Surface plasma treatment effects on the molecular structure at polyimide/air and buried polyimide/epoxy interfaces

Polyimides are widely used as chip passivation layers and organic substrates in microelectronic packaging. Plasma treatment has been used to enhance the interfacial properties of polyimides, but its molecularmechanism is not clear. In this research, the effects of polyimide surface plasma treatment on the molecular structures at corresponding polyimide/air and buried polyimide/epoxy interfaces were investigated in situ using sum frequency generation (SFG) vibrational spectroscopy. SFG results show that the polyimide backbone molecular structure was different at polyimide/air and polyimide/epoxy interfaces before and after plasma treatment. The different molecular structures at each interface indicate that structural reordering of the polyimide backbone occurred as a result of plasma treatment and contact with the epoxy adhesive. Furthermore, quantitative orientation analysis indicated that plasma treatment of polyimide surfaces altered the twist angle of the polyimide backbone at corresponding buried polyimide/epoxy interfaces. These SFG results indicate that plasma treatment of polymer surfaces can alter the molecular structure at corresponding polymer/air and buried polymer interfaces.     

Improvement of PBO fiber surface and PBO/PPESK composite interface properties with air DBD plasma treatment

The interface of fibrous composites is a key factor to the whole properties of the composites. In this study, the effects of air dielectric barrier discharge (DBD) plasma discharge power density on surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fiber and the interfacial adhesion of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated by several characterization methods, including XPS, SEM, signal fiber tensile strength, interlaminar shear strength, and water absorption. After the air DBD plasma treatment at a power density of 41.4 W/cm³, XPS analysis showed that some polar functional groups were introduced on the PBO fiber surface, especially the emergence of a new oxygen‐containing group (?O–C = O group). SEM observations revealed that the air DBD plasma treatment had a great influence on surface morphologies of the PBO fiber, while the signal fiber tensile strength results showed only a small decline of 5.9% for the plasma‐treated fiber. Meanwhile, interlaminar shear strength value of PBO/PPESK composite was increased to 44.71 MPa by 34.5% and water absorption of the composite decreased from 0.46% for the untreated specimen to 0.27%. The results showed that the air DBD plasma treatment can effectively improve the properties of the PBO fiber surface and the PBO/PPESK composite interface. Results obtained from the above analyses also showed that both the fiber surface and the composite interface performance would be reduced when an undue plasma discharge power density was applied. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of carbon fiber surface treatments on the flexural strength and tribological properties of short carbon fiber/polyimide composites

Pitch‐based short carbon fibers (CFs) were treated by air oxidation and cryogenic nitrogen, respectively. Thereafter the treated and untreated CFs were incorporated into polyimide (PI) matrix to form composites. The CFs before and after treatment were examined by XPS and SEM.The flexural strength of the specimen was determined in a three‐point test machine and the tribological properties of PI composites sliding against GCr15 steel rings were evaluated on an M‐2000 model ring‐on‐block test rig. The results show that the surface of the treated CFs became rougher. Lots of active groups formed on the CF surface after air oxidation.The treatment can effectively improve the mechanical and tribological properties in their PI composites due to the enhanced fiber‐matrix interfacial bonding. Copyright © 2008 John Wiley & Sons, Ltd.     

The influence of surface treatment on the tensile and tribological properties of wood fiber‐reinforced polyimide composite

In this paper, the effect of coupling agent surface treatment of wood fiber on tensile and tribological property of wood fiber‐reinforced thermoplastic polyimide (PI) composites was experimentally investigated. Experimental results revealed that coupling agent surface treatment could effectively improve the interfacial adhesion between wood fiber and PI matrix. Compared with the untreated wood fiber/PI composite, the coupling agent‐treated composite had better interfacial adhesion. The fracture surfaces and worn surface of samples were investigated by scanning electronic microscopy to analyze the effects of surface treatment methods.     

Effects of ionizing radiation on epoxy,graphite fiber and epoxy/graphite fiber composites. Part I: Surface energy changes

Surface energy changes of an epoxy based on tetraglycidyl diaminodiphenyl methane (TGDDM)/diaminodiphenyl sulfone (DDS), T-300 graphite fiber, and T-300/5208 (graphite fiber/epoxy) composites have been investigated after irradiation with 0.5 MeV electrons. The surface energy of TGDDM-DDS epoxy increases monotonically with radiation doses up to 1,000 Mrad mainly due to increased concentration of polar groups. IR and ESCA spectral evidence indicates that carbonyl groups are formed, probably from the tertiary hydrogen at the carbon where the ? OH group is attached in the cured epoxy. The polarity of the graphite fiber and the graphite fiber/epoxy interface also increases with radiation dose. These results and the roles of oxygen are discussed in connection with mechanical properties of epoxy/graphite fiber composites exposed to ionizing radiation.     

Toughened carbon fiber composites with morphology gradient

The morphology and fracture behavior of polyimide modified carbon fiber/dicyanate composites were analyzed. Composites having morphology gradient were prepared by inserting a polyimide film between prepregs of carbon fabric impregnated by dicyanate alone, and controlling the relative rate of dissolution of polyimide and the polymerization of dicyanate by adding zinc stearate catalyst. The composites having morphology gradient showed G_ic and G_iic values of 2.2 kJ/m² and 1.4 kJ/m² respectively, which showed 3–5 times of those values of unmodified carbon fiber/dicyanate composites.     

石墨纤维氧化表面处理对环氧树脂界面粘合影响的研究

<正> 由于石墨纤维表面能较低,因此石墨纤维/树脂复合材料的界面粘合情况极为重要,为了阐明界面的粘合机理,需要对石墨纤维的表面特性如表面活化能、浸润性、表面积、表面化学基团等方面进行研究,为了提高复合材料的层间剪切强度,常常用各种方法对石墨纤维的表面进行处理,以期改变纤维表面的物理和化学结构来增加纤维和环氧树脂     

Plasma treatment of carbon fiber on the tribological property of polyimide composite

The effect of different ratios of carbon fiber (CF) reinforcing polyimide (PI) and surface treatment of CF on the microstructure and wear resistance of surface layers was studied. The increase of CF content led to a gradual increase in the Interlaminar shear strength (ILSS) values, and the maximum ILSS value arises when the CF content is 15 vol%, with an improvement of 13.45% compared to virgin CF composites. The increased interfacial adhesion could be contributed mainly to the presence of branched PI at the interface region. SEM of the worn surface confirms that the plasma treatment efficiently improves the interfacial adhesion of CF/PI composite. Copyright © 2017 John Wiley & Sons, Ltd.     

Mechanical properties of plasma‐treated carbon fiber reinforced PTFE composites with CNT

This paper is concerned with the effects of the plasma surface treatment and the addition of CNT on the mechanical properties of carbon fiber/polytetrafluoroethylene (PTFE) composite. The tensile and flexural strength of composites containing CNT and plasma‐treated carbon fibers improved. The flexural strength first decreases with respect to the CF content. The flexural strength increases to 179 MPa for the plasma‐treated composite as compared with 167 MPa for the neat carbon fiber composites. The overall improvement is thus nearly 8%.     

The effect of surface modification with nitric acid on the mechanical and tribological properties of carbon fiber‐reinforced thermoplastic polyimide composite

Polyacrylamideacrylate (PAN)‐based carbon fibers were submitted to nitric acid oxidation treatments to improve the interfacial adhesion of the carbon fiber (CF)‐reinforced polyimide (CF/PI) composite. The carbon fiber surfaces were characterized by X‐ray photoelectron spectroscopy (XPS). Nitric acid oxidation not only affects the oxygen concentration but also produces an appreciable change in the nature of the chemical functions, namely the conversion of hydroxy‐type oxygen into carboxyl functions. Nitric acid oxidation treatment modifies the element constituting the fiber, the nitrogen concentration being about 1.2 times higher at the fiber external surface compared to the untreated one. The mechanical and tribological properties of the polymide (PI) composites reinforced by the carbon fibers treated with nitric acid oxidation were investigated. Results showed that the tensile strength of the CF/PI composites improved remarkably due to nitric acid treatment along with enhancement in friction and wear performance. Copyright © 2009 John Wiley & Sons, Ltd.     

Aging behavior of dielectric barrier discharge‐modified Twaron fibers in different storage environments

The aging behavior of air dielectric barrier discharge plasma treatment was investigated by storing the treated fibers respectively in air and in the oxidizing environment. Based on several testing methods, this study led us to the conclusion that the aging effects in the oxidizing environment were less obvious than that in air. X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy indicated that the decay of fiber surface polar groups was more remarkable for fibers aged in air. The atomic force microscopy photos showed that the further oxidation generated by the oxidizing chemicals such as ozone increased fiber surface roughness. Thus, there was no obvious reduction in the wettability of the modified fibers during the aging process in the oxidizing environment. These changes in surface properties could explain the variation in interlaminar shear strength of Twaron fiber reinforced composites. After the fibers were aged in air for 48 h, interlaminar shear strength of the composites declined by 18.4% while had a decrease of only 11.4% after aging for 48 h in the case of the oxidizing environment. The results were supported by the water absorption test, which also reflected the effects of different storage conditions on the composite interfacial adhesion, and showed the inhibitory effect of the oxidizing environment on plasma aging. Copyright © 2016 John Wiley & Sons, Ltd.     

共混改性聚酰亚胺中空纤维膜的压缩空气除湿性能研究

采用干／湿相转换法制备了共混聚酰亚胺中空纤维膜,并对其与聚酢亚胺(PI)中空纤维膜的除湿性能进行了比较,结果表明：在不同压力、不同流量和不同吹扫比例的情况下,共混膜的除湿性能均优于PI膜,特别是增大吹扫比例时,共混膜的优越性更为明显,虽然在抽真空的条件下,共混膜的除湿性能不如采用吹扫操作方式的,但是,同PI膜相比脱湿性能仍然好于PI膜。     

Evaluation of the hybridization effect on the thermal and thermo-oxidative stability of bamboo/kenaf/epoxy hybrid composites

Bamboo-/kenaf-reinforced epoxy hybrid composites were prepared by hand layup method. The aim of this study is to look into the hybridization effect of bamboo and kenaf fibers at different ratios on thermal and thermo-oxidative (TOD) stabilities of hybrid composites. Three types of hybrid composites were fabricated with different mass ratios of bamboo fiber mat (B) to kenaf fiber mat (K), namely B/K 70:30, B/K 50:50 and B/K 70:30 while maintaining total fiber loading of 40% by mass. The thermal stability and thermo-oxidative (TOD) stability were analyzed by thermogravimetric analyzer. Differential scanning calorimetry (DSC) was used to investigate the oxidation onset temperature (OOT) of all the composites. The results reveal that bamboo composite shows higher thermal stability than kenaf composite in both inert and oxidative atmospheres. An increase in bamboo fibers mass ratio in the hybrid composite improved the thermal and TOD stability. The thermal and TOD stabilities of the hybrid composites follow the sequence of B/K 70: 30?>?B/K 50:50?>?B/K 30:70. Pure epoxy composite recorded the highest OOT at 197.50 °C. The results show that the addition of natural fiber in the epoxy matrix has significantly reduced the OOT compared to the pure epoxy. Data obtained from this work will help us to fabricate a sustainable and biodegradable component for automotive or building materials.

     

Effects of ionizing radiation on epoxy,graphite fiber,and epoxy/graphite fiber composites. Part II: Radical types and radical decay behavior

Electron spin resonance (ESR) investigations of line shapes and radical decay behavior have been made on an epoxy based on tetraglycidyl diaminodiphenyl methane (TGDDM)/diaminodiphenyl sulfone (DDS), T-300 graphite fiber, and T-300/5208 (graphite fiber/epoxy) composites after irradiation with Co₆₀ γ-radiation or 0.5 MeV electrons. Two kinetically distinct radical species are found in the irradiated epoxy as the temperature is raised beyond 120 K following irradiation of samples at 77 K with Co₆₀ γ. One has been termed a fast-decaying species and the other a slow-decaying species. The ratio of fast-decaying/slow-decaying radicals increases as the decay temperature rises. The fast-decaying radicals at room temperature are attributed largely to alkyl type radicals residing in regions of relatively low crosslink density, while the long-lived radicals are attributed to radicals residing in the highly crosslinked regions of the epoxy. A large concentration (ca. 10₂₀ to 10₂₁ spins/g) of unpaired electrons was found in unirradiated graphite fiber which masked the ESR spectral change in irradiated composites.     

Interfacial studies on the ozone and air‐oxidation‐modified carbon fiber reinforced PEEK composites

In this work, ozone modification method and air‐oxidationwere used for the surface treatment of polyacrylonitrile(PAN)‐based carbon fiber. The surface characteristics of carbon fibers were characterized by XPS. The interfacial properties of carbon fiber‐reinforced (polyetheretherketone) PEEK (CF/PEEK) composites were investigated by means of the single fiber pull‐out tests. As a result, it was found that IFSS (interfacial shear strength) values of the composites with ozone‐treated carbon fiber are increased by 60% compared to that without treatment. XPS results show that ozone treatment increases the amount of carboxyl groups on carbon fiber surface, thus the interfacial adhesion between carbon fiber and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibers on the tribological properties of CF/PEEKcomposites was comparativelyinvestigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PEEK matrix. Thus the wear resistance was significantly improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular dynamics simulations of liquid crystal molecules on a polyimide monolayer

Preliminary results are presented on the molecular dynamics simulations of alignment of the liquid crystal molecule, 4-n-octyl-4'-cyanobiphenyl (8CB), on a polyimide (pyromelltic dianhydride-p-phenylene diamine) oligomer monolayer. We actually simulated a three-layer system, i.e., liquid crystal molecule/polyimide oligomer/a basal plane of graphite. First, simulations of the oligomers adsorbed on graphite were done in order to obtain reasonable adsorption structures, as the pre-stage simulation of the three-layer system. Then, by placing a liquid crystal layer on top, the three-layer system was simulated. The stable liquid crystal alignment direction on the polyimide monolayer was found roughly to be the polyimide chain direction with zero pretilt in this combination of liquid crystal and polymer materials. The calculated adsorption energy of an 8CB molecule to the polyimide monolayer was 128 kJ mol^-1 and the carbonyl group of the polyimide was the main adsorption site.     

Effects on surface properties of natural bamboo fibers treated with atmospheric pressure argon plasma

Argon plasma at atmospheric pressure was used to improve the wettability and dyeability of natural bamboo fibers. Optical emission spectroscopy (OES) was employed to characterize the discharge. SEM and scanning probe microscopy (SPM) analyses show that the fiber surface becomes rougher after plasma treatment because of the effects of plasma bombardment and etching. The wettability and dyeability are significantly enhanced after plasma treatment. Longer treatment time, leading to rougher surface, results in better surface wettability and dyeability. These results reveal that atmospheric pressure argon plasma treatment is an effective method to improve the performance of bamboo fibers. Copyright © 2006 John Wiley & Sons, Ltd.     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Processable polyisoimide polymer blends for application as thermally stable adhesives for composites and advanced metal alloys

Polyimides are effective thermally stable bonding agents for substrates including titanium, aluminum alloys, steel alloys, metal matrix composites, and polymer/fiber composites with good tolerance toward elevated temperature and humidity. Problems associated with polyimide adhesives, including high processing temperatures and pressures and high melt viscosity, can be partially or totally alleviated by use of blends of polyisoimides. During thermal processing, the polyisoimides are isomerized to their polyimide modifications.     

高介电常数石墨烯/聚酰亚胺复合材料的制备与性能

在原位聚合制备氧化石墨烯/聚酰亚胺复合材料的过程中,加入季铵盐表面活性剂,抑制氧化石墨烯在高温亚胺化时的聚集,同时将氧化石墨烯原位还原,获得高介电常数的石墨烯/聚酰亚胺复合材料.结果表明,采用四丁基溴化铵和四丁基碘化铵作为还原剂,利用原位化学还原方法所制备的石墨烯/聚酰亚胺复合材料的介电常数超过聚酰亚胺薄膜40倍以上,复合材料的热稳定性和机械性能也优于聚酰亚胺薄膜.热重分析结果表明,在复合材料高温亚胺化过程中,季铵盐发生热分解,未残留在复合材料中.