Study on the milling behavior of chloroprene rubber blends with ethylene–propylene–diene monomer rubber,polybutadiene rubber,and natural rubber

The viscoelastic properties of the blends of chloroprene rubber (CR) with ethylene–propylene–diene monomer rubber (EPDM), polybutadiene rubber (BR), and natural rubber (NR) at different temperature were studied using rubber processing analyzer (RPA). Mooney viscosities of compounds were measured and tight milling and sheeting appearance were observed on a two‐roll mill. The results showed that Mooney viscosities and the elastic modulus of the blends decreased with the increase of the temperature from 60 to 100°C. And the decreasing trends of pure CR, pure NR, and CR/NR blend compounds were more prominent than that of pure EPDM, pure BR, CR/EPDM, and CR/BR blend compounds. For CR/EPDM blend compounds, the decreasing trend became slower with the increase of EPDM ratio in the blend. Compared with pure CR, pure NR and CR/NR blend compounds, pure EPDM, pure BR compounds, and the blend compounds of CR/EPDM and CR/BR showed less sensibility to temperature and they were less sticky to the metal surface of rolls and could be kept in elastic state at higher temperature, easy to be milled up and sheeted. At the same blend ratio and temperature, the property of tight milling of the blends decreased in the sequence of CR/EPDM, CR/BR, and CR/NR. With the increase of EPDM, BR, or NR ratio in CR blends, its property of tight milling was improved. POLYM. COMPOS., 28:667–673, 2007. © 2007 Society of Plastics Engineers     

The morphology and photoelectronic properties of poly(9,9′‐dioctylfluorene)/ethyl‐cyanoethyl cellulose blends

The morphology and photoelectronic properties of blend films of poly(9,9′‐dioctylfluorine) (PF) and ethyl–cyanoethyl cellulose [(E‐CE)C] were investigated. It was found that the morphology of the blends was changed with the blend composition. The lateral phase separation was observed in submicron scale, and a nanoscale vertical phase separation occurred with enrichment of the (E‐CE)C at the surface of the blend films. The photoluminescent spectra of the blend films are blue‐shifted with the increase of the (E‐CE)C. The photoelectronic properties of the blends varied with the morphology of the blends. In the electroluminescent device, the turn‐on voltage was almost identical for the device with 50% or above 50 wt % PF in blend films and markedly improved for the device with only 25 wt % PF. The external quantum efficiency of the device fabricated with 75% PF is the highest among the device fabricated with the PF/(E‐CE)C blend films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Conductive polyaniline–polychloroprene blends

The electrical conductivity of polychloroprene (CR)/polyaniline (Pani) blends prepared by bulk and solution processes were investigated. Pani doped with HCl (Pani · HCl) and p-toluenesulfonic acid (Pani · TSA) were employed in vulcanized blends obtained by the bulk process. These blends showed an increase in the conductivity only for blend composition of CR/Pani = 50:50 wt %. At this composition, blends with Pani · HCl and Pani · pTSA presented conductivity values of 10⁻⁹ and 10⁻¹⁰ S · cm⁻¹, respectively. CR/Pani · HCl blend films prepared by the solution process displayed surface conductivity values of 10⁻⁴ S · cm⁻¹ with as low as 10–15 wt % of PAni · HCl. Surface analysis of these blends by X-ray photoelectron spectroscopy indicated no traces of the conductive additive. The surface composition was found to be exclusively constituted of CR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1543–1549, 1998     

Stress–strain behavior as related to surface topography and thickness uniformity in uni‐ and biaxially stretched PVDF/PMMA blends

The influence of blend composition and processing conditions on the surface roughness and thickness uniformity of PVDF/PMMA blends were investigated in uniaxial and biaxial deformation mode for PVDV and PVDF/PMMA blends 70/30, 55/45, and 40/60 wt%. The addition of PMMA retards the thermal crystallizability of the blends and this allows rapid solidification into films with little or no crystallinities. Such precursors with lowered crystallinity were found to be easily uni‐ and biaxially stretched into uniform and transparent films in the temperature range between the glass transition temperature and cold crystallization temperature where they exhibit strain hardening. Thus, these blends are suitable for processes such as tenter frame biaxial stretching, double bubble film blowing, and stretch blow molding where they will exhibit good transparency and thickness uniformity. POLYM. ENG. SCI., 47:2110–2117, 2007. © 2007 Society of Plastics Engineers     

Morphology,nanomechanical and thermodynamic surface characteristics of nylon 6/feather keratin blend films: an atomic force microscopy investigation

The surface structure and nanomechanical properties of solution‐cast nylon 6 (NY6)/feather keratin (FK) blend films were investigated using a combination of tapping‐mode atomic force microscopy (AFM) phase imaging and nanoscale indentation. A tendency for a nanoscale phase separation between NY6 and FK in their various blends was judged based on the blend phase images. The surface topography and roughness analysis of the AFM height images revealed that FK‐rich blends had coarser surfaces than NY6‐rich ones, possibly due to the heterogeneous nature of the FK chemical structure. Amplitude–phase–distance measurements involving the assignment of the darker and brighter regions of the phase images to NY6‐rich and FK‐rich, respectively, or vice versa led to the recognition of a phase inversion in the blend containing 40 wt% FK. The occurrence of the phase inversion phenomenon was related to the significant difference between the molecular weights of the blend constituents. Analysis of nanoindentation data showed that blending FK and NY6 at various ratios resulted in mixtures with modified mechanical and adhesion features. On the one hand, the NY6 component was responsible for an enhanced elastic modulus and stiffness of the blends, and on the other hand, the FK component provided higher pull‐off force and work of adhesion for the samples. A new approach is also proposed to directly determine the surface energy (γ) values of samples from the nanoindentation data. The excellent consistency between the calculated γ values and the results obtained from contact angle measurements lends credence to the proposed approach. Copyright © 2012 Society of Chemical Industry     

A comparative study of polypropylene/(chloroprene rubber) and (recycled polypropylene)/(chloroprene rubber) blends

The blends of virgin polypropylene (PP) and recycled polypropylene (RPP) with chloroprene rubber (CR) have been prepared. The effect of different blend ratios on tensile properties, swelling behavior, morphology, and crystallinity of both blends of virgin and RPP was investigated. The tensile strength and Young's modulus of both blends decreased with increasing CR in blend ratios but the elongation at break was increased. It was found that the tensile properties of PP/CR blends were better than the RPP/CR blends. The PP/CR blends showed the lower value of swelling index. The scanning electron micrograph of the tensile fractured surface of PP/CR blends indicates that a higher energy is needed to cause failure compared with RPP/CR blends. The differential scanning calorimery results indicated that the degree of crystallinity of PP/CR blends also was found to be higher than RPP/CR blends. J. VINYL ADDIT. TECHNOL., 21:122–127, 2015. © 2014 Society of Plastics Engineers     

Microstructure and miscibility of acrylonitrile–butadiene rubber/ethylene–propylene–diene monomer blends studied by positron annihilation spectroscopy

The free‐volume properties and miscibility of ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber blends with poly(vinyl chloride) used for compatibilization were investigated with positron annihilation lifetime spectroscopy and Doppler broadening of annihilation radiation. The results showed that the ortho‐positronium annihilation lifetimes and intensities as well as the S parameter had a linear relationship with a negative slope as a function of the weight percentage of acrylonitrile–butadiene rubber, which indicated the miscibility of the blend. The filling effect of silica on the free‐volume properties of an ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber (75/25) blend was also examined. On the other hand, a correlation between the size and concentration of the free‐volume holes and the electrical and mechanical properties of the aforementioned blends was established. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characterization of acrylonitrile–styrene–methylmethacrylate terpolymer as a compatibilizer for rubber blends

Acrylonitrile‐co‐styrene‐co‐methylmethacrylate (AN‐S‐MMA) terpolymer was prepared by bulk and emulsifier‐free emulsion polymerization techniques. The bulk and emulsion terpolymers were characterized by means of Fourierr transform infrared spectroscopy, ¹³C nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and elemental analysis. The kinetics of the terpolymerization were studied. The terpolymers were then incorporated into butadiene—acrylonitrile rubber (NBR)/ethylene propylene diene monomer rubber (EPDM) blends and into chloroprene rubber (CR)/EPDM blend. The terpolymers were then tested for potential as compatibilizers by using scanning electron microscopy and differential scanning calorimetry. The terpolymers improved the compatibility of CR/EPDM and NBR/EPDM blends. The physicomechanical properties of CR/EPDM and NBR/EPDM blend vulcanizates revealed that the incorporation of terpolymers was advantageous, since they resulted in blend vulcanizates with higher 100% moduli and with more thermally stable mechanical properties than the individual rubbers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3143–3153, 2003     

Mechanical and morphological properties of lyocell blends: Comparison with lyocell nanocomposites (I)

The mechanical properties and morphologies of polyblends of lyocell with three different fillers are compared. Poly(vinyl alcohol) (PVA), poly(vinyl alcohol‐co‐ethylene) (EVOH), and poly(acrylic acid‐co‐maleic acid) (PAM) were used as fillers in blends with lyocell produced through solution blending. The variations of their properties with polymer matrix filler content are discussed. The ultimate tensile strength of the PVA/lyocell blend is highest for a blend lyocell content of 30 wt %, and decreases as the lyocell content is increased up to 40 wt %. The ultimate tensile strengths of the EVOH/lyocell and PAM/lyocell blends are highest for a lyocell loading of 20 wt %, and decrease with the increasing filler content. The variations in the initial moduli of the blends with filler content are similar. Of the three blend systems, the blends with PVA exhibit the best tensile properties. Lyocell/organoclay hybrid films were prepared by the solution intercalation method, using dodecyltriphenylphosphonium–Mica (C₁₂PPh‐ Mica) as the organoclay. The variation of the mechanical tensile properties of the hybrids with the matrix polymer organoclay content was examined. These properties were found to be optimal for an organoclay content of up to 5 wt %. Even polymers with low organoclay contents exhibited better mechanical properties than pure lyocell. The addition of organoclay to lyocell to produce nanocomposite films was found to be less effective in improving its ultimate tensile strength than blending lyocell with the polymers. However, the initial moduli of the nanocomposites were found to be higher than those of the polyblend films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Film formation from pigmented latex systems: Drying kinetics and bulk morphologies of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) blend films

The drying kinetics and bulk morphology of pigmented latex films obtained from poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex particles functionalized with carboxyl groups and ground calcium carbonate blends were studied. Latex/pigment blends with higher carboxyl group coverage on the latex particle surfaces dried faster than films with few or no carboxyl groups present. The latex/pigment dispersions also dried faster when there was more stabilizer present in the blend system because of the hydrophilic nature of the stabilizer. The net effect of increasing the pigment volume concentration in the blend system was to shorten the drying time. The bulk morphologies of the freeze‐fractured surfaces of the pigmented latex films were studied with scanning electron microscopy. Scanning electron microscopy analysis showed that increased surface coverage of carboxyl groups on the latex particles in the latex/pigment blends resulted in the formation of smaller pigment aggregates with a more uniform size distribution in the blend films. In addition, the use of smaller latex particles in the blends reduced the ground calcium carbonate pigment aggregate size in the resulting films. Scanning electron microscopy analysis also showed that when the initial stabilizer coverage on the latex particles was equal to 18%, smaller aggregates of ground calcium carbonate were distributed within the copolymer matrix of the blend films in comparison with the cases for which the initial stabilizer coverage on the latex particles was 8 or 36%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2267–2277, 2006     

Preparation and characterization of a methyl methacrylate/ethyl acrylate/acrylic acid terpolymer to improve the homogeneity of ethylene–propylene–diene monomer rubber/poly(vinyl chloride) blends

The emulsion terpolymerization of methyl methacrylate (MMA), ethyl acrylate (EA), and acrylic acid (AA) was carried out under a nitrogen atmosphere at 70°C. The final terpolymer conversion was determined gravimetrically. The synthesized MMA–EA–AA terpolymer was characterized with ¹H‐NMR spectroscopy, thermal analysis, and gel permeation chromatography. Glass‐transition temperatures of the MMA–EA–AA terpolymer were determined with a differential scanning calorimeter. Ethylene–propylene–diene monomer rubber (EPDM)/poly(vinyl chloride) (PVC) blends were prepared with different blend ratios (10/90, 20/80, 30/70, 40/60, and 50/50) in the presence and absence of MMA–EA–AA as a compatibilizer. The morphology of those blends was examined with the aid of a scanning electron microscope. The scanning electron micrographs in the presence of the MMA–EA–AA terpolymer illustrated the disappearance of the macroscale phase separation of EPDM/PVC blends as a result of the incorporation of MMA–EA–AA into that blend, indicating an improvement of the homogeneity. The mechanical properties of the EPDM/PVC blend films and the dielectric properties of the melt blends were investigated. The swelling behavior of the cured blends in the brake fluid was also discussed. The results illustrated that the mechanical properties, the weight swelling values, and the dielectric constant values showed linear behavior versus the blend ratios after the incorporation of the terpolymer. However, those values showed deviations from linearity in the absence of the terpolymer. That, in turn, ensured the results obtained with the scanning electron microscope. The results reveal that the MMA–EA–AA terpolymer prepared can be used successfully to improve the homogeneity of EPDM/PVC blends used in hose and oil seal applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Evidences of solvent‐induced miscibility in polychloroprene‐co‐ethylene‐propene diene terpolymer blends

Solvent dependent changes in the compatibility behavior of Polychloroprene/Ethylene–propylene–diene terpolymer blends (CR/EPDM) have been investigated using dilute solution viscometry and solvent permeability analysis. To predict the compatibility of rubber blends of different compositions in solvents of different cohesive energy densities, Huggins interaction parameter (ΔB), hydrodynamic interaction (Δη) and Sun's parameter (α) were evaluated from the analysis of the specific and reduced viscosity data of two and three‐component polymer solutions. Miscibility criteria were not satisfied for CR/EPDM blends over the entire composition range in toluene, xylene, and carbon tetrachloride (CCl₄), however, a narrow miscibility domain was observed in chloroform (CHCl₃) for CR/EPDM/CHCl₃ system. These results were further corroborated with the analysis of heat of mixing (ΔH_m) and polymer–polymer interaction parameter (χ₁₂), for all rubber blend compositions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical,thermal, and morphological characteristics of compatibilized and dynamically vulcanized polyoxymethylene/ethylene propylene diene terpolymer blends

Dynamically vulcanized blends of polyoxymethylene (POM) and ethylene propylene diene terpolymer (EPDM) with and without compatibilizer were prepared by melt mixing in a twin screw extruder. Maleic anhydride (MAH) grafted EPDM (EPDM‐g‐MAH) has been used as a compatibilizer. Dicumyl peroxide was used for vulcanizing the elastomer phase in the blends. Mechanical, dynamical mechanical, thermal, and morphological properties of the blend systems have been investigated as a function of blend composition and compatibilizer content. The impact strength of both dynamically vulcanized blends and compatibilized/dynamically vulcanized blends increases with increase in elastomer content with decrease in tensile strength. Dynamic mechanical analysis shows decrease in tanδ values as the elastomer and compatibilizer content increased. Thermograms obtained from differential scanning calorimetric studies reveal that compatibilized blends have lower T_m values compared to dynamically vulcanized blends, which confirms strong interaction between the plastic and elastomer phase. Scanning electron microscopic observations on impact fractured surface indicate reduction in particle size of elastomer phase and its high level of dispersion in the POM matrix. In the case of compatibilized blends high degree of interaction between the component polymers has been observed. POLYM. ENG. SCI., 47:934–942, 2007. © 2007 Society of Plastics Engineers     

片状粉末表面特性的分形分析

根据片状粉末表面几何特征,提出了用分形方法对其进行描述. 将数码相机拍摄的不同片状粉末的显微照片输入计算机,采用计算分形盒子维的DBC算法对其灰度值进行编程计算,可获得颗粒表面的分形维数. 计算得到的分维数的数值在2~3之间,且粉体表面越不光滑,表现在灰度值的起伏越大,则分维数的数值也越大,与人们视觉上对粗糙表面的观察相吻合. 在一定程度上可有效地反映粉体表面的光滑性,从而为片状粉体表面特性的分析和研究提供了一个新思路.     

Rheological properties of poly(methyl methacrylate)/rigid ladderlike polyphenylsilsesquioxane blends

A series of poly(methyl methacrylate) (PMMA) blends with rigid ladderlike polyphenylsilsesquioxane (PPSQ) were prepared at weight ratios of 100/0, 95/5, 90/10, 85/15, and 80/20 by solution casting and then hot‐pressing. Their rheological properties have been studied under both dynamic shear and uniaxial elongation conditions. Their rheological properties depend on the compositions. The storage modulus, G′, loss modulus, G″, and dynamic shear viscosity, η*, of the PMMA/PPSQ 95/5 blend were slightly lower than those of pure PMMA. However, the values of G′, G″, and η* for the other PMMA/PPSQ blends are higher than those of PMMA. The G′ values increase with an increase in PPSQ content from 5% through 15% PPSQ at low frequencies and then drop as the PPSQ content increases to 20%. Uniaxial elongational viscosity (η_E) data demonstrate that PMMA/PPSQ blends exhibit slightly weaker (5% PPSQ) and much weaker (10% PPSQ) strain‐hardening than PMMA. In contrast, the PMMA/PPSQ 85/15 blend shows strain‐softening. Neither strain‐hardening nor strain‐softening was observed in the 80/20 blend. The special rheological properties for the 95/5 blend is probably due to a decrease in PMMA entanglements brought by the specific PMMA–PPSQ interactions. Rheological properties of PMMA/PPSQ blends with higher PPSQ content (≥10%) are mainly affected by formation of hard PPSQ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 352–359, 2007     

Film formation from pigmented latex systems: Mechanical and surface properties of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex blend films

The mechanical and surface properties of films prepared from model latex/pigment blends were studied using tensile tests, surface gloss measurements, and atomic force microscopy. Functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA)] and ground calcium carbonate (GCC) were used as latex and extender pigment particles, respectively. The critical pigment volume concentration of this pigment/latex blend system was found to be between 50 and 60 vol % as determined by surface gloss measurement and tensile testing of the blend films. As the pigment volume concentration increased in the blends, the Young's modulus of the films increased. Nielsen's equations were found to fit the experimental data very well. When the surface coverage of carboxyl groups on the latex particles was increased, the yield strength and Young's modulus of the films both increased, indicating better adhesion at the interfaces between the GCC and latex particles. When the carboxyl groups were neutralized during the film formation process, regions with reduced chain mobility were formed. These regions acted as a filler to improve the modulus of the copolymer matrix and the modulus of the resulting films. The carboxyl groups on the latex particle surfaces increased the surface smoothness of the films as determined by surface gloss measurement. When the initial stabilizer coverage of the latex particles was increased, the mechanical strength of the resulting films increased. At the same time, rougher film surfaces also were observed because of the migration of the stabilizer to the surface during film formation. With smaller‐sized latex particles, the pigment/latex blends had higher yield strength and Young's modulus. Higher film formation temperatures strengthen the resulting films and also influence their surface morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4550–4560, 2006     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility in crystalline polymer blends: Isotactic polypropylene and linear low‐density polyethylene

The phase behavior and the crystallization kinetics of blends composed of isotactic polypropylene (iPP) and linear low‐density polyethylene (LLDPE) were investigated by differential scanning calorimetry. The phase behavior indicates the formation of separate crystals of iPP and LLDPE at each investigated blend composition. The crystallization trace reveals that iPP crystallizes in its normal range of temperatures (i.e., at temperatures higher than that of LLDPE), when its content in the blend is higher than 25% by weight. In the blend whose iPP content is as high as 25%, at least a portion of iPP crystallizes at temperatures lower than that of LLDPE. This behavior has been proposed by Bassett to be attributed to a change in the kind of nucleation from heterogeneous to homogeneous. From the Avrami analysis of the isothermal crystallization of iPP in the presence of molten LLDPE, n values close to 2 are always obtained. According to our previously proposed interpretation of the Avrami coefficient, it can be related to the crystallite fractal dimension, through d = n + 1, which gives values close to 3, according to the spherulitic observed morphology. The kinetics parameter, i.e., the half‐time of crystallization, and the kinetic constant k show that a decrease in the overall rate of crystallization of iPP occurs on blending. Optical microscopy photographs, taken during the cooling of the samples from the melt, confirm the above results and show increasingly less resolved spherulite texture on increasing LLDPE content in the blend. The diffusion parameters evaluated for the neat polymers and for the blends in dichloromethane, which give information on the miscibility in the amorphous state, show that the diffusional behavior of the blends is governed by iPP, suggesting a two‐phase amorphous state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3338–3346, 2003     

Effect of different biopolymers and polymers on the mechanical and permeation properties of extruded PHBV cast films

The biopolymer poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a promising material for packaging applications but its high brittleness is challenging. To address this issue, PHBV was blended with nine different biopolymers and polymers in order to improve the processing and mechanical properties of the films. Those biopolymers were TPS, PBAT, a blend of PBAT + PLA, a blend of PBAT + PLA + filler, PCL and PBS, and the polymers TPU, PVAc, and EVA. The extruded cast films were analyzed in detail (melting temperature, crystallinity, mechanical properties, permeation properties, and surface topography). A decrease in crystallinity and Young's modulus and an increase in elongation at break and permeability were observed with increasing biopolymer/polymer concentration. In PHBV‐rich blends (≥70 wt % PHBV), the biopolymers/polymers PCL, PBAT, and TPU increased the elongation at break while only slightly increasing the permeability. Larger increases in the permeability were found for the films with PBS, PVAc, and EVA. The films of biopolymer/polymer‐rich blends (with PBAT, TPU, and EVA) had significantly different properties than pure PHBV. A strong effect on the properties was measured assuming that at certain biopolymer/polymer concentrations the coherent PHBV network is disrupted. The interpretation of the permeation values by the Maxwell–Garnett theory confirms the assumption of a phase separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46153.     

Surface segregation of siloxane containing component in polysiloxane‐block‐polyimide and s‐BPDA/ODA polyimide blends

Surface segregation in polymer blend systems between 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐diaminodiphenyl ether (s‐BPDA/ODA) polyimide and block copolymer based on polysiloxane‐block‐polyimide (SPI) has been investigated. These polyimide blends, having various compositions of the SPI, were processed by a solution casting method. The glass substrate used in the film‐casting process shows significant effect on the migration of surface segregated species to enrich the air‐exposed surface, whereas the more polar s‐BPDA/ODA tends to remain close to the polar glass substrate. X‐ray photoelectron spectroscopy reveals that even at low SPI concentration, the siloxane moieties in the block copolymer tend to segregate into the air side surface. Contact angle measurement evidently indicates an enrichment of the hydrophobic siloxane fraction on the blend film surface. The average water contact angle of glass side surface is 77°C whereas that of the air side is about 102°C in every blend ratio. This behavior confirms the surface segregation phase separation in these polymer blends. Finally, the surface morphology observed by atomic force microscopy also suggests segregation type of phase separation in these blend systems. POLYM. ENG. SCI., 47:489–498, 2007. © 2007 Society of Plastics Engineers.