Journal of Colloid and Interface Science 336 (2009) 872–878

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Journal of Colloid and Interface Science
www.elsevier.com/locate/jcis

An investigation into the improvement of adhesive strength of polyimides by incorporation of elastomeric nanoparticles
Sepideh Khoee a,*, Ali Reza Mahdavian b, Warahram Bairamy a, Mohsen Ashjari b
a b

Polymer Laboratory, Chemistry Department, School of Science, University of Tehran, P.O. Box 14155-6455, Tehran, Iran Polymer Science Department, Iran Polymer & Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran

a r t i c l e

i n f o

a b s t r a c t
Copoly(styrene–butyl acrylate–ethyleneglycoldimethacrylate) (St–BA–EGDMA) nanoparticles were prepared using miniemulsion polymerization technique. Then the dispersed nanoparticles in DMAc were added to in situ condensation polymerization media of pyromellitic dianhydride (PMDA) and oxydianiline (ODA) and consequently, homogenous polyamic acid solution containing the nanoparticles was obtained. Novel polymer–polymer nanocomposites were prepared by casting of PMDA–ODA polyamic acid solution with various content of the above elastomeric nanoparticle (ENP) on a glass plate followed by thermal imidization. All samples were characterized after preparation by FT-IR spectroscopy, transition electron microscopy (TEM), thermal gravimetry analysis (TGA) and differential scanning calorimetery (DSC). To investigate the adhesion strength of polyimides filled with (St–BA–EGDMA) nanoparticles, lap shear strength (LSS) test was examined on different metallic surfaces. Effect of nanoparticles content on the adhesion properties of this polymer was considerable for aluminum surface. Lapshear strength and adhesive energy of the bonded samples were found to initially increase with the increase in ENP wt%, but decrease after a critical value. It was shown that by increasing the nanoparticles amount up to 25 wt%, the adhesion strength of polyimides increased due to the good wetability of surfaces. After that and by increasing the nanoparticles amount, the adhesion strength decreased according to the diminished strength between polyimide chains. Scanning Electron Microscopy (SEM) micrographs of the fractured surfaces were taken to determine the failure mode. They showed that by increasing the nanoparticle content in the polyimide matrix, failure mode was converted from adhesion failure to cohesion one. Ó 2009 Published by Elsevier Inc.

Article history: Received 23 November 2008 Accepted 22 April 2009 Available online 3 May 2009 Keywords: Polymer–polymer nanocomposites Polyimide adhesive Elastomeric nanoparticles Ultrasound

1. Introduction Polyimides (PIs) are a family of heterocyclic polymers that have received extensive evaluation as adhesives, fibers, films, molding, composite matrices, coatings and membranes. As a class of polymers, polyimides posses a favorable combination of properties, that make them attractive for many applications. The high thermal, thermo-oxidative and chemical stability coupled with good mechanical properties, makes these polymers particularly attractive for use in harsh environments [1]. Several polyimides have displayed excellent properties as adhesives. High-performance adhesives are needed for joining metals, composites, ceramics and plastics to themselves and to each other. These adhesives find use in a variety of applications in the aerospace, automotive, electronic, domestic household, oil and other industries. High performance adhesive polyimides should have high molecular weight. These polyimides impart good mechanical
* Corresponding author. Fax: +98 21 6649 5291. E-mail address: Khoee@Khayam.ut.ac.ir (S. Khoee). 0021-9797/$ - see front matter Ó 2009 Published by Elsevier Inc. doi:10.1016/j.jcis.2009.04.067

and thermal properties but on the other hand, limit their applications as they are insoluble in most organic solvents and have high melting temperature in the range of 300–400 °C. The processing of such PIs involves use of temperature higher than 400 °C, which often leads to degradation of the polymer [2]. High melting temperature (Tm) leads to increase the flow temperature of polyimide adhesives and results in poor wetting ability of these adhesives, which limit their applications. The subject of many contemporary researches is to overcome this limitation. Preparation of polyimide containing oxyalkylene units [3], partially fluorinated polyimide [4], polyimide sulphone [5] and polyimides containing aliphatic segments [6] are typical methods for changing in the chemical structure of primary polyimides. Another method is using polyimide with low molecular weight or oligoimides that have low glass transition temperature (Tg) [7]. All of these methods improve wettability of the adhesives but has improper effect on their mechanical properties. Saeed and Zhan used two different types of nanoparticles namely multi-walled carbon nano-tubes and aluminum nitride (AlN) nanopowder to reinforce PI adhesive matrices which had lowest effect on their melt flow [8,9].

the . Vespel is the trademark of this durable high-performance polyimide manufactured by DuPont [13]. KG) and the probe type was a titanium microtip MS-73 with 3 mm in diameter. Here. 2. lubricity. such as chemical-free initiation and low reaction temperature. SONOPULS Ultrasonic homogenizer. both particle nucleation and subsequent propagation reaction occur primarily in submicrometer monomer droplets. TEM micrographs were taken by a ZEISS 902A (Germany) at an acceleration voltage of 80 keV. Mean particle size was measured by SEMATECH light scattering (France) with 633 nm wavelength. decreases the viscosity substantially. It combines heat resistance. The PI samples were suspended in DMAc and diluted up to 20 times. Preparation of PAA containing nanoparticles A predetermined amount of St–BA–EGDMA nanoparticles were mixed with DMAc and homogenized by pulsy ultrasonic and intensive agitation. Polyimides inherently show a very high melt viscosity due to their rigid aromatic backbone. crushing.04 Â 10À3 mol) ODA and 1. nitrogen inlet and a drying tube to afford a homogenous poly (amic acid)/ ENP solution. N.3 mm/ min and testing temperature was maintained at 25 ± 2 °C. stained with OsO4 and dropped on a copper grid for TEM analysis. Model HF-GM 2200 (BANDELIN electronic GmbH & Co. Materials and methods 2. This rather expensive polymer is mostly used in aerospace. creamy solutions of PAA containing nanoprticles were obtained. to form a stable transparent suspension. It was found that lowering the Tg to 177 °C. 2. Miniemulsion polymerization St–BA–EGDMA monomers with molar ratios of 0.3. (analytical grade) was washed with 5% sodium hydroxide aqueous solution (wt%) to remove the inhibitor.03 were polymerized isothermally through miniemulsion copolymerization in a 500 ml four necked round bottomed glass reactor.1. In this study.S. dimensional stability. Wetting of the substrate and good interfacial contact are critical points in obtaining a strong and durable interface. emulsifying. Because of miniemulsification.2. The monomers were premixed through ultrasonication for 5 min at room temperature in order to reach the optimum dispersion of the monomeric phase. prepared by shearing a system containing oil. After preparing polymeric matrix. The nanoelastomeric filled poly(amic acid)s (PAA)s were prepared by addition of 1. 2. The surface morphology was studied by Cambridge S-360 SEM scanning electron microscopy (SEM). Ultrasonically initiated miniemulsion polymerization has many advantages. Apparatus The equipment employed in this research was a 20 kHz ± 500 Hz ultrasonic generator. This has been one of their major drawbacks and efforts have continued to lower their viscosity to improve their processability.IFS 48 spectrophotometer (Germany) using KBr pellets. PMDA was recrystalized in dry acetic anhydride and ODA was purified by sublimation before use. head speed was 1. During the tests.N-dimethylacetamide (DMAc) was dried over BaO and then distilled under reduced pressure.09 gr (5. Materials Styrene (St) from Merck Chemical Co. Lap-shear strength (LSS) of bonded joints was measured in accordance with ASTM D1002. a mechanical stirrer and a nitrogen gas inlet. the elastomeric St–BA–EGDMA nanoparticles were added to the above matrix.5. Preparation of polyimidic nanocomposites The nanoelastomeric filled poly(amic acid)s (PAA)s in DMAc was casted onto glass plates. The glass transition temperature (Tg) of the copolymers was measured according to their thermograms. / Journal of Colloid and Interface Science 336 (2009) 872–878 873 A miniemulsion is an aqueous dispersion of relatively stable oil droplets with a size range of 50–500 nm. Ultrasound has been widely used in chemical industries. surfactant and hydrophobe (cosurfactant). Determination of LSS at high temperature was carried out at 250 °C. raising the temperature to 150 and 200 °C and remaining at each of these temperatures for 1 h and finally to 250 °C for 2 h. The initial charge was stirred at 300 rpm and heated up to 75 °C by using of a thermostatic bath and the polymerization reaction was progressed under N2 atmosphere for 10 h. This polymer has a Tg of approximately 289 °C. nanoparticles with 98% conversion relative to the initially added non-volatile components were obtained. On the other hand. while still produces breakable adhesives. samples were exposed to test temperature in a furnace (mounted on tensile testing machine) for 1 h and then subjected to load for measuring LSS. 2. the monomer droplets can effectively capture the radicals and become the dominant sites for particle nucleation in a miniemulsion polymerization process [10]. The system was cooled to room temperature and the final latex was obtained without any post-preparative treatments.00 Â 10À3 mol) PMDA to the homogeneous dispersions of St–BA–EGDMA nanoparticles at 5 °C and then stirring for 6 h at 20 °C in a three-necked round bottomed flask equipped with a magnetic stirrer. the polyimide is based on pyromellitic dianhydride (PMDA) and oxydianiline (ODA). were used without further purification. HD as a hydrophobic agent and BPO as an initiator were dissolved in the monomeric phase and the obtained mixture was added into the water phase containing SDS and a definite amount of double distilled water. water. Finally. hexadecane (HD) and benzoyl peroxide (BPO) from Merck Chemical Co. The above miniemulsion was moved into the reaction vessel. Thermal imidization was achieved by holding the samples at 100 °C for 24 h. semiconductor and transportation technologies. dried over calcium chloride and stored at 0 °C. Butyl acrylate (BA) and ethylene glycol dimethacrylate (EGDMA) from Fluka. Because of the small droplet size and large surface area. sodium dodecyl sulfate (SDS) from Aldrich.97:1:0.4. The first step in the adhesion study was selection of an appropriate Tg for the binding polyimide. St–BA–EGDMA nanoparticles were prepared using miniemulsion polymerization technique and the obtained nano-size elastomeric particles were applied to improve wettability of polyimide adhesives. After completion of the cycle. ultrasonic irradiation is a useful technique for preparing novel materials with unusual properties. Due to the guide lines provided by ASTM D1002. FT-IR spectra were recorded on a FT-IR BRUKER.01 gr (5. chemical and creep resistance of those used in hostile and extreme environmental conditions. Khoee et al. 2. After removing water. such as dispersing. Differential scanning calorimetry thermograms of the copolymers were obtained using a computer-interfaced calorimeter (Perkin-Elmer Pyres DSC) under a nitrogen atmosphere and a heating rate of 10 °C/min from ambient to 350 °C. SANS 100 kN tensile testing machine equipped with a PC was used to acquire data. the final mixture was ultrasonicated for 10 min until a white milky miniemulsion obtained. which was equipped with a reflux condenser. Thermogravimetric analysis (TGA) were recorded on a Pyris1 Perkin-Elmer under N2 atmosphere with heating rate of 20 °C/min. organic synthesis and initiating polymerization of the monomers [12]. In miniemulsion polymerization. Each of those droplets can be regarded as an individual nanophase reactor [11].

Size of the sample was 108 Â 25. dried in an oven and subsequently wiped with acetone. The aluminum. However.874 S. .62 mm and the bonded area of the joint was 25. polyimide matrices and PI-ENP nanocomposite film. The films were carefully stripped off the glass plates and dried for another 24 h at 100 °C under vacuum. Khoee et al. The solution was mixed till a consistent paste-like mixture was obtained. The paste was then applied on the adherents’ surface on the required Scheme 1.7. different surface treatments were evaluated. 2.8 mm2). the surface was polished with a grade 1000 emery paper for appearance of the new chemically active surface after removal of the protective oxide layer [14]. / Journal of Colloid and Interface Science 336 (2009) 872–878 plates were allowed to cool down to room temperature before removal from the oven. Surface treatment In order to make a strong interface. PI/ENP nanocomposite powders were poured in DMAc to prepare a 50 wt% solution. The coupons utilizing the standard blasting were washed in water. copper and steel coupons used in this study were free of any rust or other surface contaminations.4 Â 12.7 mm (317.4 Â 1. Schematic representation of preparation process of elastomeric copolymer.6. Preparation of samples for lap-shear strength (LSS) analysis Samples for LSS analysis were prepared in accordance with ASTM standard D 1002 [15]. 2.

01 1.09 1.-) and DMAc (—) obtained from dynamic light scattering analysis. The required amount for preparation of a polyimide precursor solution containing ENP dispersions. 3.03 mol HD 7. The bonds at 2854 and 2924 cmÀ1 correspond to aliphatic CAH stretching modes. The adherents were then placed in an oven and heated till 200 °C for 2 h to facilitate the evaporation of volatile materials such as DMAc. The obtained mean particle size diameter was about 114 nm (Fig. This will result in disappearing of micelles and consequently.5 wt% b SDS 3. The characteristic peak of butyl acrylate and ethylene glycol dimethacrylate appears at 1730 cmÀ1. Miniemulsion polymerization As shown in Scheme 1.63 0.09 1. This shows the presence of termonomers in the prepared copolymer. FT-IR spectra were recorded to confirm the structure of copolymer (Fig. crosslinked nanoparticles with copoly(styrene–butyl acrylate–ethyleneglycol dimethacrylate) composition were prepared. monomer droplets are formed with a range of 50– 500 nm depending on the SDS/HD ratio [16].94 16. Polyimide synthesis Uniform nanoparticles of ENP.78 12. 2.01 1.5 11.84 PMDA (g) 1. During miniemulsification process. The polyimide samples were synthesized by adding the equimolar amounts of solid PMDA and ODA in DMAc to a sufficient amount of ENP in dry DMAc at 5 °C to obtain a 10.57 25. Cure cycle for bonded joints After matching. good wetting of the adherent surface was provided. Particles size of the obtained latex and their distribution were determined by dynamic light scanning (DLS) technique. During this stage. the ultrasonic waves can break up the monomer droplets.5 Yield (%) 98. the temperature was raised up to 250 °C under 1.4 98. 40 wt% for elastomer concentration as shown in Table 2.5 99.87 DMAc (ml)b 18.3. These data are in good accordance with our previously reported spectrum [18]. Those characteristic peaks for styrene monomers are at 700 and 760 cmÀ1 relating to phenyl groups.7 9.S. the other half was placed in a way that an overlap of 12. meanwhile this diameter may be 10–20 lm in the conventional emulsions.7 mm was obtained. Fig. Absorption bands at 1450 and 1377 cmÀ1 proves the presence of CH2 and CH3 groups of BA and EGDMA segments too. BA and EGDMA) was prepared as an oil phase at first. In the second step. the oil phase was dispersed in the water phase including SDS and HD in order to form minidroplets.a Components Amounts a b Fig. 3. The required amount for preparation of ENP dispersions.8.2. 20. 25. Based on the total weight of monomers. 200 °C for 60 min and 250 °C for 2 h (Scheme 1. When an ultrasonicator is used to form a miniemulsion.6 96. 2). in the polymer matrix without any aggregation. For samples prepared with PI/ENP nanocomposites. 2. .09 1. Here. 3.09 1. The mean particle size diameter of the above dispersed nanoparticles in DMAc was about 140 nm.01 1. step 1. which corresponds to the stretching vibration of BA carbonyl group.5 13.525 0. impossibility of nucleation in the continuous phase.8 MPa pressure.97 mol BA 1 mol EGDMA 0. Due to the combined and synergistic effect of surfactant and hydrophobe.09 ODA (g) 1. After drying process.7 4.21 0. 30. The obtained PI nanocomposites were removed from the glassy plates and dried under vacuum at 100 °C for another 24 h. The FT-IR spectrum of copoly(styrene–butyl acrylate–ethyleneglycol dimethacrylate).8 St 0.5 wt%b The amount of ingredients were set to have a latex with 20 wt% solid content.0 98. Five samples were prepared for each test condition and average of LSS for five samples was reported as the final result. Sample 0 10 20 25 30 40 a b ENP (g) 0 0. Results and discussion 3. coupons were placed under hot press for curing cycle.9 16.09 1. 3. 1). Step 2). which is above the recorded Tg and held for 2 h.. Then the reaction was allowed to stir for 6 h at 20° to afford a homogenous poly (amic acid)/ENP solution. Khoee et al. / Journal of Colloid and Interface Science 336 (2009) 872–878 875 area using a spatula.1.5 wt% b BPO 1. The conversion of polyamic acid to polyimide could be observed by increasing the two Table 2 Amount of reactants in preparation of PI/ENP.31 9. 150 °C for 60 min. a stepwise thermal imidization procedure was utilized. processing. FT-IR analysis of PI/ENP nanocomposites FT-IR spectra of nanocomposite specimens containing different percent of ENP have been shown in Fig. 1. monomer droplets will become stable enough to prevent diffusion of monomers to the continuous phase. The prepared nanocomposites were thermally cured under vacuum at 100 °C for 24 h. In the next step.01 1.01 1.3 97.42 0. a mixture of three monomers (St. It is also notable that the droplet size may have an inverse proportionality with ultrasonication time and latex particles will follow this trend subsequently [17].01 DMAc (ml)a — 4. The detailed amounts of ingredients have been listed in Table 1. Mean particle sizes of dispersed nanoparticles in the latex (. were obtained via dispersing of the ENP film in the reaction solvent (DMAc) by sonication prior to further Table 1 The recipe for miniemulsion polymerization.

overlapped imidic carbonyl peaks at 1720 (imide C@O asymmetric stretching) and 1780 cmÀ1 (imide C@O symmetric stretching). (d) 25. all the nanocomposite degradation graphs show a two-step transition. These parameters can adversely affect recrystallization of the polyimide and indeed this seems to be a useful case for most of the semicrystalline thermoplastic polyimides. Due to the organic characteristics of the applied nanoparticles.e. The first degradation stage appeared at 348. 2). they were enwrapped well in the PI matrix and consequently. 4. (c) 20.5. it can be seen that the thermal stability of pure PI film is more than PI/ENP hybrid films. The unreacted polyamic acid. According to the specific application of these PIs. Thermal analysis Thermogravimetric analysis is a convenient method for evaluation of the thermal stability of polyimides. Thermal degradation of pure PI and PI/ENP samples has been displayed in Fig. 3. the reactants were heated 2 h instead of 4 h in the final step of thermal imidization and consequently. FT-IR spectra of the PI nanocomposites with (a) 0. could be found by appearance of a broad acidic hydroxyl peak in all samples at 3300–3500 cmÀ1. The primary nanoparticles and their dispersion in DMAc are about 114 and 140 nm (Fig. The second stage took place at 551.876 S. TEM micrograph of PI nanocomposites with 30 wt% of ENP. thermal degradation occurred in two stages. butyl acrylate–ethyleneglycol dimethacrylate. . According to Table 3. which confirms the presence of a new phase. 3b to 3e proves the presence of nanoparticles in polymeric matrices. For PI/ENP nanocomposite films. / Journal of Colloid and Interface Science 336 (2009) 872–878 Fig. All of the spectra exhibited a strong absorbance at 1377 (CAN stretching) and 723 cmÀ1. 3. the degradation stage took place at 579. 4 shows the morphology of modified PI by TEM.4. Khoee et al. imidization step was not completed and some amic acid remained unchanged during thermal cyclization process. which shows the presence of the imidic heterocycle in these polymers. Consequently. TGA thermograph of nanocomposite filled with (a) 0.6 °C according to the degradation of imide segment [19]. For pure PI. Flow viscosity is also an important property for applying thermoplastic adhesives.85 °C according to the degradation of imide segments. despite thermal imidization. This phenomenon may occur above glass transition temperature of the polymer without any significant weight loss. Appearance of a new peak at 2854 and 2924 cmÀ1 in FT-IR spectrum of PI/ENP nanocomposites and its accretion in Fig. Generally. These amic acid groups could react with adherent surfaces during the curing cycle. (d) 30 and (e) 40 wt% of ENP. However. It is attributed to the fact that addition of the elastomeric moieties and disordered structure of PI/ENP hybrid films could reduce thermal stability of the resulting PI/ENP films. Fig. 3. the obtained nanocomposite shows smaller particles with good dispersion. the ENP particles must degrade before imide segments and promote the direct thermal decomposition of polymer matrix. it was observed that after introducing nanoelastomeric particles in the PI matrix. (b) 10. Fig. (e) 30 and (f) 40 wt% ENPs. Determination of particle size and morphology of PI/ENP nanocomposites Fig. the remained char yield decreased by increasing the elastomer weight percent.21 °C because of the degradation of aliphatic segments of elastomeric repeating unit i. wetting ability characteristics must be investigated if the polyimides are going to be chosen as a good candidate for adhesive materials. (b) 10. Unlike the pure PI. The mechanism of dispersion of nanoparticles may be influenced by the type of chemical or physical interactions between nanoparticle–nanoparticle and nanoparticle–media. (c) 20. It seems that the nanoparticles’ media could affect on their aggregation degree. It could be seen that the spherical elastomeric nanoparticles with particle size of about 40–60 nm are well dispersed. such as the Van der Waals or polar interactions and etc. 5. 5.

melt temperature. Sample 0 10 20 25 30 40 IDT (°C)a 348. This poor interaction hinders the proper and strong adhesion to the adherent surfaces and results in a reduced LSS. Any way.S.43 410. 6. 3. Due to the presence of St–BA–EGDMA nanoparticles with low Tg. It was expected that during this stage. adhesion time and pressure are three important parameters that would affect the degree of spreading. Jointing of two coupons for LLS analysis. 7. 6 represents the glass transition temperature (Tg) of pure PI and PI/ENP hybrid films measured by DSC.6.8 MPa pressure at 250 °C. 3. this problem is especially important. b Temperature at which 5% weight loss was recorded by TGA with a heating rate of 20 °C/min under N2 atmosphere. Types of failure in adhesive bonds. Fig.20 327. 9 [22]. most hotmelt adhesives can be used above their Tg and afford low viscosities. 9.71 327. whereas the adhesive layer between copper or stainless steel coupons were very fragile after setting.14 378. a reduction in LSS was observed (Fig. Measurement of LSS by subjecting single lap joints to tensile loads is a method for determination of adhesion strength of the bonded joints.63 370. However. Fig.01 T10 (°C)c 560. This method allows analyzing the failure modes in the bonded joints in addition to the measurement of LSS as shown in Fig. For enhancing the spread-ability and for the ease of applicability of the adhesive.71 401. At high nanoparticles’ percentage. LSS analysis It is well known that for any hot-melt adhesive application. In order to attain good adhesion. a good wetting of adherent surfaces was provided. It is Fig. The fractured surface of the broken lap-shear samples was analyzed using SEM and micrographs have been shown in Fig. Despite the increase in wetability of the adhesive with the increase in ENP wt%.45 45. copper and stainless steel were selected as adherents.65 38. Variation in glass transition temperature of PI nanocomposites with respect to the ENP wt%. / Journal of Colloid and Interface Science 336 (2009) 872–878 Table 3 Thermal properties of some polyimide–silica hybrid films obtained from TGA thermograms.57 385. Therefore. 8. the results are presented for specimens that were held for 2 h under 1.38 314. d Weight percent of the non-decomposed material by TGA at 700 °C with a heating rate of 20 °C/min under N2 atmosphere. According to Table 4 and due to the differences in thermal expansion coefficient of adhesive and adherent.67 Y700 (%)d 55. for rigid chain polymers like aromatic polyimides.69 37.97 335. 10. 8). In this study. 7. a trend in the decrease of Tg is observed by increasing the elastomeric nanoparticles content in the PI films. However. as illustrated in Fig. For aluminum coupons jointed by PI/ENP nanocomposite.7.27 36. it is well known that the degree of interactions also affects mechanical properties of the polymer. a substantial improvement is observed in the properties. high nanoparticle content resulted in the poor polymer chain entanglements. Material LTECa a Unfilled PI 45 [13] Al 23 [21] Cu 17 [21] Stainless steel 11–13 [21] Linear thermal expansion coefficient (10À6/°K). LSS amounts were found to increase initially with the increase in nanoparticles weight percent. which often show very high flow viscosities. lower viscosity is required [20]. entanglements of the polymer chains are reduced and mechanical properties of the adhesives are diminished. the viscosity increases with an increase in the above mentioned entanglements and consequently. some thermal stresses may build up and lead to failure of the adhesive layer. The highest lap-shear strength was obtained for aluminum specimen.08 877 a IDT (initial decomposition temperature) is the temperature at which initial mass loss was observed.09 32. three kinds of coupons: aluminum.21 T5 (°C)b 432. Fig.96 375. Low difference between expansion coefficient of the adhesive and aluminum would be the reason for the presence of stronger adhesion. But at the low nanoparticles’ percentage. which is well above the recorded Tg. this requirement is obtainable in the presence of lower polymer chain interaction or by using suitable diluents [20]. Fig. Often.71 378. .06 390.41 321.34 421.32 391. Table 4 Thermal expansion of adhesive and different adherents. Khoee et al. Investigation of the failure surface The failure of adhered joints can occur inside the adhesive layer (cohesion failure with adhesive residues on both surfaces) or at the interface between the adhesive layer and the adherent surface (adhesive failure). these parameters need to be properly controlled [20]. Pure PI exhibits the highest Tg value of 289 °C. Here. c Temperature at which 10% weight loss was recorded by TGA with a heating rate of 20 °C/min under N2 atmosphere. When the nanoparticle content exceeded more than 25 wt%. using high temperature could degrade the polymeric adhesive and the interface may lead to failure at the working temperature as a consequence. LSS measurement of PI/ENP nanocomposites.

Prog.pdf>. K. Adhesives and Sealants. vol. OH. N.M. J. S. 110 (2008) 1242. [7] V. Landfester. J. in: K. Magn. The fractured bonded surfaces were examined by scanning electron microscopy to determine failure patterns.878 S. (c) 20.40 -oxydianiline (PMDA–ODA) and copoly(styrene–butyl acrylate–ethyleneglycol dimethacrylate) (St–BA–EGDMA) nanoparticles. [6] D. Polym.e. 2001. W. [14] K.B. due to the decrease in polymer chain entanglements. Anhui Science & Technology Publishing House. Int. Mater. Sci. USA. Yamaguchi. The results showed that an appropriate amount of ENP in PI matrix could effectively reduce melt flow temperature of the PI adhesive and restrain the formation of crystalline PIs. [18] A. 10b shows the SEM micrograph of the fractured bonded surfaces prepared with PI nanocomposite containing 25 wt% of ENP. ASTM International. [21] D.). S. 1990. Sci 32 (2007) 623. Li. p. P. A. 2004–2005. Magn. C. J. Sundararajan. the failure mode moved toward ‘‘adhesive” with decreasing ENP wt% and toward ‘‘cohesive” with increasing ENP wt%. Fujii. Polyimides. Cassidy. Zhan. The (St–BA–EGDMA) nanoparticles solutions with 60 nm diameter as elastomeric nanoparticles (ENP) were mixed with high content (10–40 wt%) during synthesis at PAA stage and through mechanical agitation. SEM micrograph of fractured surfaces (a) 0. Polym. ASM International. Fluoropolymers 2. A. 1992. [17] Z. New York. Materials Park. P.S. Int. Int.A. 1995. [3] G.M. Antinietti. Adhes. Adhesive strengths for pure PI and its hybrids were measured on single-lap joints test method. J. 1984. Sci. Yang. 27 (2007) 319. 104 (2007) 3228. [8] M. J. (b)10. Polymer 42 (2001) 6173. [22] A. McGrath. Johns. It can be noted that failure mode was totally ‘‘adhesive” in nature as the adhesive matrix had a very poor melt flow behavior. Appl. 4. Polymer 46 (2005) 4390. Salehi-Mobarakeh. T. Polym. Engineered Materials Handbook. K. [2] S. Saeed. [11] K. (e) 30 and (f) 45 wt% samples. Stenzenberger. H. Khoee et al. Polym. F.E. St. Hefei. H. D. evident that with 10 wt% ENP. Prog. CRC Press. Ayambem. H. Ding. Above this amount.E. p. Sci. This kind of rough fractured surface is not common for most high-performance adhesives. Yao. Wang. 16 (1996) 219. Landfester. [16] M. Sci. Lide. Tong. These behaviors were attributed to the effect of Tg and chemical interactions of ENP nanoparticles with PI matrix.R. 18 (1998) 385. 27 (2007) 306. T. The PIs were prepared via a two-step method involving poly(amic acid) (PAA) step followed by thermal imidization to obtain polyimide in powder form. Plenum Press. Tamai. A. [9] M. The fracture energy of the hybrid with 25 wt% ENP was the highest one among the other PI nanocomposites.Z. Polym. Mittal (Ed. Wilson. Kawagoe. Adhes.dupont. 80. M. Yoshida. The fracture energy of the PI hybrids was firstly increased and then decreased with the increase in the elastomeric nanoprticle content. the nanocomposite provides a very rough and deformed fracture surface. 2002.S. Handbook of Chemistry and Physics. In fact.M.R. 20 (1999) 81. Fig.D. Adhes. H. Adhes. 85th ed. Available from: <http://www2.K.L. 1.H. G.R. Y. [10] J. Ikegami. Saeed. Macromol. [12] N. Int. Wilkes. J. several PIs were successfully synthesized through an in situ polymer– polymer nanocomposite preparation from pyromellitic dianhydride–4. Foroutan. Xu. K. / Journal of Colloid and Interface Science 336 (2009) 872–878 Fig. S. [15] Standard test method for apparent shear strength of single-lap joint adhesively bonded metal specimens by tension loading (Metal-to-metal). K. M. 10. Clair.M. P.L. (d) 25. Ratta. Kelly. Antonietti. [13] Original DuPont Datasheets. Similar features were observed on both sides of the fractured lap-shear specimen. [5] T. Khoee. Adhes. Gauthier. Adhes. Kluwer Academic Publishers. Shibuya. 3.). Mahdavian. Consequently. D.. New York. Hergenrother. T. M. . Wang. Nohon. [4] M. T. Sugibayashi. Hougham. 27 (2002) 689. increases the LSS strength of the composite adhesive. New York. Properties. J. Zhan. Adhes. Kyogoku. [20] M. Sonochemistry and its Applications. 99. On the other hand. the viscoelastic behavior of PI–ENP composites changed from solid-like to liquid-like by increasing elastomeric content. Adhes. vol. Yamaki. Deng. Davidson (Eds. J. Z.Y.. Fu. 27 (2002) 1283. the change in viscoelastic behavior of PIs by ENP causes an increase in wetting of the adherent surfaces and shows good metal–adhesive adhesion. H. Foster. A mixed failure mode i. Feng.com/ Vespel/en_US/Literature/sp1. Asua. Motoie. Appl. the lap-shear strengths decreased too. Bochthhold.L.L. cohesive/adhesive was observed for this matrix. Polymer 42 (2001) 2373. Sheppard. Rapid Commun. 277 (2004) 136. Summary In order to investigate the effect of elastomers on the adhesive properties of thermoplastic polyimides (PI) at nanoscale.C. Polyimides. L. Thus.B. PA. M. Blackie & Son Ltd. Prog. Kuroki. ASTM D1002. an increase in ENP up to 25 wt%. References [1] D. [19] M. Ashjari.

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