Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Filled reactive ethylene terpolymer primers for cathodic disbondment mitigation

A reactive ethylene terpolymer (RET) with inorganic fillers of clay, talc, and zinc was examined for its cathodic disbondment (CD) performance and as a potential coating primer material for pipeline applications. The filler type and volume fraction influenced the mechanical, thermal, adhesion, and CD resistance of the coatings. The tensile modulus and strength of the RETs increased at higher loadings of selected fillers. The dry adhesive strength of the clay‐filled RET maintained the same level of adhesion up to approximately 23 vol %, whereas the talc‐ and zinc‐filled RETs showed decreases in adhesive performance. CD resistance was significantly improved with 18–23 vol % clay, whereas the overall disbondment area was reduced approximately 82% from pure RET. However, the post‐cathodic‐disbondment adhesive strength for the clay‐filled RET decreased as a result of the degradation of the primer/topcoat interface caused by moisture absorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal,mechanical, and adhesive properties of HDPE/reactive ethylene terpolymer blends

Blends of high‐density polyethylene (HDPE) and a reactive ethylene terpolymer (RET) were developed as a protective coating material for steel. A morphological study with scanning electron microscopy (SEM) indicated that blends of HDPE and RET are immiscible, while high interaction between these two phases was found. Crystallization and thermomechanical behavior of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystallinity of HDPE decreased with the incorporation of RET slightly due to the disturbance of the highly viscous RET melt during crystallization. Tensile tests indicated that the addition of RET reduced both strength and modulus but increased the strain‐to‐break. Adhesion to steel substrates was improved with the incorporation of the RET component. An optimum composition of RET loading was detected to be in the range of 25–33 wt %, leading to the best adhesive performance, high tensile strength, and strain‐to‐failure of the blend material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 331–338, 2007     

Cathodic disbondment of epoxy coating with zinc aluminum polyphosphate as a modified zinc phosphate anticorrosion pigment

As an approach to improve the resistance of protective coatings to the disbondment, modification of the formulation through incorporation of zinc aluminum polyphosphate anticorrosion pigment representing third generation phosphates was examined in this paper. The data obtained from cathodic disbonding test, electrochemical impedance spectroscopy and pull-off indicated that introduction of zinc aluminum polyphosphate within epoxy coating could provide improved resistance to cathodic disbonding as well as superior adhesion strength. The superiority in the presence of the modified pigment was connected to deposition of a layer at the disbonding front and locally controlled pH as well. The precipitation restricting active zone available for electrochemical reaction was confirmed by SEM.     

Compatibilisation of PPE/SAN blends by triblock terpolymers: Correlation between block terpolymer composition, morphology and properties

Immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) with a weight composition of 60/40 were compatibilised by polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) using a two-stage melt-processing approach. In order to investigate the influence of the SBM composition on the compatibilisation efficiency, the block lengths of the triblock terpolymers were systematically varied. The resulting morphological features of the blend systems as function of SBM composition and processing parameters are correlated with the resulting thermal and thermo-mechanical properties. In the ideal case, SBM should be located at the interface as PS is miscible with PPE while PMMA is miscible with SAN. The elastomeric middle block as an immiscible component should remain at the interface. This particular morphological arrangement is known as the ‘raspberry morphology’. A detailed TEM analysis of the blend morphologies following initial extrusion-compounding revealed a high compatibilisation efficiency of the SBM types with equal lengths of the end blocks and, furthermore, the desired raspberry morphology was achieved. In contrast, high PS contents in comparison to the other blocks led to a pronounced micelle formation in the PPE phase. Further evaluation of the blend structures following injection-moulding indicated that the morphologies remain relatively stable during this second melt-processing step. A detailed thermal analysis of all blend systems supports the interpretation of the observed morphological features. The fundamental correlation between SBM composition and blend morphology established in this study opens the door for the controlled development of interfacial properties of such compatibilised PPE/SAN blends during melt-processing.     

Properties and morphologies of PVC/nylon terpolymer blends

A new kind of blends of polyvinyl chloride (PVC)/nylon terpolymer was reported in this article. Two compatibilizers were used in this study: one is a terpolymer of ethylene–n‐butyl acrylate–monoxide (EnBACO); the other is terpolymer of EnBACO grafted with maleic anhydride (EnBACO‐g‐MAH). The observation of scanning electron microscope (SEM) reveals that the PVC/nylon terpolymer blends have a two‐phase structure; and the nylon terpolymer phase is the continuous phase, and PVC domains in the PVC/nylon terpolymer/EnBACO‐g‐MAH blends have fine dispersion over a broad range of the PVC/nylon terpolymer ratio. EnBACO‐g‐MAH is more compatible with the nylon terpolymer than EnBACO. EnBACO and EnBACO‐g‐MAH have different effects on the glass transition temperatures of the PVC phase and nylon terpolymer phase in the blends. The notched Izod impact strength, tensile strength, elongation at break, Vicat softening temperature (VST), and melt flow index (MFI) critically depend on PVC/nylon terpolymer ratio, the kinds and concentration of the compatibilizers. The PVC/nylon terpolymer/EnBACO‐g‐MAH blends display a good combination of high toughness, high flowability, and high VST under low load. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2823–2832, 2001     

Poly(ethylene terephthalate)/polypropylene reactive blends through isocyanate functional group

To evaluate the compatibilization effects of an isocyanate group on poly(ethylene terephthalate)/polypropylene (PET/PP) blends through a reactive blend, PP grafted with 2‐hydroxyethyl methacrylate‐isophorone diisocyanate (PP‐g‐HI) was prepared and blended with PET. In view of the blend morphology, the presence of PP‐g‐HI reduced the particle size of the dispersed phase by the reduced interfacial tension between the PP and PET phases, indicating the in situ copolymer (PP‐g‐PET) generated during the melt blending. The DSC thermograms for the cooling run indicated that the PET crystallization in the PP‐g‐HI rich phase was affected by the chemical reactions of PET and PP‐g‐HI. The improved mechanical properties for the PET/PP‐g‐HI blends were shown in the measurement of the tensile and flexural properties. In addition, the water absorption test indicated that the PET/PP‐g‐HI blend was more effective than the PET/PP blend in improving the water resistance of PET. The positive properties of PET/PP‐g‐HI blends stemmed from the improved compatibilization of the PET/PP blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1056–1062, 2001     

Rheological behavior and processability of polypropylene blends with rubber ethylene propylene diene terpolymer

A study of the dynamic complex and steady shear viscosity of isotactic polypropylene (iPP), ethylene–propylene diene terpolymer rubber (EPDM) and three different blends of both polymers are presented over a range of temperatures and frequencies. Moreover, the processability of these materials is studied through torque measurements during blend mixing. The results obtained show that the viscosity gradually increases with rubber content in the blend and decreases with both temperature and frequency. Plots of η″ versus η′ (Cole–Cole plots) show that the blend with the lower rubber content (25%), has a certain rheological compatibility with neat PP. Furthermore, torque curves measured during blend mixing confirm these results, demonstrating that the blend with 25% of elastomer has a similar behavior of iPP during processing. To analyze the morphological structure of the blends, a dynamic mechanical analysis of the solid state is also presented. It is observed that the blends have two distinct values of T_g close to the corresponding values of the pure polymers, confirming that this type of blends based on a semicrystalline polymer and an amorphous elastomer forms a two‐phase system with a limited degree of miscibility between both components. In addition, the polymer present with the higher concentration forms the continuous phase and controls the rheological properties of the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1–10, 2001     

Properties of poly(ethylene terephthalate) and maleic anhydride-grafted polypropylene blends by reactive processing

The properties of poly(ethylene terephthalate) (PET) and polypropylene (PP) blends and PET/maleic anhydride-grafted PP (MAgPP) reactive blends were investigated. Two blend systems were immiscible based on tan δ measured by dynamic mechanical analyzer (DMA). In case of PET/MAgPP blends, the reaction of ester groups of PET and MA sites on MAgPP occurred during melt mixing at 280°C for 30 min. The reaction was confirmed by a new peak between the glass transition temperatures of PET-rich and MAgPP-rich phase on tan δ curves, as well as from the rheological properties. From the morphology, the improvement of the dispersibility in PET/MAgPP reactive blends was observed. The modulus of PET/MAgPP blends was higher than that of PET/PP blends, and the strength of PET/MAgPP blends showed the good adhesion compared with the PET/PP blends. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 389–395, 1998     

Miscibility of blends of ethylene‐propylene‐diene terpolymer and polypropylene

The miscibility of polymers is not only an important basis for selecting a proper blending method, but it is also one of the key factors in determining the morphology and properties of the blends. The miscibility between ethylene‐propylene‐diene terpolymer (EPDM) and polypropylene (PP) was explored by means of dynamic mechanical thermal analysis, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results showed that a decrease in the PP content and an increase of the crosslinking density of EPDM in the EPDM/PP blends caused the glass‐transition temperature peaks of EPDM to shift from a lower temperature to higher one, yet there was almost no variance in the glass‐transition temperature peaks of PP and the degree of crystallinity of PP decreased. It was observed that the blends prepared with different mixing equipment, such as a single‐screw extruder and an open mill, had different mechanical properties and blends prepared with the former had better mechanical properties than those prepared with the latter. The TEM micrographs revealed that the blends were composed of two phases: a bright, light PP phase and a dark EPDM phase. As the crosslinking degree of EPDM increased, the interface between the phases of EPDM and PP was less defined and the EPDM gradually dispersed in the PP phase became a continuous phase. The results indicated that EPDM and PP were both partially miscible. The mechanical properties of the blends had a lot to do with the blend morphology and the miscibility between the blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 315–322, 2002     

Study of propylene‐1‐butene‐ethylene terpolymer and reactor blend by TREF and 13C‐NMR

A terpolymer of propylene‐1‐butene‐ethylene (TERPO) and a reactor mixture of TERPO with an ethylene‐1‐butene copolymer (BLEND) were completely characterized by TREF, ¹³C‐NMR, DSC, and GPC, from which special equations for quantitative ¹³C‐NMR were derived. TERPO was shown to be composed mainly of highly isotactic propene and similar amounts of ethylene and 1‐butene. BLEND fractions were composed of variable amounts of TERPO and a random copolymer of ethylene‐1‐butene. The blend of TERPO and copolymer acts as two independent phases, each having its own elution temperatures dependent only on its crystallizability, itself only influenced by the comonomer content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1880–1890, 2001     

Toughening of immiscible PPE/SAN blends by triblock terpolymers

The mechanical performance of immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) and the subsequent influence of compatibilisation by tailored polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) on the mechanical performance under static and dynamic loads is analysed in detail. A PPE/SAN 60/40 blend was selected as a base system for the compatibilisation experiments. The observed static tensile behaviour is described by micromechanical models and correlated to the blend microstructures as observed by transmission electron microscopy. In most cases, the addition of the SBM triblock terpolymers further enhances the ductility of the blend while only leading to a minor reduction of modulus and strength. Triblock terpolymers with symmetric end blocks, mainly located at the interface between PPE and SAN, led to nearly isotropic specimens. In contrast, SBM materials with a longer polystyrene block predominantly formed micelles in the PPE phase and the blends revealed a highly anisotropic morphology. Comparative investigations of the fatigue crack growth behaviour parallel to the direction of injection also reflected this variation in mechanical anisotropy of the compatibilised blends. A poor toughness and a predominant interfacial failure were observed in the case of the SBM with a long polystyrene block. In contrast, a considerable improvement in properties as a result of pronounced plastic deformations was observed for blends compatibilised by triblock terpolymers with symmetric end blocks. The systematic correlation between morphology and mechanical performance of compatibilised PPE/SAN blends established in this study provides an efficient way for the desired selection of suitable and effective compatibilising agents, ensuring both a superior multiaxial toughness as well as a high strength and modulus of the overall system.     

Comparison of ethylene‐propylene diene terpolymer composites filled with natural and synthesized micas

In this paper, EPDM/mica composites were prepared by filling synthesized mica and natural mica separately into ethylene‐propylene diene terpolymer (EPDM) using melt blending technique. Microstructures, electrical properties, gas resistance, and mechanical properties of two EPDM/mica composites were investigated systematically. FTIR show that hydroxyl groups exist on the surface of the micas. These structural hydroxyls could be active sites conducive to the surface modification of mica. XRD analyses reveal that the natural mica is crystalline and the synthesized mica is amorphous. After being modified with silane coupling agent Si69, mica was only exfoliated into smaller micron agglomerates dispersing in EPDM, but the dispersion of amorphous synthesized mica was better. So the EPDM/synthesized mica composite possessed better mechanical property, electrical insulation property, and gas permeability resistance. It is expected that better improvement would be achieved, if mica is exfoliated further into nanosheets dispersing in the rubber matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

The effects of dynamic vulcanization and compatibilizer on properties of paper sludge‐filled polypropylene/ethylene propylene diene terpolymer composites

The effects of dynamic vulcanization (DV) and dynamic vulcanization plus compatibilizer (DVC) of paper sludge (PS) filled polypropylene/ethylene propylene diene terpolymer (PP/EPDM) composites on torque development, mechanical properties, water absorption, morphology, and thermal properties were studied. Results show that DV and DVC composites exhibit higher stabilization torque than unvulcanized composites (UV). The dynamic vulcanized (DV) and dynamic vulcanized plus compatibilizer (DVC) composites exhibit higher tensile strength, elongation at break, and Young's modulus but lower water absorption than unvulcanized composites. The scanning electron microscopy (SEM) study of tensile fracture surface of DV and DVC composites shows the improved interfacial interaction between PS and PP/EPDM matrix. The DV and DVC composites also exhibit better thermal stability and higher crystallinity than unvulcanized PP/EPDM/PS composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of compatible blends of poly(methyl methacrylate) used in dentistry with a reactive terpolymer containing maleic anhydride and their thermomechanical characterization

This study focuses on the preparation of compatible blends with the poly(methyl methacrylate) (PMMA) using a reactive terpolymer maleic anhydride–styrene–vinyl acetate (MA–St–VA). In the first series of experiments, binary blends of the PMMA and the MA–St–VA terpolymer have been prepared in tetrahydrofurane. The PMMA and the MA–St–VA terpolymer formed the compatible blends. The effects on thermomechanical properties of MA–St–VA terpolymer ratio in the blends were studied. The glass transition temperatures (T_g), thermal expansion coefficient (α), and other thermomechanical parameters for the blends have been established by TMA method and the compatibility of two polymers has been evaluated by these TMA parameters. The addition of MA–St–VA terpolymer to PMMA made a plasticizing effect on PMMA. This effect regularly changed with the increasing of the terpolymer in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 363–367, 2006     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

Reactive compatibilization of ABS/Nylon 6,6 blends: Effects of reactive group concentration and blending sequence

Styrene-acrylonitrile-glycidyl methacrylate (SAG) copolymers with various glycidyl methacrylate (GMA) contents have been used to compatibilize the incompatible blends of acrylonitrile-butadiene-styrene (ABS) and nylon 6,6 (N66) by varying the blending sequences. When the epoxy group of SAG copolymer makes contact and reacts with the amine endgroup of N66, the resultant grafted products, SAG-g-N66, tend to reside at interface and act as compatibilizers of the blends. For a SAG copolymer with lower GMA content (SG2), a better compatibilized blend is achieved by sequential blending of the SAG2 with N66 then with ABS. When a higher GMA content SAG (SAG 10) is employed, on the contrary, a better compatibilized blend is obtained by preblending SAG10 with ABS then with N66. A grafted SAG-g-N66 molecule is considered as an effective compatibilizer when it anchors along the interface with the ungrafted SAG, or the SA segments, penetrating into the ABS phase while the branched N66 chains protruding into the N66 phase. The conventional one-step three-component blending usually results in less compatibilized blend than the properly selected sequential blending. The trend of mechanical properties observed closely match the compatibility of the blend in terms of domain size. However, the overall improvement of the resultant mechanical properties of the compatibilized blend over the uncompatibilized one is not substantial.     

团状模塑料/三元乙丙橡胶共混物的表征及其性能的影响因素

用团状模塑料(DMC)与三元乙丙橡胶(EPDM)共混,以EPDM为连续相、DMC为分散相,制备了DMC/EPDM共混物,并对其微观结构进行了表征,研究了DMC与EPDM的质量比、过氧化物硫化荆的种类和用量以及白炭黑的用量对共混物性能的影响.结果表明,DMC和EPDM的界面作用强,相容性好;过氧化苯甲酰(BPO)作硫化荆要好于用过氧化二异丙苯;当DMC与EPDM的质量比为90/100、BPO为5份、白炭黑为50份时,共混物的力学性能和耐热老化性较好.