxy blend shows single composition-dependent glass transition temperature over the entire compositions, indicating that the hydrogen bonding exists between the hydroxyl of PVPh and hydroxyl of phenoxy. The negative T _g deviation of the PVPh/phenoxy blend indicates the strong intermolecular hydrogen-bonding interaction. The inter-association constant for the PVPh/phenoxy blend is significantly higher than self-association constants of PVPh and phenoxy, revealing that the tendency toward hydrogen bonding between PVPh and phenoxy is more favorable than the intra-hydrogen bonding of the PVPh and phenoxy in the blend.     

Miscible blends of styrene–cinnamic acid copolymers with poly(ethyl methacrylate)

Differential scanning calorimetry and inverse gas chromatography have been used to investigate the miscibility behaviour of blends of poly(ethyl methacrylate) (PEMA) with styrene–cinnamic acid statistical copolymers PSCA5, PSCA8, PSCA23 having compositions of, respectively, 5, 8 and 23 mol% of cinnamic acid. Several probes with different chemical nature and polarity have been used to determine the polymer–solute and polymer–polymer interaction parameters. DSC and CPGI measurements indicate that poly(ethyl methacrylate) is miscible with each poly[(styrene)‐co‐(cinnamic acid)] copolymer as established from the observation of a single composition‐dependent glass transition temperature. This deduction is corroborated by the IGC data; comparison of the experimental retention volume of the blend with the algebraic average retention volumes of the pure components, together with negative values of the apparent polymer–polymer interaction parameter, establish the miscibility of the studied systems. Furthermore, the polymer–polymer interaction parameters are found to show marked probe dependence; this is discussed in terms of the Δχ effect. As indicated by the variation of the glass transition temperature with blend composition, the application of the Kwei and the Schneider approaches to the calorimetric results suggests the occurrence of strong specific interactions within the blends; the strength of these intermolecular interactions increases with the cinnamic acid content in the PSCA copolymer. © 2001 Society of Chemical Industry     

Melt rheology of poly(ϵ‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors a_T can be expressed by the Williams–Landel–Ferry equation: log a_T = ?8.86(T ? T_s)/(101.6 + T ? T_s). The compositional dependency of T_s represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001     

Study on the Crystallization,Miscibility, Morphology,Properties of Poly(lactic acid)/Poly(ε-caprolactone) Blends

A series of blends of poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) with different mass ratio were prepared by means of the melt blending method to study their crystallization, miscibility, morphology, and thermal and mechanical properties. The result of DSC tests showed that the melting temperatures of PLA and PCL shifted toward each other, and that the largest shift appeared at the PLA₇₀PCL₃₀ blend. This result reveals that the PLA₇₀PCL₃₀ blend gives the strongest interaction intensity among the blends. Combined the result of dynamic mechanical analysis and SEM morphologies, it was found that PLA and PCL form a partial miscible blend, in which an amount of amorphous PCL (amorphous PLA) is dissolved in the PLA-rich phase (PCL-rich phase), leading to a depression of the T_g. value. The polarized optical micrographs showed that PCL can serve as a nucleating agent to promote PLA crystallization in the PLA/PCL blend. Moreover, the PLA₇₀PCL₃₀ blend gave the largest growth rate of PLA spherulite. Finally, the mechanical property of PLA/PCL blends indicated that PLA can easily be tuned from rigid to ductile by the addition of PCL.     

Effects of the energy dissipation rate and surface erosion on the biodegradation of poly(hydroxybutyrate‐co‐hydroxyvalerate) and its blends with synthetic polymers in an aquatic medium

The anaerobic biodegradation of polymers by soil microorganisms was investigated in shaking flask cultures at different rotation speeds or energy dissipation rates. The polymers included poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV), poly(?‐caprolactone) (PCL), polystyrene (PS), two binary PHBV/PCL blends (80/20 and 25/75 w/w), and a triple PHBV/PCL/PS blend (76/5/19 w/w/w). The specific degradation rate of PHBV found from the specimen's residual mass fraction with time was constant after a lag phase and was significantly affected by the agitation strength (<0.5 day^?1 at 60 rpm or lower and >15 day^?1 at 120 rpm or greater). Tiny polymer fragments were formed on the specimen surface and observed with scanning electron microscopy during degradation. The detachment of those fragments under high hydraulic shear stress caused surface erosion and renewal, resulting in the high degradation rate. The hydraulic shear stress (0.6 Pa) at an energy dissipation rate of 0.5 W/kg was a threshold level, above which the external force did not increase the degradation rate very much. PHBV degradation in the binary blends with compatible PCL was retarded, depending on the blend composition. Blending PHBV with noncompatible PS did not affect PHBV degradation, and the overall degradation rate of the triple blend was faster than the rate of PHBV alone because of the surface erosion of both PHBV and nondegradable PS fragments from the specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1036–1045, 2002     

Use of Flory–Huggins parameters in the characterization of polymer–filler compositions

Any quantitative information on the strength of interactions between an inorganic filler and polymer is substantial for the future application of the composite. The magnitude of adhesion of two phases may be deduced from results collected by various experimental techniques. A Flory–Huggins interaction parameter (χ₂₃^′) was earlier successfully used in the characterization of polymer blends. We propose to express the magnitude of modified filler/polymer interactions by using χ₂₃^′. It was calculated from retention data of test solutes during an inverse gas chromatography (IGC) experiment. IGC is an extension of conventional gas chromatography in which a nonvolatile material to be investigated is immobilized on a column. Parameters determined during IGC experiments may be successfully used in the characterization of polymers and their blends, composites, fillers, and other materials and the quantification of the interactions between the components of polymer mixtures, including the interactions between polymeric components and filler surfaces. Here this method is applied to the characterization of a series of poly(ether urethane)/modified carbonate–silicate filler systems containing different amounts of a filler (5, 10, and 20 wt %). The possibilities and limitations of the IGC method are shown. The usefulness of some methods for minimizing the Δχ effect (the dependence of χ₂₃^′ on the type of test solute) is examined and discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008