Poly(dimethylsiloxane)-polyimide blends in the formation of thick polyimide films

Thick polyimide layers can be formed by using some unique properties of poly(dimethylsiloxane)-polyimide (PDMS/PMDA–ODA) blends followed by surface modification and deposition of a second layer of polyimide precursor chemicals. The method is based on the micro-phase separation characteristics of these blends to yield surfaces that have PDMS-like character. Upon modification with UV/ozone treatment, a surface that is essentially SiO _x and hydrophilic in nature is produced. This surface is amenable to reaction and deposition of a second polyimide layer from polyimide precursors. The thicker polyimide layer has enhanced adhesion between the original layer of the blend and the new polyimide layer and this approach finds extensive applications for products that require thick polymer layers. Changes in surface energy for various blend compositions were monitored by measurement of advancing contact angle with de-ionized water. Contact angle for unmodified polyimide films was on the order of 70° and it increased to about 104° after blending with PDMS and curing. UV/ozone treatment reduced the contact angle of the doped polyimide to less than 5°. X-ray photoelectron spectroscopy (XPS) and angle resolved XPS (ARXPS) measurements were used to monitor the chemical compositions of the various surfaces. High-resolution XPS spectra in the Si2p region confirm the transformation of O–Si–C bonds in PDMS to SiO _x , where x is about 2. Scanning electron microscopy (SEM) of some selected samples shows that the blends contain phase separation of the polymers at the surfaces of the samples. Atomic force microscopy (AFM) of siloxane-free polyimide, and PDMS/PMDA–ODA blends both prior to and after UV/ozone exposure, show that the films are essentially flat at short treatment times (less than 60 min). AFM also reveals the separation of PDMS into micro-domains at the cured film surface and throughout the layer below the surface of the blended films. Adhesion of a subsequently deposited polyimide layer to the modified polyimide surface was found to be greatly improved when compared to the adhesion obtained for deposition onto a pristine polyimide surface.     

Synthesis of porous methylphenylsiloxane/poly(dimethylsiloxane) composite using poly(dimethylsiloxane)-poly(ethylene oxide) (PDMS-PEO) as template

Poly(dimethylsiloxane)-poly(ethylene oxide) (PDMS-PEO) diblock copolymer has been used as template in methylphenylsiloxane (MPS) resin matrix to fabricate porous MPS/PDMS composite. The structure of resulting materials has been characterized by transmission electron microscopy (TEM), nitrogen-sorption measurements, and ¹H NMR. Experiments show that MPS/PDMS composites with pore structures and large pore sizes have been obtained. The BET surface area, pore volume, and mean pore size of porous MPS/PDMS composites are calculated to be 285 m²/g, 0.21 cm³/g, and 24.2 nm, respectively.     

Studies on poly (hydroxy alkanoates)/(ethylcellulose) blends

Biodegradable polymers represent one of the most significant area of research today. Among these polymers, poly (β-hydroxy butyrate co β′-hydroxy valerate) i.e. PHBV have received special attention because of their unique combination of properties. They are perfectly biocompatible, biodegradable polymers and can be processed by any conventional technique. In the present study an attempt has been made to develop the biodegradable blends of PHBV by blending them with ethyl cellulose (EC). Ethyl cellulose has been selected to monitor the biodegradation rate of PHBV and also for making the blends cost effective. The blends are thoroughly characterized for their compatibility, by the measurement of viscosity of blends and through FT-IR. Various applications of PHBV/EC blend in agriculture and pharmaceutical industries are being explored. Paper presented at the 5th IUMRS ICA98, October 1998, Bangalore.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Tensile behaviour of blends of poly(vinylidene fluoride) with poly(methyl methacrylate)

Blends of poly(vinylidene fluoride) (PVF₂) and poly(methyl methacrylate) (PMMA) were prepared over a wide concentration range and tested in tension at the same relative temperature below the glass transition. Testing was performed at strain rates ranging from 10 to 0.01 min^–1 at test temperatures fromT _g-40 toT _g-10. By normalizing the test temperature to fixed increments belowT _g, blends and homopolymers can be compared on the basis of PVF₂ and PMMA composition and crystallinity. In nearly all blends, under conditions favouring disentanglement, (decrease in strain rate, or increase in test temperature), the yield stress and drawing stress decreased while the breaking strain increased. For materials with about the same degree of crystallinity, those with a higher proportion of amorphous PVF₂ exhibited brittle-like behaviour as a result of interlamellar tie molecules. In the semicrystalline blends, yield stress remains high as the test temperature approachesT _g, whereas in the amorphous blends the yield stress falls to zero nearT _g. Results of physical ageing support the role of interlamellar ties which cause semicrystalline blends to exhibit ageing at temperatures aboveT _g.     

Viscoelastic properties of poly(butylene terephthalate)/poly(ethylene naphthalate) blends

Melt blends of poly(butylene terephalate) (PBT) and poly(ethylene naphthalate) (PEN) with 30 and 60 wt% PEN were prepared using a single screw extruder and an injection moulding machine. Stress relaxation tests for the specimens of PBT/PEN blends and the homopolymers were carried out using an Instron testing machine in an Instron environmental chamber. The Taguchi method of experimental design analysed how different levels of temperature, PEN content and initial stress affected the relaxation behaviour of PBT/PEN blends and homopolymers. From the response tables and analyses of main and interaction effects, it was shown that the most significant factor was temperature, followed by PEN content and then the initial stress. Consequently, high temperature, low PEN content and high initial stress speeded up stress relaxation rate of specimens. Interaction effects between factors were insignificant. To fit the relaxation curves of the PBT/PEN blends and the homopolymers at different temperatures, PEN contents and the initial stresses, four different equations were attempted with Matlab™, which determined the coefficients of these functions using the experimental data of stress change with time. The simulated curves from the most suitable function among them were shown using the calculated coefficients to predict the relaxation behaviour of PBT/PEN blends (50% PEN) at temperatures of 30 and 60°C with an initial stress of 7 MPa.     

Mechanical properties of blends of poly(methyl methacrylate) and poly(vinylidene fluoride)

The mechanical properties of blends of the crystallizable polymer poly(vinylidene fluoride) and the amorphous material poly(methyl methacrylate) have been investigated as a function of composition both for glassy amorphous materials and for partially crystalline materials. The data obtained were interpreted in terms of the molecular and super-molecular structure of the blends and in terms of their dynamic properties.The main conclusions were that the mechanical properties are not strongly dependent on details of the distribution of the two components in the material nor on the crystal modifications present. The mechanical properties were found to depend primarily on the location of the glass transition temperature relative to the elongation temperature and on the presence or absence of crystalline regions. The degree of crystallinity was found to play an important role in determining the properties only at lower values of this quantity. The advantage of these blends is that the important parameters, namely, the degree of crystallinity and the location of the glass transition temperature, can be adjusted at will by varying the composition appropriately. This allows well-defined variations of the mechanical properties to be achieved.     

Microcellular extrusion foaming of poly(lactide)/poly(butylene adipate-co-terephthalate) blends

Foamed poly(lactide) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends were processed via the microcellular extrusion process using CO₂ as a blowing agent. Talc has been added to promote heterogeneous nucleation. Two types of PLA/PBAT blend systems were investigated: Ecovio, which is a commercially available compatibilized PLA/PBAT blend; and a non-compatibilized PLA/PBAT blend at the same PLA/PBAT ratio (i.e., 45:55 by weight percent). Six different formulations were investigated: pure PLA, PLA-talc, Ecovio, Ecovio-talc, non-compatibilized PLA/PBAT blend, and non-compatibilized PLA/PBAT-talc. The effects of various processing parameters such as die temperature, talc and compatibilization on various foaming properties such as cell morphology, volume expansion ratio (VER), open cell content (OCC) and crystallinity were investigated. As per the DSC thermograms, it was observed that compatibilization has merged the two distinctive melting peaks of PLA and PBAT into a single peak while lowering the peak temperature. In general, the addition of talc has decreased the average cell size and VER and increased the cell density and crystallinity; however, it has varying effects on the open cell content. Compatibilization has reduced the average cell size and volume expansion but increased the cell density and had varying and no effects on the OCC and crystallinity, respectively. Similar to compatibilization, the die temperature was found to have varying and no effects on the OCC and crystallinity, respectively. Except for PLA and non-compatibilized PLA/PBAT blend, the cell size and VER of all other formulations did not vary much throughout the entire temperature range (130–150 °C). The cell density was found to be insensitive to die temperatures except for Ecovio and Ecovio-talc.     

Characterization of hydrogel blends of poly(vinyl pyrrolidone) and poly(vinyl alcohol-vinyl acetate)

Hydrogel blends were prepared from water-soluble polymers of poly(vinyl alcohol-vinyl acetate) and poly(vinyl pyrrolidone). The method of preparation was optimized and different compositions of blends were characterized. The effect of thermal treatment and the introduction of an aldehydic crosslinking agent in the blend was also studied. The swelling characteristics of the various compositions, their thermal behaviour and the state of water was examined. Mechanical properties of the hydrogels were determined and it was observed that blends containing glutaraldehyde produced materials with good mechanical integrity and high water contents.     

In situ polymerization preparation of blends of poly(methyl methacrylate) and poly(styrene-co-acrylonitrile)

The in situ polymerization of methyl methacrylate (MMA) with poly(styrene-co-acrylonitrile) (SAN) was studied. The PMMA/SAN in situ polymerization blends obtained were examined by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), tensile tests and scanning electron microscopy (SEM). The blends with compositions of 95/5, 80/20, 70/30, and 60/40 in weight ratios were miscible and had a single phase structure. However, the 90/10 PMMA/SAN in situ polymerization blend obtained was inhomogeneous and had a two-phase structure; polymerization-induced phase separation occurred during the preparation process of the blend. Both tensile strength and elongation at break increase with increasing SAN content up to 30 wt%. The degradation temperature and thermal stability of PMMA increased remarkably on incorporation of SAN up to 30 wt%.     

Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride) blends

Isothermal crystallisation of blends of Poly(ethylene oxide) and Poly(vinyl chloride), PEO/PVC, was analysed by differential scanning calorimetry (DSC). The influence of the amorphous polymer, PVC, on crystallisation rate of PEO was investigated using pure PEO as reference. Pure PEO and PEO/PVC blends were submitted to different crystallisation temperatures (from 40 to 58°C) and crystallisation times (from 1 to 72 h). Using the Hoffman-Weeks plot procedure, the equilibrium melting temperature, T _m°, was determined for pure PEO and for PEO/PVC blends with compositions (in wt%): 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70 and 20/80. The lamellar thickness factor of PEO crystals for pure PEO and for the blends showed a strong decrease when the PVC content was higher than 60 wt%. A small depression in T _m° was verified as the composition of PVC was increased. From the depression in T _m° the polymer-polymer interaction parameter, ₁₂, was evaluated using the Nishi-Wang equation. The results indicate that the miscibility between PEO and PVC in the molten state depends on the blend composition. The crystallisation rate also depends on the blend composition: the richer in PVC is the blend, the slower the crystallisation process.     

Effect of blend composition on the rheology property of polypropylene/poly (ethylene-1-octene) blends

In the present study, the dynamic viscoelastic properties for binary blends consisting of polypropylene (PP) and poly (ethylene-1-octene) (POE) were investigated using a Stresstech Rheometer in molten states at 210 °C. The results show that the blends with different content of POE present diversified rheological behaviors. Meanwhile, the blends with 10 wt% and 20 wt% POE show especial rheological behaviors. The dynamic complex viscosity of the blends with 10 wt% and 20 wt% POE are higher than that of others. The storage modulus and loss modulus of the blends with 10–40 wt% POE are different from other blends, and the blends with 10 wt% POE present the largest relaxation time. This behavior is probably related to the miscibility and long chain branch of POE in the PP/POE blends.     

Design,synthesis and physical properties of poly(styrene-butadiene-styrene)/poly(thiourea-azo-sulfone) blends

A new aromatic azo-polymer, poly(thiourea-azo-sulfone), has been synthesized using 1-(4-thiocarbamoylaminophenylsulfonylphenyl)thiourea and diazonium salt solution. Conducting and thermally stable rubbery blends of poly(styrene-block-butadiene-block-styrene) (SBS) triblock copolymer and poly(thiourea-azo-sulfone) (PTAS) were produced by solution blending technique. PTAS possessed fine solubility in polar solvents and high molar mass 63 × 10₃ g moL^?1. Microscopic analysis on SBS/PTAS blends revealed good adhesion between the two polymers without macro phase separation. Electrical conductivity measurement recommended that blending of SBS with 60% PTAS was sufficiently conducting 1.43 S cm^?1. A relationship between PTAS loading and thermal stability of blends was observed. With the increasing PTAS content, 10% gravimetric loss was increased from 481 to 497 °C, while glass transition improved from 123 to 136 °C (better than neat SBS but lower than PTAS). The blends also established higher tensile strength (52.40–59.96 MPa) relative to SBS. Fine balance of properties renders new SBS/PTAS, potential engineering plastics for a number of aerospace relevance.     

Fracture behaviors of isotactic polypropylene/poly(ethylene oxide) blends: Effect of annealing

As a part of serial work about the toughening of isotactic polypropylene (iPP) during annealing treatment, this work reports the effect of annealing on fracture behaviors of iPP blend with a little of poly(ethylene oxide) (PEO). Injection-molded bars of an iPP/PEO blend were annealed at different temperatures (50-160 °C) for 12 h and at 100 °C for different durations (12-96 h). The fracture behaviors of the annealed samples, including notched Izod impact fracture, universal tensile fracture, and single-edge notched tensile (SENT) fracture, were comparatively investigated to establish the role of annealing in improving the fracture resistance of the sample. The results showed that the annealing treatment greatly influences the fracture resistance of the blend. The impact-fractured surface morphologies were characterized by scanning electron microscope (SEM) to clarify the possible mechanisms for the improvement of the fracture resistance. It was proposed that, the excellent fracture resistance of iPP with a minor phase of which exhibits relatively low melting temperature can be easily achieved through the simple annealing treatment, even if the minor phase is immiscible with iPP.     

Dynamic mechanical characterization of hydrogel blends of poly(vinyl alcohol-vinyl acetate) with poly(acrylic acid) or poly(vinyl pyrrolidone)

Transparent hydrogels were prepared by blending solutions of poly(vinyl alcohol-vinyl acetate) with either poly(acrylic acid) or poly(vinyl pyrrolidone) in the presence of glutaraldehyde as a crosslinking agent. The network obtained from the poly(vinyl pyrrolidone) system was subjected to various thermal treatments, the effects of which have been studied. Dynamic mechanical analysis was used to characterize the hydrogels and to establish the suitability of these blends for use in biomedical applications. The swelling behaviour was followed under dynamic loads as well as by mass difference. Different frequencies were used to study the dynamic properties of the hydrogel blends which showed an increase in storage modulus with increasing frequency. A comparison of modulus values obtained dynamically were in agreement with data obtained mechanically in tension.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials. Oporto, Portugal, 10–13 September.     

Effect of starch type on miscibility in poly(ethylene oxide) (PEO)/starch blends and cytotoxicity assays

This study reports results on the miscibility of polymer blends based on PEO and different starches (unmodified, cationic, and hydrophobic) and their respective cytotoxicity. Films of PEO/starch blends at different weight ratios (95/05, 90/10, 80/20, 70/30, 65/35, and 60/40), as well as films of pure PEO as control, were prepared by casting methodology. Several techniques, such as SEM, WAXS, FTIR, and FT-Raman spectroscopy were used in this study for evaluating blend miscibility. The results revealed that the miscibility of such blends is dependent on the type of starch used. Regarding the PEO/unmodified starch blends, it was concluded that the system is miscible in the ratio range from 90/10 to 65/35. Although the PEO/hydrophobic starch blends are miscible in all the studied range, blends of PEO and cationic starch are immiscible, regardless the blend ratio. The different samples presented distinct cytotoxic behaviors. PEO and hydrophobic starch presented no relevant toxicity (CC_50/72 > 2.5 mg/mL). Otherwise, the cationic starch was the most harmful for the cells. The blends presented cytotoxicity values between those of PEO and cationic starch.     

Toughened blends of poly(butylene terephthalate) and BPA polycarbonate

The morphologies of melt blends of poly(butylene terephthalate) (PBT) and bisphenol A polycarbonate (PC) toughened with a core/shell impact modifier have been characterized by transmission and scanning electron microscopy. Selective staining with ruthenium and osmium tetroxide and etching with diethylene triamine have been used to assess the distribution of the various blend components and investigate the effects of thermal history on morphology. Strong evidence for partial melt miscibility of PC and PBT and rate-dependent segregation during cooling is presented.     

Review Properties of blends and composites based on poly(3-hydroxy)butyrate (PHB) and poly(3-hydroxybutyrate-hydroxyvalerate) (PHBV) copolymers

Poly(3-hydroxy)butyrate (PHB) and poly(3-hydroxybutyrate-hydroxyvalerate) (PHBV) copolymers are microbial polyesters presenting the advantages of biodegradability and biocompatibility over other thermoplastics with useful mechanical properties. However, their costs and performances must be adjusted by blending with suitable polymers. In this article the miscibility, morphology, mechanical behaviour and other prominent characteristics of a representative number of blends and composites of PHB and PHBV are summarized. In particular, blends with a few polyethers, polyesters, polyvinylacrylates and polysaccharides are illustrated. Furthermore, a brief paragraph deals with PHB/vegetal fiber composites. A wide range of properties emerges by blending with polymers having very different molecular structures and characteristics, such as crystallinity, glass transition and melting temperatures. The microstructure of the blends, resulting from thermodynamic and kinetic factors, is regarded as an important factor in controlling the mechanical and the biodegradation behaviours. Moreover, some considerations upon the nature of the driving force of the miscibility have been made in order to explain miscibility behaviour differences.     

Study of poly(methyl methacrylate)/poly(ethylene oxide) blends in solution. I

Determination of polymer-polymer interaction parameters (b₂₃) has been made by viscometry for poly(methyl methacrylate)/poly (ethylene oxide) blends, in solution, of a wide range of molecular weights of both polymers. The results obtained show that the compatibility of the polymer pair PMMA/PEO in 1.2-dichloroethane depends not only on the molecular weight of the samples used but also on the concentration of one polymer in relation to another.