Experimental investigation into the effect of adhesion properties of PEEK modified by atmospheric pressure plasma and low pressure plasma

High performance polymer, Polyether Ether Ketone (PEEK) (service temperature ?250°C to +300°C, tensile strength: 120 MPa) is gaining significant interest in aerospace and automotive industries. In this investigation, attention is given to understand adhesion properties of PEEK, when surface of the PEEK is modified by two different plasma processes (i) atmospheric pressure plasma and (ii) low pressure plasma under DC Glow Discharge. The PEEK sheets are fabricated by ultra high temperature resistant epoxy adhesive (DURALCO 4703, service temperature ?260°C to +350°C). The surface of the PEEK is modified through atmospheric pressure plasma with 30 and 60 s of exposure and low pressure plasma with 30, 60, 120, 240, and 480 s of exposure. It is observed that polar component of surface energy leading to total surface energy of the polymer increases significantly when exposed to atmospheric pressure plasma. In the case of low pressure plasma, polar component of surface energy leading to total surface energy of the polymer increases with time of exposure up to 120 s and thereafter, it deteriorates with increasing time of exposure. The fractured surface of the adhesively bonded PEEK is examined under SEM. It is observed that unmodified PEEK fails essentially from the adhesive to PEEK interface resulting in low adhesive bond strength. In the case of surface modified PEEK under atmospheric pressure plasma, the failure is entirely from the PEEK and essentially tensile failure at the end of the overlap resulting in significant increase in adhesive bond strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of plasma treatment and electron beam radiations on the strength of nanofilled adhesive‐bonded joints

This investigation highlights the adhesion performance of carbon fiber‐ and glass fiber‐reinforced polyphenylene sulfide when joined by high‐performance neat epoxy adhesive and nanofilled epoxy adhesive. A significant increase in the surface energy of these materials is observed after the surface modification with atmospheric plasma treatment. An increase in surface roughness is observed after exposing the surface to plasma. Lap shear testing of untreated and plasma‐treated joints is carried out to correlate the improvement in adhesion properties with the joint strength. A considerable increase in joint strength is observed when the surfaces of these materials are modified by atmospheric pressure plasma. There is a further increase in joint strength when the composites are joined by nanofilled epoxy adhesive, and subsequent exposure to electron beam radiations results in minor increase in the joint strength. Finally, the fractured surfaces of the joints are examined and the analysis is performed. POLYM. ENG. SCI., 50:1505–1511, 2010. © 2010 Society of Plastics Engineers     

Process optimization of solvent based polybenzimidazole adhesive for aerospace applications

The use of adhesive bonding for high temperature applications is becoming more challenging because of low thermal and mechanical properties of commercially available adhesives. However, the development of high performance polymers can overcome the problem of using adhesive bonding at high temperature. Polybenzimidazole (PBI) is one such recently emerged high performance polymer with excellent thermal and mechanical properties. It has a tensile strength of 160 MPa and a glass transition of 425 °C. Currently, PBI is available in solution form with only 26% concentration in Dimethyl-acetamide solvent. Due to high solvent contents, the process optimization required lot of efforts to form PBI adhesive bonded joints with considerable lap shear strength. Therefore, in present work, efforts are devoted to optimize the adhesive bonding process of PBI in order to make its application possible as an adhesive for high temperature applications. Bonding process was optimized using different curing time and temperatures. Epoxy based carbon fiber composite bonded joints were successfully formed with single lap shear strength of 21 Mpa. PBI adhesive bonded joints were also formed after performing the atmospheric pressure plasma treatment of composite substrate. Plasma treatment has further improved the lap shear strength of bonded joints from 21 MPa to 30 MPa. Atmospheric pressure plasma treatment has also changed the mode of failure of composite bonded joints.     

Durability of PBI adhesive bonded joints under various environmental conditions

Structural adhesives are finding increasing use in many applications. However, their utilization at elevated temperature has always been a challenge due to their low thermal and mechanical properties. However, in recent years, the development of high performance polymers have overcome the problem of using adhesive bonding at high temperature to some extent. Polybenizimidazole (PBI) is one such recently emerged high performance polymer with excellent thermal and mechanical properties. It has a tensile strength of 160 MPa and a glass transition temperature (T_g) of 425 °C. Due to its excellent thermal and mechanical properties, it has the potential to be used as an adhesive under various environmental conditions. In the present work, efforts are devoted to explore the potential of using PBI at high temperature and in hot-wet environmental conditions. M21 and DT120 epoxy based carbon fiber composite bonded joints were prepared and tested. Both M21/carbon composite and DT120/carbon composite have exhibited a reduction in joint strength of about 16% and 25% respectively after 1000 h of conditioning in a hot-wet environment. However, a reduction in lap shear strength of 52% and 56% is observed when composite bonded joints were tested at 80 °C.     

High-performance nanoadhesive bonding of titanium for aerospace and space applications

In this investigation, attempts are made to prepare high-performance nanoadhesive bonding of titanium for its essential applications to aviation and space. The high-performance nanoadhesive is prepared by dispersing silicate nanoparticles into the ultra-high-temperature-resistant epoxy adhesive at 10 wt% ratio with the matrix adhesive followed by modification of the nanoadhesive after curing under high-energy radiation for 6 h in the pool of SLOWPOKE-2 nuclear reactor with a dose rate of 37 kGy/h to promote crosslink into the adhesive. Prior to bonding, the surfaces of the titanium sheets are mechanically polished by wire brushing, ultrasonically cleaned by acetone and thereafter the titanium sheets are modified by plasma ion implantation using plasma nitriding. The titanium surface is characterized by X-ray photoelectron spectroscopy (XPS). The thermal characteristics of the epoxy adhesive and the high-performance nanoadhesive are carried out by thermal gravimetric analysis (TGA). The TGA studies clearly shows that for the basic adhesive there is a weight loss of the adhesive, however, in the case of epoxy–silicate nanoadhesive, there is almost 100% retention of weight of the adhesive, when the adhesive is heated up to 350 °C. Lap shear tensile strength of the joint increases considerably, when the titanium surface is modified by plasma-nitriding implantation. There is a further massive increase in joint strength, when the plasma-nitriding implanted titanium joint is prepared by nanosilicate–epoxy adhesive and further modification of the adhesive joint under high-energy radiation results a further significant increase in joint strength. In order to simulate with aviation and space climatic conditions, the joints are separately exposed to cryogenic (?196 °C) and elevated temperature (+300 °C) for 100 h and thermal fatigue tests of the joints are carried out under 10 cycles by exposing the joint for 2 h under the above temperatures. When the joint completely kept at ambient condition and the joint strength compared with those joints exposed to aviation and space climatic conditions, it is observed that the joint could retain 95% of the joint strength. Finally, to understand the behavior of the high-performance silicate–epoxy nanoadhesive bonding of titanium, the fractured surfaces of the joints are examined by scanning electron microscope.     

Viscoelastic and adhesive properties of single‐component thermo‐resistant acrylic pressure sensitive adhesives

Poly(butyl acrylate‐vinyl acetate‐acrylic acid) based acrylic pressure sensitive adhesives (PSAs) were synthesized by solution polymerization for the fabrication of high performance pressure sensitive adhesive tapes. The synthesized PSAs have high shear strength and can be peeled off substrate without residues on the substrate at temperature up to 150°C. The PSAs synthesized in the present work are single‐component crosslinked and they can be used directly once synthesized, which is convenient for real applications compared to commercial multi‐component adhesives. The results demonstrated that the viscosity of the PSAs remained stable during prolonged storage. The effects of the preparation conditions such as initiator concentration, cross‐linker amount, organosiloxane monomer amount and tackifier resin on the polymer properties, such as glass transition temperature (T_g), molecular weight (M_w), surface energy and shear modulus, were studied, and the dependence of the adhesive properties on the polymer properties were also investigated. Crosslinking reactions showed a great improvement in the shear strength at high temperature. The addition of tackifier resin made peel strength increase compared to original PSAs because of the improvement of the adhesion strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40086.     

Preparation of polysiloxane phosphonic acid doped polybenzimidazole high‐temperature proton‐exchange membrane

Polysiloxane phosphonic acid doped polybenzimidazole (PBI) high‐temperature membranes were fabricated in this study. Polysiloxane phosphonic acid instead of phosphoric acid was used as a proton conductor to prevent acid from leaking. The membrane samples with different amounts of PBI were prepared and characterized with respect to the structure, thermal properties, oxidative stability, proton conductivity, and mechanical properties. The Fourier transform infrared results show that hydrogen bonds formed between PBI and polysiloxane phosphonic acid. Thermal analysis confirmed that the temperature at which membrane experienced 10% weight loss was above 230°C. None of the membrane samples broke into pieces after Fenton reagent testing. The proton conductivity of the membrane samples with 5% PBI was up to 0.034 S/cm at 140°C under nominally anhydrous conditions. The tensile strength of the membrane samples with 10% PBI was 18.3 MPa. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42956.     

Grafting of N‐carbamyl maleamic acid onto a styrene–butadiene–styrene copolymer

A styrene–butadiene–styrene block copolymer (SBS) was functionalized with N‐carbamyl maleamic acid (NCMA) using two peroxide initiators with the aim of grafting polar groups onto the molecular chains of the polymer. The influence of the concentration of benzoyl peroxide (BPO) and 2,5‐dimethyl, 2,5‐diterbuthylperoxihexane (DBPH) was studied. The concentration of peroxy groups ranged between 0.75 and 6 × 10^?4 mol % while the concentration of NCMA was constant at 1 wt %. The reaction temperature was chosen according to the type of peroxide employed, being 140°C for BPO and 190°C for DBPH. FTIR spectra confirmed that NCMA was grafted onto the SBS macromolecules. It was found that the highest grafting level was achieved at a concentration of peroxy groups of about 3 × 10^?4 mol %. Contact angle measurements were used to characterize the surface of the SBS and modified polymers. The contact angle of water drops decreased with the amount of NCMA grafted from 95°, the one corresponding to the SBS, to about 73°. T‐peel strength of polymer/polyurethane adhesive/polymer joints made with the modified polymers was larger than those prepared with the original SBS. The peel strength of SBS modified with 1.5 and 3 × 10^?4 mol % of peroxy groups from BPO were five times larger than that of the original SBS. The materials modified using BPO showed peel strengths higher than the ones obtained with DBPH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4468–4477, 2006     

Crosslinking of polybenzimidazole membranes by divinylsulfone post‐treatment for high‐temperature proton exchange membrane fuel cell applications

Phosphoric acid‐doped polybenzimidazole (PBI) has been suggested as a promising electrolyte for proton exchange membrane fuel cells operating at temperatures up to 200 °C. This paper describes the development of a crosslinking procedure for PBI membranes by post‐treatment with divinylsulfone. The crosslinking chemistry was studied and optimized on a low‐molecular‐weight model system and the results were used to optimize the crosslinking conditions of PBI membranes. The crosslinked membranes were characterized with respect to chemical and physiochemical properties, showing improved mechanical strength and oxidative stability compared with their linear analogues. Fuel cell tests were further conducted in order to demonstrate the feasibility of the crosslinked membranes. Copyright © 2011 Society of Chemical Industry     

Atmospheric pressure plasma surface modification of titanium for high temperature adhesive bonding

In this investigation surface treatment of titanium is carried out by plasma ion implantation under atmospheric pressure plasma in order to increase the adhesive bond strength. Prior to the plasma treatment, titanium surfaces were mechanically treated by sand blasting. It is observed that the contact angle of de-ionized water decreases with the grit blast treatment time. Optical microscopy and scanning electron microscopic (SEM) analysis of untreated and atmospheric plasma treated titanium are carried out to examine the surface characteristics. A substantial improvement in the surface energy of titanium is observed after the atmospheric pressure plasma treatment. The surface energy increases with increasing exposure time of atmospheric pressure plasma. The optimized time of plasma treatment suggested in this investigation results in maximum adhesive bond strength of the titanium. Unmodified and surface modified titanium sheets by atmospheric pressure plasma were adhesively bonded by high temperature resistant polyimide adhesive. The glass transition temperature of this adhesive is 310 °C and these adhesively bonded joints were cured at high temperature. A substantial improvement in adhesive bond strength was observed after atmospheric pressure plasma treatment.     

Adhesion of glow discharge polymers to metals and polymers

Adhesion of glow discharge polymers to metals and polymers in an adhesive joint was measured by lap-shear test and immersion in hot water of 70°C °C for an extended time. A glow discharge polymer was deposited onto polymers [polyethylene and poly(tetrafluoroethylene)] and metals (aluminum and stainless steel) prior to when the polymer and metal were joined. It is found that the lap-shear strength is enhanced by coating the surfaces of these substrates with plasma film produced from methane, ethylene, and acetylene, and that deterioration of the adhesive bonding part, when immersed in hot water of 70°C, is strongly dependent on the gas used as well as operational conditions where a polymer film is formed. The adhesion of a polymer produced from methane on the polymer and metal is strong enough to apply for durable, adhesive joints.     

Mechanical behavior of SiC joints brazed using an active Ag‐Cu‐In‐Ti braze at elevated temperatures

The behavior of SiC ceramic joints brazed with commercially available Incusil ABA (Ag‐32.25Cu‐12.5In‐1.25Ti, in wt.%) was characterized especially with respect to the mechanical performance at temperatures up to 550°C using four‐point bending and torsional shear tests. The failure mechanisms with changing temperature were investigated with the aid of fractography. Additionally, the microstructure of brazed specimens was characterized in detail by high resolution scanning electron microscopy. The test geometry and setup for the high temperature torsional shear test is presented. The change in mechanical behavior of the joints as a function of temperature is shown and discussed. The brazed joints interestingly showed that flexural bending strength was maintained with only a small decrease up to 300°C. Above 300°C, the bending strength decreased much faster. For the first time, this joint system was characterized in torsional shear test at temperatures up to 550°C to achieve the intrinsic shear strength values. Very strong joints were achieved, resulting in failure through the ceramic base materials up to (torsional shear) testing temperatures of 400°C. The results indicate that SiC joints brazed with Incusil ABA exhibit excellent mechanical performance for applications up to 300°C.     

Polysilazane‐based heat‐ and oxidation‐resistant coatings on carbon fibers

Carbon fibers must be protected from a high‐temperature oxidizing environment because, at approximately 500°C and above, the fibers exhibit reduced mass and strength stability. The fibers can be protected by the application of thermal coatings, which simultaneously improve the adhesive properties of the carbon fibers in the composite materials. Polysilazanes are a new family of heat‐resistant polymer coatings that are converted into silicone carbide or silicone nitride ceramic structures at high temperatures. The converted ceramics are resistant to the effects of high temperatures. In this research work, polysilazane‐based coatings were applied to carbon filament (CF) rovings with the dip‐coating method. Tensile testing at room temperature and under thermal stress was carried out to assess the mechanical and thermomechanical properties of both coated and uncoated rovings. Scanning electron microscopy and energy‐dispersive X‐ray analysis were performed to evaluate the surface topographical properties of the coated and uncoated rovings. Thermogravimetric analysis was executed to determine the thermal stability of the polymer coatings. The coating performance on the CF rovings was determined by assessment of the test results obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hygrothermal ageing of adhesive joints with nanoreinforced adhesives and different surface treatments of carbon fibre/epoxy substrates

The effect of water absorption on the strength of single lap adhesive joints subjected to accelerated hygrothermal ageing (55 °C, 95% relative humidity, 800 h) was analysed. Two different variables were studied: the surface treatment of the carbon fibre/epoxy laminates (peel ply, grit blasting and atmospheric pressure plasma) and the addition of carbon nanofillers (0.5 wt% nanofibres and 0.25 wt% nanotubes) to the epoxy adhesive. The joint strength and the failure mode of the joints were investigated. Furthermore, the amount of water absorbed by the adhesive was determined.Adhesive joints with peel ply-treated laminates exhibit an increase in their strength, which is attributed to a relaxation of stresses in the adhesive/laminate interface; with grit blasting, this property remains almost constant. Plasma treatment provides the worst ageing behaviour because this treatment results in a surface with a higher surface free energy, which is more susceptible to environmental attack. The nanoreinforcement of the adhesive has a beneficial effect: it decreases the amount of absorbed water.     

Effect of Temperature on the Joints Strength of an Automotive Polyurethane Adhesive

In this paper, the performance of an automotive polyurethane adhesive was studied through adhesive joints tests. Butt joints and single lap joints were fabricated and tested at seven temperature measuring points (TMPs). It is shown that both the tensile strength and lap shear strength decrease with the increasing of temperature. Quadratic polynomial expression obtained by the least square method can represent the tensile and lap shear strength as a function of temperature very well. ?40°C, 0°C, and 90°C were selected as the most ideal TMPs for this adhesive through the comparison of the residual sums of squares of 35 fitting curves with different combination of TMPs. Scarf joints with adhesive angles of 60° and 30° were fabricated and tested at ?40°C, 0°C, and 90°C. It also showed a decrease in joint strength with the increasing temperature. Joint strength as a function of adhesive angle is presented. It was found to closely follow a linear behaviour. A three-dimensional surface, consisting of temperature, adhesive angle, and joint strength, is presented finally to facilitate the design of automotive bonding structures.     

Effect of temperature on the joint strength of a silyl-modified polymer-based adhesive

Temperature is a very important factor that must be fully considered in the study on the adhesive joint strength. In this paper, a silyl-modified polymer-based adhesive ISR 70-08 which is widely used in engineering was studied. Dog-bone specimens were fabricated and tested at ?40°C, room temperature (RT), and 90°C. Results show a decrease in the main mechanical properties with increasing temperature. Butt joints (BJs), single-lap joints (SLJs), and Scarf joints (SJs) were fabricated and tested at different temperatures. A quadratic polynomial expression was an ideal choice to express the joint strength as a function of temperature which was obtained using the least-squares method. Temperature combinations of ?40°C, 0°C, and 90°C were obtained to study the effect of temperature on the joint strength more easily for this adhesive. A three-dimensional surface, consisting of temperature, adhesive angle, and joint strength was presented to facilitate the application of bonding structures in engineering     

Influence of the filler material on the thermal stability of one‐component moisture‐curing polyurethane adhesives

Filler materials are part and parcel for the adjustment of adhesives, in particular, their rheological and mechanical properties. Furthermore, the thermal stability of adhesives can be positively influenced by the addition of an expedient filler, with inorganic types common practice in most cases. In this study, one‐component moisture‐curing polyurethane adhesives for engineered wood products based on isocyanate prepolymers with different polymer‐filled polyether polyols were investigated with regard to the filler's potential to increase the thermal stability of bonded wood joints. The property changes due to the addition of fillers were determined by means of mechanical tests on bonded wood joints and on pure adhesive films at different temperatures up to 200°C. Additional analyses by atomic force and environmental scanning electron microscopy advanced the understanding of the effects of the filler. The tested organic fillers, styrene acrylonitrile, a polyurea dispersion, and polyamide, caused increases in the cohesive strength and stiffness over the whole temperature range. However, the selected filler type was hardly important with regard to the tensile shear strength of the bonded wood joints at high temperatures, although the tensile strength and Young's modulus of the adhesive films differed over a wide range. Prepolymers with a lower initial strength and stiffness resulted in worse cohesion, in particular, at high temperatures. This disadvantage, however, could be compensated by means of the filler material. Ultimately, the addition of filler material resulted in optimized adhesive properties only in a well‐balanced combination with the prepolymer used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

ROMP‐based boron nitride composites

The present work focuses on the investigation of the thermal and dielectric properties of composites obtained by surface‐modified hexagonal boron nitride (hBN) and ring‐opening metathesis polymerization (ROMP) based polymer. A new kind of high performance composites was developed based on using amino silane functionalized hBN (AS‐hBN) and bromine functional group possessing homo and copolymers synthesized via ROMP pathway. Aminosilane capped boron nitride (BN) and bromine bearing polymer backbone enhance the interaction between filler and the polymer chains. The effects of surface‐modified BN (AS‐hBN) and its content on the dielectric properties, and thermal resistance of composites, are systematically investigated and discussed. The resultant composites possess high electrical break over voltages. While all of the ROMP‐based films exhibit low ?′ value in a wide frequency range, in the case of the composite with 20% AS‐hBN and poly(bromooxanorbornene‐co‐cyclooctadiene) (ROMP‐BN‐6) displays very low dielectric constants in around 1.5 up to 1 MHz at 20 °C. This value is significantly lower than that of common polymer dielectrics, which is usually in the range of 3–6. Besides the lowest dielectric constant of ROMP‐BN‐6, it has also the smallest dielectric loss tangent even at high temperatures. Tan δ of ROMP‐BN‐6 is 0.003 and 0.0067 at 10 Hz–1 MHz at 20 °C, respectively. Thermal stability of polymers was also improved by introducing surface‐modified hBN. Polymers bearing 20% AS‐hBN are highly thermally stable up to ～350 °C and gave 25% char yield at 800 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45658.     

Epoxy–imide resins from N‐(4‐ and 3‐carboxyphenyl)trimellitimides. I. Adhesive and thermal properties

Epoxy–imide resins were obtained by curing Araldite GY 250 (diglycidyl ether of bisphenol‐A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac–epoxy resin; polyfunctional) with N‐(4‐ and 3‐carboxyphenyl)trimellitimides derived from 4‐ and 3‐aminobenzoic acids and trimellitic anhydride. The adhesive lap shear strength of epoxy–imide systems at room temperature and at 100, 125, and 150°C was determined on stainless‐steel substrates. Araldite GY 250‐based systems give a room‐temperature adhesive lap shear strength of about 23 MPa and 49–56% of the room‐temperature adhesive strength is retained at 150°C. Araldite EPN 1138‐based systems give a room‐temperature adhesive lap shear strength of 16–19 MPa and 100% retention of room‐temperature adhesive strength is observed at 150°C. Glass transition temperatures of the Araldite GY 250‐based systems are in the range of 132–139°C and those of the Araldite EPN 1138‐based systems are in the range of 158–170°C. All these systems are thermally stable up to 360°C. The char residues of Araldite GY 250‐ and Araldite EPN 1138‐based systems are in the range of 22–26% and 41–42% at 900°C, respectively. Araldite EPN 1138‐based systems show a higher retention of adhesive strength at 150°C and have higher thermal stability and T_g when compared to Araldite GY 250‐based systems. This has been attributed to the high crosslinking possible with Araldite EPN 1138‐based systems arising due to the polyfunctional nature of Araldite EPN 1138. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1729–1736, 2000     

Wedge test of carbon‐nanotube‐reinforced epoxy adhesive joints

Epoxy adhesives reinforced with carbon nanotubes (CNTs) were developed. The distribution of the CNTs in the epoxy matrix was observed with transmission electron microscopy. Joints were formed by unclad 2024‐T3 aluminum adherents bonded with the CNT‐filled epoxy adhesives. The durability of the joints was studied with a wedge test under water at 60°C. The addition of CNTs to the epoxy greatly improved the adhesive joint durability. The initial crack length of the joint with 1 wt % CNTs, which was obtained before the wedge specimen was put into water, was only about 7% of that with neat epoxy. After immersion of the specimens in 60°C water, the joint with neat epoxy failed after 3 h, but all of the joints adhered with different fractions of CNTs were still bound together after the experimental time of 90 h. The significant enhancement by CNTs of the adhesive joint durability was mainly attributed to the high mechanical properties of the CNTs and their ability to resist water. Nevertheless, the experimental results also reveal that the durability of the joints showed an optimum value at approximately 1 wt % CNTs, beyond which a decrease in the property was observed. In addition, the failure mechanism of the joints was also investigated in terms of interfacial failure and cohesive failure. Cohesive dominated failure was found for the joint bonded with 1 wt % CNT‐filled epoxy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009