Aromatic imide polymers for high-temperature adhesives

During the past decade the aerospace industry has sought materials for bonding stainless-steel and titanium alloys that have a high degree of thermal and oxidative stability. The Air Force Materials Laboratory has anticipated these requirements and sponsored many development programs aimed at achieving these goals. This paper describes the results of one such program devoted to development of high-temperature adhesives from aromatic imide polymers. The family of polymeric materials known as aromatic polyimides possess excellent thermal and oxidative resistance at temperatures up to 650°F. Mechanical and electrical properties of glass-fiber-reinforced laminates prepared with these polymers have been reported. This work has been extended to the development of structural adhesives that will withstand long-time exposure in air at 600°F. Stainless steel and titanium have been successfully bonded with adhesives made from aromatic imide and benzimidazole imide polymers. Bonds made with stainless steel have retained approximately 80% of their original strength at 600°F. after 1000 hr. of aging at 600°F. Adhesives made with benzimidazole imide polymers are the prepared materials for bonding titanium. Initial bond strengths of 1300 psi have been measured at 600°F. After 1000 hr. at 600°F. the bond strengths drop to 800 psi. The processing conditions for making a bond are quite moderate, except that a high temperature is required. The preparation and processing conditions associated with these adhesives are described. A large number of aromatic imide and amide-imide polymers have been prepared and adhesives formulated. By comparing the bond strengths obtained with these adhesives it is possible to deduce the effect of molecular weight and various molecular components on bond strength.     

AI polymer laminates for high temperature stability

Amoco AI amide imide polymer is an all aromatic polymer which is currently being used as a high temperature wire enamel. It also looks promising as a high temperature laminating material. It is available in a stable solid form and is readily formulated in its laminating solvents. B-Staged coated glass cloth with excellent shelf stability is easily prepared. AI laminates retain their initial flexural strength after four weeks at 500°F. They retain 50% of their initial flexural strength after one week at 572°F. Other modifications of this type of polymer are being investigated as laminating materials.     

Geopolymer reinforced with E‐glass leno weaves

This study explores the viability of fiberglass‐geopolymer composites as an intermediate temperature structural ceramic composite. E‐glass fibers are cheap, readily available, resistant to heat, electricity and chemical attack. Geopolymers are refractory and can be processed at room temperature. However, pure geopolymers have low tensile strength and fracture toughness, as is typical of ceramics. In this work, tensile and flexure properties of metakaolin‐based sodium and potassium geopolymers reinforced with E‐glass leno weaves were measured and the data was analyzed by Weibull statistics. The average tensile and flexural strengths for sodium geopolymer reinforced with E‐glass leno weaves were 39.3 ± 7.2 MPa and 25.6 ± 4.8 MPa, respectively. For potassium geopolymer reinforced with E‐glass leno weaves, the average tensile and flexural strengths were 40.7 ± 9.9 MPa and 15.9 ± 4.0 MPa, respectively. The composites were heat treated for one hour at two temperatures, 300°C and 550°C and their flexure properties were studied at room temperatures. The average flexural strengths for sodium geopolymer reinforced with E‐glass leno weaves were reduced to 6.6 ± 1.0 MPa after heat treatment at 300°C, and 1.2 ± 0.3 MPa after heat treatment at 550°C, respectively. For potassium geopolymer reinforced with E‐glass leno weaves, the average flexural strengths were 6.1 ± 1.5 MPa and 1.3 ± 0.3 MPa after heat treatment at 300°C and 550°C, respectively. SEM and EDS were performed to observe the fiber‐matrix interface. XRD was done to check if the geopolymer was amorphous as expected.     

Low Temperature‐Based Flexural Properties of Carbon Fiber/Epoxy Composite Laminates Incorporated with Carbon Nanotube Sheets

This study introduces carbon nanotube buckypaper (CNTBP) into the easily fractured sites of [0°]₁₆ and [0°/90°]_4S composite laminates, and comparatively explores how the CNTBP affects the flexural properties of the laminates at 25, ?15, and ?55 °C. Compared to the base [0°]₁₆ and [0°/90°]_4S laminates at the same temperature, improvements of the flexural strengths in the order of 4.0–15.3% and 6.5–31.0% are respectively obtained from the corresponding CNTBP‐reinforced [0°]₁₆ and [0°/90°]_4S laminates. Importantly, the lower the temperature is, the higher the strength improves. In fact, the CNTBP has little effect on the flexural moduli of the studied laminates, although there is an increasing trend with decreased temperature. Moreover, the introduced CNTBP would significantly change the fracture mechanism of the laminates at low temperature. The present work reveals that the CNTBP exhibits more positive reinforcing capability to the polymer matrix‐based composite laminates at relatively low temperatures.     

Preparation and properties of glass cloth‐reinforced polyimide composites with improved impact toughness for microelectronics packaging substrates

A series of glass cloth‐reinforced thermosetting polyimide composites (EG/HTPI) were prepared from E‐glass cloth (EG) and polyimide matrix resins. The polyimide resins were derived from 1,4‐bis(4‐amino‐2‐ trifluoromethyl‐phenoxy)benzene, p‐phenylenediamine, diethyl ester of 3,3′,4,4′‐benzophenonetetracarboxylic acid, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid. Based on the rheological properties of the B‐staged polyimide resins, the optimized molding cycles were designed to fabricate the EG/HTPI laminates and the copper‐clad laminates (Cu/EG/HTPI). Experimental results indicated that the EG/HTPI composites exhibited high thermal stability and outstanding mechanical properties. They had flexural strength of >534 MPa, flexural modulus of >20.0 GPa, and impact toughness of >46.9 kJ/m². The EG/HTPI composites also showed good electrical and dielectric properties. Moreover, the EG/HTPI laminates exhibited peel strength of ～ 1.2 N/mm and great isothermal stability at 288°C for 60 min, showing good potential for application in high density packaging substrates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reinforced poly(vinyl chloride)—the ultimate rigid vinyl

Rigid poly(vinyl chloride) was reinforced with 10 to 40 phr of 1/4-inch glass fiber. This improved flexural modulus up to 140 percent, flexural strength 40 percent, and heat-deflection temperature 8°C; and reduced creep by 90–95 percent, and the coefficient of thermal expansion by 50 percent. Thus a typical Type I rigid vinyl with glass reinforcement had flexural modulus 1,164,000 psi, flexural strength 16,500 psi, notched Izod impact strength 5.1 fpi; creep only 12 percent of normal unreinforced material, coefficient of thermal expansion only 50 percent of normal unreinforced material, and heat-deflection temperature 79°C. Such balance of properties elevates rigid vinyl from a commodity plastic up to an engineering thermoplastic, capable of much wider and more economical utilization in high-performance applications.     

Tris-benzil crosslinked polyphenylquinoxalines

Polyphenylquinoxalines (PPQ) were crosslinked with a tris-benzil comonomer, to alleviate the inherenthigh temperature thermoplasticity, and evaluated as matrices in graphite reinforced composites. The room temperature flexural strength/modulus of Modmor IJ laminates were as high as 245,000 psi/16,6 × 10⁶ psi. Essentially 100 percent retention of ambient mechanical properties was obtained at 371°C using a PPQ matrix from the fully-crosslinked polymer prepared from 4,4′-bis(4″-oxybenzilyl) benzil (BOBB) and 3,3′-diaminQbenzrdine. The degree of high temperature thermoplasticity in the composite was found to be more closely related to the final postcure temperature than to the BOBB crosslink density. The thermoplasticity essentially disappeared when the BOBB comonomer-PPQ laminates were postcured at 482–510°C in nitrogen. Substitution of DMAC for the commonly used m-cresol solvent system allowed facile preparation of prepreg to fabricate low-void laminates and NOL rings.     

Evaluation of polyglycidyl esters as cryogenic adhesives

Polyglycidyl esters of aromatic polycarboxylic acids were evaluated as adhesives for aluminum over the temperature range ?453 to +400°F. The esters were cured either with amines or anhydrides. Cyclopentanetetracarboxylic acid dianhydride was found to be a superior curing agent and gave adhesives with tensile shear strengths in excess of 1000 psi at 400°F.     

Strength of polybenzimidazole and phenolic laminate-to-metal joints

Stress concentration effects and strengths of bonded and bolted butt joints were investigated for a glass fabric polybenzimidazole lalminate at room temperatuer and 700°F for a gloass fabric phenolic laminate at room temperature and 500°F. Specimen configurations included: (1) standard tensile specimen, (2) stress concentration specimen, (3) bolted double shear butt joint, (4) bolted single shear butt joint, (5) bonded double shear butt joint and (6) bonded single shear butt joint. Both polybenzimidazole and phenolic laminates exhibited high room temperature tensile strengths and little degradation of that strength occured as a result of elevated temperature exposure. However, low joint effencies (22 to 32%) were obtained for bolted butt joint specimens. Although bonded joints exhibited higher efficiencies, they suffered from a thermal expansion mismatch between the plastic laminate and the Inconel butt plates.     

Blends of poly(ethylene terephthalate) and epoxy as matrix material for continuous fibre reinforced composites

Abstract

The morphology and mechanical properties of poly(ethylene terephthalate) (PET)–epoxy blends and the application of these blends in continuous glass fibre reinforced composites have been investigated. Epoxy resin was applied as a reactive solvent for PET to obtain homogeneous solutions with a substantially decreased melt viscosity. The epoxy resin in these solutions was cured using an amine hardener according to two different schedules. In the first, high temperature curing at 260°C preceded low temperature crystallisation of the PET at 180°C. In the second, the PET was allowed to crystallise prior to low temperature curing at 180°C. After cure, all blends revealed a phase separated morphology of dispersed epoxy in a continuous PET matrix. The flexural strength and failure strain of all cured blends showed an increase with increasing epoxy content, whereas the high temperature cured blends exhibited overall lower flexural properties than those cured at the lower temperature. Microstructural analysis and flexural properties of continuous glass fibre reinforced PET–epoxy laminates showed that the composites obtained had a low void content. These PET–epoxy laminates had increased inplane shear strength in comparison with unmodified PET based laminates, indicating considerably increased fibre–matrix adhesion.     

Processing robustness for a phenylethynyl‐terminated polyimide composite

The processability of a phenylethynyl‐terminated imide resin matrix (PETI‐5) composite was investigated. Unidirectional prepregs were made through the coating of an N‐methylpyrrolidone solution of an amide acid oligomer (PETAA‐5/NMP) onto unsized IM7 fibers. Two batches of prepregs were used: one was made by the National Aeronautics and Space Administration in house, and the other was from an industrial source. The composite processing robustness was investigated with respect to the prepreg shelf life, the effect of B‐staging conditions, and the optimal processing window. The prepreg rheology and open hole compression (OHC) strengths were not to affected by prolonged ambient storage (i.e., up to 60 days). Rheological measurements indicated that the PETAA‐5/NMP processability was only slightly affected over a wide range of B‐stage temperatures (from 250 to 300°C). The OHC strength values were statistically indistinguishable among laminates consolidated under various B‐staging conditions. An optimal processing window was established with response surface methodology. The IM7/PETAA‐5/NMP prepreg was more sensitive to the consolidation temperature than to the pressure. A good consolidation was achievable at 371°C (700°F)/100 psi, which yielded a room‐temperature OHC strength of 62 ksi. However, the processability declined dramatically at temperatures below 350°C (662°F), as evidenced by the OHC strength values. The processability of the IM7/PETI‐5 prepreg was robust. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3212–3221, 2006     

The mechanical and thermal properties of graphite fiber reinforce polyphenylquinoxaline and polyimide composites

Comparative studies were made on the fabrication characteristics, mechanical properties and thermal stabilities of three commercially available composite systems based on linear monoether polyphenylquinoxaline, P13N polyimide, and Skybond 703 polyimide, reinforced with Modmor II graphite fibers. Fabrication parameters and prepreg conditions were related to the properties of the laminates. Interlaminar shear strength and flexural properties were evaluated before and after the thermal aging at 600°F for periods up to 500 hrs. Thermal degradation of composites at various stages of thermal' aging was studied using optical and scanning electron microscopes.     

A comparison study: The new extended shelf life isopropyl ester PMR technology versus the traditional methyl ester PMR approach

Polymerization of monomeric reactants (PMR) monomer solutions and carbon cloth prepregs of PMR II‐50 and VCAP‐75 were prepared using both the traditional limited shelf life methanol based PMR approach and a novel extended shelf life isopropanol based PMR approach. The methyl ester and isopropyl ester based PMR monomer solutions and PMR prepregs were aged for up to 4 years at freezer and room temperatures. The aging products formed were monitored using high pressure liquid chromatography (HPLC). The composite processing flow characteristics and volatile contents of the aged prepregs were correlated versus room temperature storage time. Composite processing cycles were developed and six‐ply cloth laminates were fabricated with prepregs after various extended room temperature storage times. The composites were then evaluated for glass transition temperature (T_g), thermal decomposition temperature (T_d), initial flexural strength (FS), and modulus (FM), long term (1000 h at 316°C) thermal oxidative stability (TOS), and retention of FS and FM after 1000 h aging at 316°C. The results for each ester system were comparable. Freezer storage was found to prevent the formation of aging products for both ester systems. Room temperature storage of the novel isopropyl ester system increased PMR monomer solution and PMR prepreg shelf life by at least an order of magnitude, while maintaining composite thermal and mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3549–3564, 2006     

Preparation and properties of bisphenol A‐based bis‐phthalonitrile composite laminates

A series of bisphenol A (BPA)‐based 2,2‐bis‐[4‐(3,4‐dicyanophenoxy)phenyl]propane (BAPh) prepolymers and polymers were prepared using BPA as a novel curing agent. Ultraviolet–visible and Fourier transform infrared spectroscopy spectrum were used to study the polymerization reaction mechanism of the BAPh/BPA polymers. The curing behaviors were studied by differential scanning calorimetry and dynamic rheological analysis, the results indicated that the BAPh/BPA prepolymers exhibit large processing windows (109.5–148.5°C) and low complex viscosity (0.1–1 Pa·s) at moderate temperature, respectively. Additionally, the BAPh/BPA/glass fiber (GF) composite laminates were manufactured and investigated. The flexural strength and modulus of the composite laminates are 548.7–632.8 MPa and 25.7–33.2 GPa, respectively. The thermal stabilities of BAPh/BPA/GF composite laminates were studied by thermogravimetry analysis. The temperatures at 5% weight loss (T_5%) of the composite laminates are 508.5–528.7°C in nitrogen and 508.1–543.2°C in air. In conclusion, the BAPh/BPA systems can be used as superior matrix materials for numerous advanced composite applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of quartz‐fiber‐cloth‐reinforced,polymerization‐of‐monomer‐reactant‐type polyimide substrates with a high impact strength

A series of novel quartz‐fiber‐cloth‐reinforced polyimide substrates with low dielectric constants were successfully prepared. For this purpose, the A‐stage polyimide solution was first synthesized via a polymerization‐of‐monomer‐reactant procedure with 2,2′‐bis(trifluoromethyl)benzidine and 3,3′,4,4′‐oxydiphthalic anhydride as the monomers, and cis?5‐norbornene‐endo‐2,3‐dicarboxylic anhydride as the endcap. Then, an A‐stage polyimide solution (TOPI) was impregnated with quartz‐fiber cloth (QF) to afford the prepregs, which were thermally molded into the final substrate composites. The influence of the curing temperature and the resin content on the mechanical properties of the composite were examined. The composites exhibited a high glass‐transition temperature over 360°C, a low and steady dielectric constant below 3.2 at a test frequency of 1–12 GHz, and a volume resistance over 1.8 × 10¹⁷ Ω cm. Meanwhile, they also showed a high mechanical strength with flexural and impact strengths in ranges 845–881 MPa and 141–155 KJ/m², respectively. The excellent mechanical and thermal properties and good dielectric properties indicated that they are good candidates for integrated circuit packaging substrates. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42358.     

Mechanical,thermal, electrical,and interfacial properties of high‐performance bisphthalonitrile/polyarylene ether nitrile/glass fiber composite laminates

Bisphthalonitrile (BAPh)/polyarylene ether nitrile end‐capped with hydroxyl groups (PEN‐OH) composite laminates reinforced with glass fiber (GF) have been fabricated in this article. The curing behaviors of BAPh/PEN‐OH prepolymers have been characterized by differential scanning calorimetry and dynamic rheological analysis. The results indicate that with the introduction of PEN‐OH the curing temperature of BAPh has decreased to 229.6–234.8°C and BAPh/PEN‐OH prepolymers exhibit large processing windows with relatively low melt viscosity. The BAPh/PEN‐OH/GF composite laminates exhibit tensile strength (272.4–456.5 MPa) and modulus (4.9–10.0 GPa), flexural strength (507.1–560.9 MPa), and flexural modulus (24.0–30.4 GPa) with high thermal (stable up to 538.3°C) and thermal stabilities (stable up to 475.5°C). The dielectric properties of BAPh/PEN‐OH/GF composite laminates have also been investigated, which had little dependence on the frequency. Meanwhile, scanning electron microscopy results show that the BAPh/PEN‐OH/GF composite laminates display excellent interfacial adhesions between the matrix and GFs. Herein, the BAPh/PEN‐OH matrix can be a good matrix for high‐performance polymeric materials and the advanced BAPh/PEN‐OH/GF composite laminates can be used under high temperature environment. POLYM. COMPOS., 34:2160–2168, 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of melt‐processable polyimides derived from 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene

A series of molecular‐weight‐controlled imide resins end‐capped with phenylethynyl groups were prepared through the polycondensation of a mixture of 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene and 1,3‐bis(4‐aminophenoxy)benzene with 4,4′‐oxydiphthalic anhydride in the presence of 4‐phenylethynylphthalic anhydride as an end‐capping agent. The effects of the resin chemical structures and molecular weights on their melt processability and thermal properties were systematically investigated. The experimental results demonstrated that the molecular‐weight‐controlled imide resins exhibited not only meltability and melt stability but also low melt viscosity and high fluidability at temperatures lower than 280°C. The molecular‐weight‐controlled imide resins could be thermally cured at 371°C to yield thermoset polyimides by polymer chain extension and crosslinking. The neat thermoset polyimides showed excellent thermal stability, with an initial thermal decomposition temperature of more than 500°C and high glass‐transition temperatures greater than 290°C, and good mechanical properties, with flexural strengths in the range of 140.1–163.6 MPa, flexural moduli of 3.0–3.6 GPa, tensile strengths of 60.7–93.8 MPa, and elongations at break as high as 14.7%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Polyphenylquinoxalines containing alkylenedioxy groups

A series of new polyphenylquinoxalines (PPQ) containing alkylenedioxy units within the backbone were prepared in high molecular weight forms (η_inh = 0.82–1.5 dL/g). The glass transition temperatures ranged between 203 and 241°C, decreasing with increasing length of the alkylenedioxy groups. Solution-cast films gave tensile strength, tensile modulus, and elongation at room temperature as high as 14,400 psi, 378,000 psi, and 8.1%, respectively. The PPQ were readily compression molded to provide compact tension specimens that gave fracture energy (G_Ic) as high as 10.5 in. lb/in.² Titanium to titanium tensile shear specimens provided average strengths of 4400 psi at 26°C, 3100 psi at 177°C, and 2010 psi at 203°C. The PPQ were resistant to normal aircraft fluids but were soluble in chlorinated solvents.     

Cyclic Oxidation of Ternary Layered Ti2AlC at 600–1000°C in Air

The cyclic oxidation of bulk Ti₂AlC at intermediate temperatures of 600–1000°C in air was studied by thermogravimetric analysis. It was demonstrated that Ti₂AlC exhibited good cyclic‐oxidation resistance at temperatures above 700°C. The cyclic‐oxidation kinetics approximately follows a parabolic rate law at 700–1000°C range. The surface scales are dense, resistant to spalling and adhesive to Ti₂AlC substrate. An abnormal oxidation whose cyclic‐oxidation kinetics obeys a linear law is observed at 600°C. As revealed by scanning electron microscope (SEM), oxidation‐induced cracks present at 600°C results in poor protectivity and accounts for the abnormal oxidation. The cracks are caused by the stress associated with the volume expansion due the formation of anatase TiO₂ in the scale.     

Hybrid fiber fabric composites from poly ether ether ketone and glass fiber

Poly ether ether ketone (PEEK) polymer was extruded into filaments and cowoven into unidirectional hybrid fabric with glass as reinforcement fiber. The hybrid fabrics were then converted into laminates and their properties with special reference to crystallization behavior has been studied. The composite laminates have been evaluated for mechanical properties, such as tensile strength, interlaminar shear strength (ILSS), and flexural strength. The thermal behavior of the composite laminates were analyzed using differential scanning calorimeter, thermogravimetric analyzer, dynamic mechanical analyzer (DMA), and thermomechanical analyzer (TMA). The exposure of the fabricated composite laminates to high temperature (400 and 500°C) using radiant heat source resulted in an improvement in the crystallanity. The morphological behavior and PEEK resin distribution in the composite laminates were confirmed using scanning electron microscope (SEM) and nondestructive testing (NDT). Although DMA results showed a loss in modulus above glass transition temperature (T_g), a fair retention in properties was noticed up to 300°C. The ability of the composite laminates to undergo positive thermal expansion as confirmed through TMA suggests the potential application of glass–PEEK composites in aerospace sector. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1446–1459, 2010