From carbon nanotube coatings to high‐performance polymer nanocomposites

Since their discovery at the beginning of the 1990s, carbon nanotubes (CNTs) have been the focus of considerable research by both academia and industry due to their remarkable and unique electronic and mechanical properties. Among numerous potential applications of CNTs, their use as reinforcing materials for polymers has recently received considerable attention since their exceptional mechanical properties, combined with their low density, offer tremendous opportunities for the development of fundamentally new material systems. However, the key challenge remains to reach a high level of nanoparticle dissociation (i.e. to break down the cohesion of aggregated CNTs) as well as a fine dispersion upon melt blending within the selected matrices. Therefore, this contribution aims at reviewing the exceptional efficiency of CNT coating by a thin layer of polymer as obtained by an in situ polymerization process catalysed directly from the nanofiller surface, known as the ‘polymerization‐filling technique’. This process allows for complete destructuring of the native filler aggregates. Interestingly enough, such surface‐coated carbon nanotubes can be added as ‘masterbatch’ in commercial polymeric matrices leading to the production of polymer nanocomposites displaying much better thermomechanical, flame retardant and electrical conductive properties even at very low filler loading. Copyright © 2007 Society of Chemical Industry     

Modification of high‐performance polymer composite through high‐energy radiation and low‐pressure plasma for aerospace and space applications

In this investigation, attempts are made to modify a high‐performance polymer such as polybenzimidazole (PBI) (service temperature ranges from ?260°C to +400°C) through high‐energy radiation and low‐pressure plasma to prepare composite with the same polymer. The PBI composites are prepared using an ultrahigh temperature resistant epoxy adhesive to join the two polymer sheets. The service temperature of this adhesive ranges from ?260°C to +370°C, and in addition, this adhesive has excellent resistance to most acids, alkalis, solvents, corrosive agents, radiation, and fire, making it extremely useful for aerospace and space applications. Prior to preparing the composite, the surface of the PBI is ultrasonically cleaned by acetone followed by its modification through high‐energy radiation for 6 h in the pool of a SLOWPOKE‐2 (safe low power critical experiment) nuclear reactor, which produces a mixed field of thermal and epithermal neutrons, energetic electrons, and protons, and γ‐rays, with a dose rate of 37 kGy/h and low‐pressure plasma through 13.56 MHz RF glow discharge for 120 s at 100 W of power using nitrogen as process gas, to essentially increase the surface energy of the polymer, leading to substantial improvement of its adhesion characteristics. Prior to joining, the polymer surfaces are characterized by estimating surface energy and electron spectroscopy for chemical analysis (ESCA). To determine the joint strength, tensile lap shear tests are performed according to ASTM D 5868–95 standard. Another set of experiments is carried out by exposing the low‐pressure plasma‐modified polymer joint under the SLOWPOKE‐2 nuclear for 6 h. Considerable increase in the joint strength is observed, when the polymer surface is modified by either high‐energy radiation or low‐pressure plasma. There is further significant increase in joint strength, when the polymer surface is first modified by low‐pressure plasma followed by exposing the joint under high‐energy radiation. To simulate with spatial conditions, the joints are exposed to cryogenic (?196°C) and high temperatures (+300°C) for 100 h. Then, tensile lap shear tests are carried out to determine the effects of these environments on the joint strength. It is observed that when these polymeric joints are exposed to these climatic conditions, the joints could retain their strength of about 95% of that of joints tested under ambient conditions. Finally, to understand the behavior of ultrahigh temperature resistant epoxy adhesive bonding of PBI, the fractured surfaces of the joints are examined by scanning electron microscope. It is observed that there is considerable interfacial failure in the case of unmodified polymer‐to‐polymer joint whereas surface‐modified polymer essentially fails cohesively within the adhesive. Therefore, this high‐performance polymer composite could be highly useful for structural applications in space and aerospace. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1959–1967, 2006     

Triazine‐containing benzoxazine and its high‐performance polymer

A new synthetic route was designed to significantly increase the content of triazine structure in benzoxazine resin. 2,4,6‐Tri(4‐hydroxylphenyl)‐13,5‐s‐triazine (TP) was synthesized by cyclotrimerization of 4‐cyanolphenol and then benzoxazine monomer‐containing triazine [2,4,6‐tri(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazin‐6‐yl)‐1,3,5‐s‐triazine (BZ‐ta)] was synthesized via Mannich reaction from TP. Finally, the cross‐linked polymer P(BZ‐ta) was produced by thermal polymerization of BZ‐ta. BZ‐ta was characterized by nuclear magnetic resonance spectroscopy (NMR), fourier transform infrared spectroscopy (FTIR), mass spectrum, elemental analysis, and viscosity measurement. Curing behavior of BZ‐ta was studied by differential scanning calorimetry, FTIR, and gel permeation chromatography. The structure and properties of P(BZ‐ta) were investigated by powder X‐ray diffraction, dynamic mechanical analysis, and thermogravimetric analysis. The results showed that the P(BZ‐ta) had high glass temperature (T_g = 322°C), excellent thermal oxidation stability (5 and 10% weight loss temperatures in air up to 403 and 453°C, respectively), high char yield (64%, 800°C in nitrogen), and high flame‐retardance (limiting oxygen index, 39.7). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal aging of a blend of high‐performance fibers

The focus of this work is the study of the thermal aging of high‐performance fibers used in the making of fire protective garments. Accelerated thermal aging tests were carried out on fabric samples made up of a blend of Kevlar® (poly p‐phenylene terephthalamide) and PBI (poly benzimidazole) staple fibers, as well as on yarns pulled from this fabric, by means of exposure to elevated temperatures, comprised between 190°C and 320°C. All samples underwent loss of breaking force retention. The material thermal life, defined as the time required for the fibers to attain a 50% reduction of the original breaking force, ranged between a dozen of days at the lowest exposure temperature, to less than an hour at the highest. Breaking force data were fitted using the Arrhenius model following two different approaches, namely the extrapolated thermal life value and the shift factors yielded by the time‐temperature superposition (TTS). The Arrhenius model seemed to describe appropriately the overall aging process, as inferred from the excellent fit obtained when using both approaches, although activation energies provided from both approaches are different. To follow the chemical evolution of the material with thermal aging, Fourier‐transform infrared (FTIR) analyses were conducted. The qualitative analysis of the FTIR spectra showed little evidence of chemical changes between the aged and the nonaged samples, indicating either that the aging process carries on without significant modification of the chemical structure of the fibers, or that FTIR is not an appropriate method to spot such a modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Functionalization of sisal fibers and high‐density polyethylene by cold plasma treatment

Chopped sisal fibers and finely powdered high‐density polyethylene were surface functionalized using dichlorosilane (DS) under radio frequency (RF)‐plasma conditions and characterized by electron spectroscopy for chemical analysis (ESCA) and fluorescence labeling techniques. A high‐capacity (10 L), rotating, 13.56 MHz, electrodeless plasma installation, specially designed to allow the uniform surface modification of powdery and particulate matter of irregular shape, was used. A three‐factor fractional experimental design was employed to evaluate the effect of RF‐power, pressure, and reaction time on the ESCA‐based relative atomic composition of plasma‐treated samples. It was demonstrated that ? SiH_xCl_y functionalities are present on plasma‐exposed surfaces and these functionalization reactions can be controlled by selecting proper plasma parameters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2145–2154, 2002     

Producing high‐quality precursor polymer and fibers to achieve theoretical strength in carbon fibers: A review

The precursor fiber quality has a large impact on carbon fiber processing in terms of its performance, production yield, and cost. Polyacrylonitrile precursor fibers have been used commercially to produce strong carbon fibers with average tensile strength of 6.6 GPa. There is a scope to improve the average tensile strength of carbon fibers, since only 10% of their theoretical strength has been achieved thus far. Most attempts to increase the tensile strength of carbon fibers have been made during the conversion of precursor fiber to carbon fiber. This review highlights the potential opportunities to enhance the quality of the polyacrylonitrile‐based precursor fiber during polymer synthesis, spinning, and postspinning. These high‐quality precursor fibers can lead to new generation carbon fibers with improved tensile strength for high‐performance applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43963.     

Evaluation of optimum condition for designing high‐performance electro‐driven polymer hydrogel systems

This study investigated a parameter that determines an optimum condition of the content of the ionic group and the concentration of outer solution for high‐performance electro‐driven polymer hydrogel membranes. The optimum condition for quick bending was determined by a simple method that identified the initial conditions based on Donnan equilibrium theory. Since the bending behavior depends on the initial conditions of the ionic group content and the concentration of the outer solution, it can be predicted by the ratio of the ionic concentrations at the membrane–solution interface; the inverse of the Donnan ratio (1/K) at the initial condition. The bending rate of the membranes showed a maximum value at around 1/K = 0.15. The relationship between several interrelated control factors and the bending dynamics of the gel membranes was established by using the initial system parameters alone. 1/K is the effective simple parameter to determine the optimum condition of the content of the ionic group and the concentration of the outer solution for high‐performance membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 111–118, 2000     

Highly crystalline and oriented high‐strength poly(ethylene terephthalate) fibers by using low molecular weight polymer

High‐strength poly(ethylene terephthalate) (PET) fibers were obtained using low molecular weight (LMW) polymervia horizontal isothermal bath (hIB), followed by postdrawing process. We investigated the unique formations of different precursors, which differentiated in its molecular orientation and crystalline structures from traditional high‐speed spinning PET fibers. Sharp increase in crystallinity was observed after drawing process even though the fibers showed almost no any crystallinity before the drawing. Properties of as‐spun and drawn hIB and control filaments at different process conditions were compared. As would be expected, performances of resulted treated undrawn and drawn fibers have dramatically improved with developing unique morphologies. Tenacities more than 8 g/d for as‐spun and 10 g/d for drawn treated fibers after just drawn at 1.279 draw ratio were observed. These performances are considerably higher than that of control fibers. An explanation of structural development of high‐strength fibers using LMW polymer spun with hIB is proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42747.     

Tribological and thermal properties of hexagonal boron nitride filled high‐performance polymer nanocomposites

High‐performance polymer nanocomposites based on poly(aryletherketone) (PAEK) as matrix and hexagonal boron nitride (h‐BN) nanopowder as reinforcement were fabricated using planetary ball mill followed by hot pressing. The addition of h‐BN (0–5 wt %) to the matrix enhanced the microhardness and thermal stability compared to pure matrix. For a constant sliding speed, the wear rate of the nanocomposites determined by using Pin‐on‐Disk tribometer was reduced approximately 22 times compared to pure matrix. The coefficient of friction of the nanocomposites is slightly increased but it is stable compared to that of pure matrix. It was also investigated that the thermal stability of the debris of the nanocomposites was decreased compared to the pure matrix and its nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44409.     

Ethylene/ ammonia plasma polymer deposition for controlled adhesion of graphite fibers to PEEK

Plasma polymerization of ethylene and ammonia gas mixtures is used to obtain uniform polymer coatings on the surface of AS4 graphite fibers. The polymer deposition rates were determined for processing parameters such as composition of the monomer mix, monomer flow rate, chamber pressure, and power input of the radio frequency field. Plasma formed polymers were characterized using Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). XPS spectra were collected at 75° and 30° takeoff angles to obtain elemental composition and functional group populations at different sampling depths. Plasma deposition rate was the smallest for 100% ethylene and increased by three to four fold when ammonia was added to the monomer mixture. The polymer coatings were of uniform thickness and exhibited a complex crosslinked structure. The 100% ethylene plasma polymer was strongly hydrocarbon in nature but had some oxygen and nitrogen containing groups. Plasma polymers from ethylene/ammonia mixture were much more polar and contained reactive and polar group constituents, including carbonyl, ether, primary and secondary amines, and hydroxyl groups. The presence of oxygen and nitrogen functionalities is presumed to arise primarily from the reaction of trapped radicals with oxygen and nitrogen when exposed to air. Small amounts of silicon were also detected in the plasma formed films.     

Stability of high‐bandwidth graded‐index polymer optical fiber

The properties of poly(methyl methacrylate) (PMMA)‐based graded‐index polymer optical fiber (GI POF), including the thermal stability, thermal humidity, and mechanical properties, were studied for polymer optical fiber research and applications. The glass‐transition temperature of the fiber core was 103°C in the presence of the dopant, which was close to that of the PMMA matrix without the dopant. A special refractive‐index profile derived from the distribution of the dopant was stable at 60°C. Moreover, GI POF exhibited good mechanical properties. The excellent performance indicated that GI POF could be applied not only for indoor use but also for outdoor use. However, PMMA‐based GI POF exhibited poor hot‐water/humidity resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2330–2334, 2004     

Compatibilization of polymer blends with high‐molecular‐weight peroxides

A novel approach for the compatibilization of heterogeneous polymer blends with interface‐active high‐molecular‐weight peroxides is presented. This three‐step approach includes the synthesis of an anchor peroxide copolymer, the preparation of an interface‐active, peroxide‐containing graft copolymer (precompatibilizer) on its basis, and the localization of the precompatibilizer at the interfaces of the polymer blends during reactive blending with the in situ formation of compatibilizer macromolecules. We found that the precompatibilizer incorporating polypropylene fragments compatibilized blends of polypropylene with polystyrene, polyethylene, and unsaturated polyester resin. This verified a certain universality of the approach proposed for the compatibilization of polymer blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 232–242, 2005     

Optimization of single‐zone drying of polymer solution coatings using mathematical modeling

Optimal conditions for drying polymer–solvent coatings result from a trade‐off between minimizing the residual solvent level and creating defects. This article describes an application of automated constrained optimization with a detailed mathematical drying model to find the optimal drying conditions for a prototypical coating in a single‐zone oven. The optimization process seeks oven conditions that minimize the residual solvent level for a fixed oven residence time without boiling the solvent within the coating. The optimal oven conditions include the air temperature and coating‐side and substrate‐side heat‐transfer coefficients. The conditions are constrained to physically reasonable values. According to our results, the optimal coating‐side heat‐transfer coefficient is always equal to or greater than the optimal substrate‐side heat‐transfer coefficient. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 149–165, 2000     

Mahua‐oil‐based resins for the high‐temperature curing of fly ash coatings

We attempted to prepare medium‐oil‐length glycerol alkyds based on Mahua oil. Fatty acids were isolated from the oil and used in the preparation of alkyds by the fusion method. The resins were characterized by IR spectroscopic analysis. The physicochemical and film properties of these resins were also studied. IR analysis of the resins revealed the formation of phthalate esters showing characteristic peaks at 1720 cm^?1. The resin was modified with melamine formaldehyde, which cured at high temperatures. Alternatively, the resin was made to air dry with ester gum, and the curing behavior was studied. The suitability of these resins for high‐temperature curing fly ash coating applications was established. Coatings were formulated with these resins and with 40% fly ash as an extender. The coatings were characterized by standard techniques, particularly for their anticorrosive and antiabrasive properties. Resistance to corrosion was evaluated in humidity and in salt‐spray conditions. We conducted a high‐stress (two‐body) abrasion test to test the abrasive wear resistance of the coatings. The Mahua‐oil‐resin‐based fly ash coatings were suitable for application in moderately corrosive and abrasive environments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 110–120, 2003     

Polyethylene composite fibers. I. Composite fibers of high‐density polyethylene

Polymer matrix composites are generally studied in the form of bulk solids, and very few works have examined composite fibers. The research described here extended such bulk studies to fibers. The question is whether or not what has been reported for bulk polymers will be the same in fibers. In this article are reported studies of high‐density polyethylene (HDPE), whereas those of linear low‐density polyethylene are reported in part II of this article series. Two types of filler were used, that is, organically modified montmorillonite (OMMT), in which the nanosized filler particles had a high aspect ratio, and microsized calcium carbonate (CaCO₃), with an aspect ratio nearer to unity. Composite fibers of both as‐spun and highly drawn forms were prepared, and their structures, morphology, and mechanical properties were studied. It was found that the microsized particles gave HDPE composite fibers with mechanical properties that were the same as those of the neat polymer. In the case of clay composite fibers, the clay interfered with the yield process, and the usual yield point could not be observed. The particle shape did not affect the mechanical properties. The fibers showed different deformation morphologies at low draw ratios. The CaCO₃ composite fibers showed cavities, which were indicative of low interaction between the polymer and the filler. The OMMT composite fibers showed platelets aligned along the fibers and good polymer–filler interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhanced adhesion of silica for epoxy molding compounds (EMCs) by plasma polymer coatings

Silica for epoxy molding compounds (EMCs) was coated via plasma polymerization using an RF plasma (13.56 MHz) as a function of the plasma power, gas pressure, and treatment time. The monomers utilized for the plasma polymer coatings were 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan, and allyl alcohol. The EMC samples were prepared from biphenyl epoxy resin, phenol novolac, triphenyl phosphine, and plasma polymer-coated silica, and the loading of silica was controlled to 60 wt%. The EMC samples were cured at 175°C for 4 h and subjected to T_g, CTE, and water absorption measurements. The adhesion of silica to epoxy resin was evaluated by measuring the flexural strength of EMC samples and the fracture surfaces were analyzed by SEM. Plasma polymer coatings were also characterized by FT-IR and coating thickness measurements. The plasma polymer coating of silica with 1,3-diaminopropane and allylamine enhanced the flexural strength of EMC samples (167 and 165 MPa), compared with the control sample (140 MPa), and exhibited a higher T_g, a lower CTE, and lower water absorption. The enhanced properties with 1,3-diaminopropane and allylamine plasma polymer coatings can be attributed to the amine functional groups in the plasma polymer coatings.     

Surface modification of polyimide fibers by novel alkaline–solvent hydrolysis to form high‐performance fiber‐reinforced composites

We modified polyimide (PI) fibers by a novel hydrolysis approach and fabricated PI‐fiber‐reinforced novolac resin (NR) composites with enhanced mechanical properties. We first used an alkaline–solvent mixture containing potassium hydroxide liquor and dimethylacetamide (DMAc) for the surface modification of the PI fibers. The results indicate that the surface roughness and structure of the PI fibers were controlled by the hydrolysis time and the content of DMAc. With the optimized hydrolysis conditions, the tensile modulus of modified PI fibers improved 15% without compromises in the fracture stress, fracture strain, or thermal stability. The interfacial shear strength between the modified PI fibers and NR increased 57%; this indicated a highly enhanced interfacial adhesion. Finally, the tensile and flexural strengths of the composites increased 72 and 53%, respectively. This research provides an effective method for the surface modification of PI fibers and expands their applications for high‐performance composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46595.     

Polybenzoxazine‐based composites as high‐performance materials

Polybenzoxazines are newly developed thermoset polymers exhibiting versatility in a wide range of applications including in the electronics and aerospace industries. When combined as composites, the attractive characteristics of both components are apparent. The chemistry of benzoxazine synthesis offers wide molecular design flexibility and thus facilitates preparation of various polybenzoxazine‐based composites. This article reviews recent developments in the preparation and thermal curing of benzoxazine composites with a focus on structure–property relations of cured materials. Copyright © 2010 Society of Chemical Industry     

Melt‐rheological behavior of high‐solid cement‐in‐polymer dispersions

The rheological behavior of a series of poly(ethylene oxide) melts containing nonhydrated cement is investigated using stress‐sweep measurements. The influence of the polymer end‐group—diol, monomethyl ether, and dimethyl ether—, molecular weight, and the particle volume fraction is examined. The data suggests that monomethyl ethers adsorb with their single OH group head‐on on the cement surface, which reduces the interparticle friction and the viscosity, but mixtures based on monomethyl ethers exhibit shear‐thickening behavior. The diols cause the formation of hydrogen‐bonded particle networks leading to high viscosities, but these mixtures exhibit shear‐thinning behavior due to the collapse of the network upon shearing. On increasing the particle volume fraction, the samples feature a nonlinear increase in viscosity. Fitting these data indicated that the maximum particle volume fraction is close to the random packing density of spheres and decreases with decreasing shear stress. As coating for glass rovings, the mixtures match the reinforcing performance of solvent‐based systems despite lower cement content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Joining of fiber‐reinforced polymer tubes for high‐pressure applications

Fiber‐reinforced polymer composites offer superior performance particularly in harsh environments; hence, they are recognized as an attractive material, especially for the transportation of pressurized fluids. However, an extensive use of these composites has been hampered, in part due to unsatisfactory solutions for the joining of subcomponents, and insufficient knowledge on the associated damage behavior. A favorable connection design for a piping system can be an adhesively bonded joint. In this study, a unique adhesive injection technique is presented that joins composite pipe sections using filament‐wound overlap sleeve couplers. The purpose of the present study was to characterize the performance and associated damage behavior of a prototype‐size pipe structure joined by the above procedure. Internal pressure and axial traction were applied to specimens at various biaxial ratios. In addition to the experimental investigation, the joint geometry was also modeled numerically employing the finite element technique. This yielded a better understanding of the damage behavior and enabled a parametric study that provided recommendations for an improved joint design. POLYM. COMPOS., 27:99–109, 2006. © 2005 Society of Plastics Engineers