Polymer molecular behaviors at buried polymer/metal and polymer/polymer interfaces and their relations to adhesion in packaging

Packaging materials are widely used in modern microelectronics. The interfacial structures of packaging materials determine the adhesion properties of these materials. Weak adhesion or delamination at interfaces involving packaging materials can lead to failure of microelectronic devices. Therefore, it is important to investigate the molecular structures of such interfaces. However, it is difficult to study molecular structures of buried interfaces due to the lack of appropriate analytical techniques. Sum frequency generation (SFG) vibrational spectroscopy has recently been used to probe buried solid/solid interfaces to understand molecular structures and behaviors such as the presence, coverage, ordering, orientation, and diffusion of functional groups at buried interfaces and their relations to adhesion in situ in real time. In this review, we describe our recent progress in the development of nondestructive methodology to examine buried polymer/metal interfaces and summarize how the developed methodology has been used to elucidate adhesion mechanisms at buried polymer/metal interfaces using SFG. We also elucidated the molecular interactions between polymers and various model and commercial epoxy materials, and the correlations between such interactions and the interfacial adhesion, providing in-depth understanding on the adhesion mechanisms of polymer adhesives.     

Molecular dynamics simulations to investigate polymer–polymer and polymer–metal oxide interactions

Polymer–polymer interactions in majority of engineering polymers are difficult to measure experimentally, since many polymers are usually insoluble in solvents, have high glass transition temperatures, and are sometimes poorly characterized. Therefore, applying molecular modeling strategies would be helpful in such situations in order to provide useful information, which would be difficult to obtain by other means. Poly(methyl methacrylate), PMMA, is a widely used engineering polymer that exists in a glassy state at room temperature. Therefore, we have selected PMMA to perform the molecular dynamics simulations to investigate its interfacial interaction with many other important polymers such as PAN, PC, PEO, PES, PMS, PU, PVAc, PVDF, PVME and PVP. Small molecular fragments of repeating units of these polymers were chosen for interaction studies, whose polymers and/or their blends with PMMA are used in many engineering applications. The COMPASS force field methodology was used in the present study for oligomers containing up to 10-mers for simulations to compute solubility parameters that are closely agreeable with the experimental data. Molecular dynamics (MD) simulations have also been performed to explore the adsorption behavior of MMA with several metal oxides (Al₂O₃, Fe₂O₃, SiO₂ and TiO₂), since such studies are important in developing polymer composites. Interfacial interactions between MMA and metal oxides have been calculated using the vibrational absorptions in order to identify the functional groups that might interact quite favorably with the PMMA.     

Interfacial and Demulsifying Behavior of Novel Fluorinated Hyperbranched Polymers

In our previous study, a series of novel hyperbranched fluoropolymers with polyglycerol as the core and poly(hexafluorobutyl acrylate) as hydrophobic arms were synthesized. As potential demulsifier for lubricants, the demulsification behavior, dynamic interfacial tension, and dilational rheological properties of the fluorinated polymers were investigated in this paper. The influence of polymer concentration and molecular structure on the interfacial properties was analyzed. We conclude that the diffusion rate of the polymers and the viscoelastic properties of the water–oil interface are critical factors in determining the demulsification performance. The longer hydrophobic chains of the fluorinated polymers leads to a faster and more effective interfacial adsorption, which is favorable to improve demulsification efficiency. In contrast, the longer hydrophobic chain also enhances the elastic property of interface due to its entangled structure, which is unfavorable to demulsification. As a result, the polymer with medium hydrophobic chain length show the best demulsification performance.     

Critical role of particle/polymer interface in photostability of nano-filled polymeric coatings

Nanoparticle-filled polymeric coatings have attracted great interest in recent years because the incorporation of nanofillers can significantly enhance the mechanical, electrical, optical, thermal, and antimicrobial properties of coatings. Due to the small size of the fillers, the volume fraction of the nanoparticle/polymer interfacial area in nano-filled systems is drastically increased, and the interfacial region becomes important in the performance of the nano-filled system. However, techniques used for characterizing nanoparticle/polymer interfaces are limited, and thus, the mechanism by which interfacial properties affect the photostability and the long-term performance of nano-filled polymeric coatings is not well understood. In this study, the role of the nanoparticle/polymer interface on the ultraviolet (UV) stability of a nano-ZnO-filled polyurethane (PU) coating system was investigated. The effects of parameters influencing the particle/polymer interfacial properties, such as size, loading, surface modification of the nanoparticles, on photodegradation of ZnO/PU films were evaluated. The nature of the interfacial regions before and after UV exposures were characterized by atomic force microscopy (AFM)-based techniques. Results have shown that the interfacial properties strongly affect chemical, thermo-mechanical, and morphological properties of the UV-exposed ZnO/PU films. By combining tapping mode AFM and novel electric force microscopy (EFM), the particle/polymer interfacial regions have been successfully detected directly from the surface of the ZnO/PU films. Further, our results indicate that ZnO nanoparticles can function as a photocatalyst or a photostabilizer, depending on the UV exposure conditions. A hypothesis is proposed that the polymers in the vicinity of the ZnO/PU interface are preferentially degraded or protected, depending on whether ZnO nanoparticles act as a photocatalyst or a photostabilizer in the polymers. This study clearly demonstrates that the particle/polymer interface plays a critical role in the photostability of nano-filled polymeric coatings.     

新型对称性两亲含硅聚合物的合成与界面性能

基于原子转移自由基聚合(ATRP)机理,以二甲基一氯硅烷封端的烯丙基-聚乙二醇为起始剂,甲基丙烯酸乙酯(EMA)为单体,通过控制反应温度,合成了一系列聚合度(DP_(NMR))分别为0. 74,1. 67和3. 07的新型对称性两亲含硅共聚物(PEMA-b-Si-PEG-Si-b-PEMA),并评价了该共聚物在氯仿/水界面的界面活性和吸附行为。结果表明:该类聚合物可以有效降低氯仿/水界面张力,具有最短PEMA链的聚合物可将氯仿/水界面张力从32 m N/m降低至约23 m N/m。动态界面张力分析表明:低浓度的共聚物在吸附的初始阶段符合扩散控制,且较短的PEMA链段有利于产生较快的扩散速率。平衡界面张力分析表明:随着界面浓度的增加,共聚物将表现出多种吸附状态,其吸附状态的数量以及聚合物在界面的偏摩尔面积将随着PEMA链长度的增加而增加。     

In situ ATR-FTIR studies of the aluminium/polymer interface upon exposure to water and electrolyte

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) with the Kretschmann configuration was applied for in situ studies of the transport of water and ionic species through a polymer film to an aluminium/polymer interface. The time dependent intensity changes of the infrared bands of water were used to follow the transport of water to the aluminium/polymer interfacial region and a NaSCN solution was employed as model electrolyte to follow the transport and accumulation of thiocyanate ions. Apart from water sorption and ion transport, the main processes identified were corrosion/oxidation of the aluminium surface and swelling of the polymer film. The method proved to be useful for detailed in situ studies of changes at a polymer coated metal surface, such as oxidation and surface film formation on the metal. It should also be possible to study the effects of defects and pores in the polymer film on the transport properties of water and ions to the metal/polymer interface, as well as adsorption and other chemical reactions and physical interactions in the metal/polymer interfacial region.     

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Reinforcement of adhesion and development of morphology at polymer–polymer interface via reactive compatibilization: A review

Polymer blending is a common and effective way to develop new materials with desirable physical and mechanical properties. Since most polymer pairs are immiscible, reactive compatibilization has been extensively studied to stabilize morphology of polymer blends and improve their mechanical properties. In the past several years, considerable interest has been expressed in understanding the fundamental kinetics and mechanisms of the interfacial reaction, investigating the reinforcement of the interfacial adhesion and the development of morphological structure at polymer–polymer interface induced by the interfacial reaction. The present review focused on some theoretical and experimental results that include the formation and growth of copolymers at the interface, and also the major factors such as reaction conditions, the concentration and bulk properties of the functionalized polymer, the thermodynamic interaction between the functionalized polymer and the matrix, which can influence the interfacial adhesion and morphological development. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

麦羟硅钠石/聚合物纳米复合材料研究进展

麦羟硅钠石（magadiite）是一种新型的层状纳米硅酸盐材料,由于其具有制备工艺简单、比表面积大、阳离子交换性能高、吸附性能强、层间膨胀性能好等优点,成为纳米材料提升聚合物性能最具有发展潜力的材料之一。本文主要综述了麦羟硅钠石/聚合物纳米复合材料的常用制备方法及其优缺点,包括聚合物插层法、单体原位插层聚合法、锚固插层聚合法。浅谈了国内外利用3种方法制备的基于聚苯乙烯、聚丙烯、环氧树脂、尼龙6、聚己内酯和聚甲基丙烯酸甲酯等多种聚合物的麦羟硅钠石/聚合物纳米复合材料,对在纳米复合材料结构中出现界面不相容、麦羟硅钠石分布不均匀的问题提出了解决方法,并阐述了麦羟硅钠石对纳米复合材料结构和性能的影响,最后展望了麦羟硅钠石/聚合物纳米复合材料的发展前景。     

Influence of polymer on dynamic interfacial tensions of EOR surfactant solutions

The effects of different types of polymers, partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM), on dynamic interfacial tensions (IFTs) of surfactant/model oil systems have been investigated by the spinning drop method in this article. Two anionic surfactants, 1,2‐dihexyl‐4‐propylbenzene sulfonate (366), 1,4‐dibutyl‐2‐nonylbenzene sulfonate (494) and an anionic–nonionic surfactant octyl‐[ω‐alkyloxy‐poly(oxyethylene)]yl‐benzene sulfonates (828) with high purity were selected as model surfactants. The influences of polymer concentration on IFT were expounded. It was found that the addition of polymer mostly results in increasing IFT because the interfacial molecular arrangement is modified owing to the interaction between polymer and surfactants. For HPAM, the polymer chains will enter the surfactant adsorption layer to form mixed‐adsorption layer. Therefore, HPAM shows strong effect on surfactant molecules with large size, such as 366. Conversely, surfactants can interact with the hydrophobic blocks of HMPAM and form mixed micelle‐like associations at interface. As a result, HMPAM shows more impact on IFT of 494 due to small steric hindrance for the formation of interfacial associations. This mechanism has been ensured by 828 molecules with two long alkyl chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40562.     

Predictions of micromechanics models for interfacial/interphase parameters in polymer/metal nanocomposites

In this paper, the polymer-metal interfacial/interphase parameters (PMIP) in polymer/metal nanocomposites are studied by modeling the mechanical properties. In this regard, the experimental results of yield strength, Young's modulus and elongation at break can be compared with the micromechanical models to evaluate the PMIP. The good agreement obtained between the experimental data of samples and the predictions confirms the applicability of models for polymer/metal nanocomposites. Many calculated parameters show the existence of a strong interphase in the reported samples. It is concluded that the fine morphology of nanoparticles and the strong interaction/adhesion at the polymer-metal interface can produce the significant PMIP in the polymer/metal nanocomposites.     

Microstructure,adhesion strength and failure path at a polymer/roughened metal interface

Metals and polymers are extensively used in microelectronics packaging where they are joined together. Since both the yield and reliability of packages are strongly affected by the interfacial adhesion between polymers and metals, extensive studies have been performed in order to improve the resistance to debonding of many resulting interfaces. In the present work, the interfacial fracture energy of representative polymer/metal interfaces commonly encountered in micoroelectronics packaging was characterized. A copper-based alloy leadframe was used as the metal and an epoxy molding compound (EMC) was used as the polymer. The leadframe surfaces were roughened by chemical oxidation in a hot alkaline solution and molded with the EMC. In general, roughening of metal surfaces enhances their adhesion to polymers by mechanical interlocking, yet often produces a cohesive failure in the polymer. Sandwiched double-cantilever beam (SDCB) specimens were employed to measure the adhesion strength in terms of interfacial fracture energy. After the adhesion test, the microstructures of metal surfaces before molding with the EMC were correlated to the adhesion strength, and the fracture surfaces were analyzed using various techniques to determine the failure path.     

Interfaces in repair,recycling, joining and manufacturing of polymers and polymer composites

A basic set of 10 thermoset polymer–polymer interfaces has been identified to play a vital role in the technical and economic aspects of composite manufacturing (RIM/RTM, compression molding, autoclave lamination), recycling, repair, welding, and joining of polymer composites. Knowledge of the chemical interactions and molecular connectivity at these interfaces and their influence on processability and mechanical properties of the polymers and polymer composite is essential, and has been the focus of this research. Presented in this report are the results of an exploratory study performed to understand the interactions at the polymer–polymer interface and their influence on the interfacial fracture toughness of a thermoset vinyl ester, which is widely used in liquid molding applications. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 775–785, 1999     

Methods to improve the properties of polymer mixtures: optimizing intermolecular interactions and compatibilization

Two methods to improve the dispersion, interfacial adhesion and properties of polymer mixtures are presented. Infrared spectroscopy and optical microscopy results document that control of the spacing of interacting moieties along the polymer chain results in optimal intermolecular hydrogen bonding and improved miscibility between two polymers. Moreover, initial results indicate that this protocol also works for polymer nanocomposites. Computational and experimental results indicate that multiblock or blocky copolymers are the most effective interfacial strengtheners among linear copolymers for polymer-polymer interfaces. ADCB and neutron reflectivity experiments provide direct evidence that multiblock copolymers that have blocks that are long enough to entangle with a homopolymer are most effective at strengthening the interface. Both sets of results provide guidelines by which multi-component polymer systems can be designed with target properties.     

Influence of corona treatment on adhesion and mechanical properties in metal/polymer/metal systems

The effect of corona treatment (CT) on the adhesion at the metal–polymer interface was studied. Metal/polymer/metal laminates were manufactured by the laboratory roll‐bonding process with preliminary corona surface treatment of the polymer core: a polyethylene and polypropylene sheet as well as steel sheet. It was treated with corona discharge to increase its surface energy and the adhesion to metal, an austenitic steel. The adhesion, which was measured by T‐peel and shear tests, was increased by 43% of crack peel and 22% of mean peel resistance respectively, after 120 s CT. On the basis of scanning electron spectroscopy observations, improvements in the adhesive properties were attributed to the change in the interfacial morphology. In mechanical tests, yield and tensile strengths were strongly influenced by CT, indicating that these laminates were sensitive to interfacial phenomena. However, elongation at rupture of the composites was found to be unchanged. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Comparative measurements of interfacial tension in a model polymer blend

This work shows the application of several experimental methods to the measurement of the interfacial tension, σ, between two immiscible polymers. A quantitative knowledge of the interfacial tension is important in view of the crucial role that this parameter plays in polymer blend processing. Common to all methods presented here are two main points. The first is that σ is obtained from experiments where the shape of the interface between the liquids is directly observed by means of optical microscopy techniques. The second point is that the interface geometry is controlled by a balance between the interfacial force and the viscous stresses generated by some flow applied to the system. Measurements have been carried out on a model polymer blend, whose constituents are a poly-isobutylene and a poly-dimethylsiloxane. both transparent and liquid at room temperature. When compared with each other, the values of interfacial tension obtained from the different methods show a good quantitative agreement. Excellent agreement is also found with results for the same system previously published in the literature.     

The level of matrix-filler interfacial adhesion in metal and polymer nanocomposites reinforced with carbon nanotubes

In this paper, the interfacial adhesion between metal matrix and carbon nanotubes (CNTs) is determined in various metal/CNT nanocomposites by several models. The models apply the experimental data to calculate the interfacial parameters. A good correlation is acquired between theoretical and experimental results which validates the current analysis. The calculated parameters reveal the formation of a perfect adhesion at the interface between the metal matrix and CNT in all reported samples. In addition, the calculations are compared with similar results for polymer nanocomposites which show a stronger adhesion at metal–CNT interface in comparison to polymer–filler interfacial adhesion in polymer nanocomposites.     

Interfacial grafting and crosslinking by free radical reactions in polymer blends

Relevant developments in polymer blends based on immiscible products have shown how efficient the amphiphilic species are in improving mechanical properties and morphological stabilization throughout successive processing steps. However, it appears that the amount of compatilizer that has to be introduced for reaching the expected level of global properties is largely higher than the calculated concentration based on the interfacial area. In order to obtain the required concentration of amphiphilic copolymer at the interface, it seems of interest to test the possibility of creating these species by in situ reactivity at the interface. As most of the polymers are hydrocarbon compounds, they are subjected to free radical reactivity by hydrogen abstraction on the different hydrocarbon sites, which may lead to crosslinking or grafting. Therefore, this work deals with reciprocal free radical reactivity of two immiscible semicrystalline homopolymers, namely, low density polyethylene (LDPE) and polyamide-11 (PA-11). The reaction has to occur mainly at the interface, where the resulting grafted copolymer has to be anchored for final stabilization of the biphasic system. Different analytical techniques help in characterizing the reacted blend and determining the level of interfacial grafting.