Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

胶粘剂固化行为对性能的影响

研究了一种中温固化耐高温胶粘剂固化行为对胶粘剂力学性能和耐久性能的影响,表明胶粘剂只有达到一定的固化程度,才能获得一定的交联密度,耐热性能、粘接强度和耐久性能。同时胶粘剂的固化时间和温度存在等效性关系。     

The influence of delayed light curing on the degree of conversion and polymerization contraction stress in dual-cured resin luting agents

The aim of the study was to assess the effect of delayed photo-initiation on the polymerization contraction stress (PCS) and degree of conversion (DC) of a dual-cure resin-luting agent. Thirty-five disk (6 mm × 1 mm) samples (n = 10 each group) of dual cure resin luting agent for PCS assessment were fabricated and polymerized using two illuminated quartz rods. Based on the delay in photo-initiation, 30 disks were divided among six groups [group A-0 min (min) delay, group B-2 min, group C-4 min, group D-6 min, group E-8 min and group F-10 min]. A non-photoinitiated group (group G – chemical cure – n = 5) was included as control. The PCS for all specimens was assessed using a Tensometer. For DC evaluation thirty-five specimens were divided into seven groups with delays in photo-initiation (group H-0 min, group I-2 min, group J-4 min, group K-6 min, group L-8 min and group M-10 min, group N-chemical cure). DC was assessed using attenuated total reflectance spectroscopic technique. Statistical comparison among groups was performed using analysis of variance (α = 0.05). The maximum and minimum PCS and DC values with delayed photo-initiation was observed in group-C (3.34 MPa) & group-F (2.44 MPa); and group-M (0.78 MPa) and group-H (0.55 MPa) respectively. Chemically cured samples showed the least PCS (group-G, 1.94) and DC (group-N, 0.53) values in their respective categories. PCS significantly decreased with delayed photo-initiation. A significant increase in DC was noticed when photo-initiation was delayed in the dual cure resin luting agent.     

Correlation of residual stress and adhesion on copper by the effect of chemical structure of polyimides for copper‐clad laminates

BACKROUND: Polyimide films coated on copper are a potential new substrate for fabricating printed circuit boards; however, adhesion between the copper and polyimide films is often poor. The relations between residual stress and adhesion strength according to the development of molecular orientation of polyimide films with different chemical backbone structure coated on copper were studied. RESULTS: The effect of chemical structures on properties including the residual stress and the adhesion strength were widely investigated for four different polyimides. Diamine 4,4′‐oxydianiline (ODA) and dianhydrides 1,2,4,5‐benzenetetracarboxylic dianhydride (PMDA), 4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) were used to synthesize polyimide. In an attempt to quantify the interaction of thermal mismatch with the polyimide films depending on various structures, residual stress experiments between polyimide film and Cu? Si wafer were carried out over a range of 25–400 °C using in situ thin film stress analysis. A universal test machine was used to conduct 180° peel test (ASTM D903‐98) of polyimide film from cooper foil. The residual stress on Cu? Si (100) wafer decreased in the order 6FDA‐ODA > BTDA‐ODA > ODPA‐ODA > PMDA‐ODA, and the interfacial adhesion strength decreased in the order BTDA‐ODA (5 N mm^?2) > ODPA‐ODA > PMDA‐ODA > 6FDA‐ODA. The results may suggest that the morphological structure, degree of crystallinity of chain orientation and packing significantly relate to the residual stress and adhesion strength in polyimide films. Wide‐angle X‐ray diffraction was used for characterizing the molecular order and orientation and X‐ray photoelectron spectroscopy was used for the analysis of components on copper after polyimide films were detached to confirm the existence of copper oxide chemical bonding and to measure the binding energy of elements on the copper surface. CONCLUSION: In this research, it is demonstrated that BTDA‐ODA polyimide has a low residual stress to copper, good adhesion property, good thermal property and low dielectric constant. Therefore, BTDA‐ODA would be expected to be a promising candidate for a two‐layer copper‐clad laminate. Copyright © 2007 Society of Chemical Industry     

Film thickness effect on texture and residual stress sign transition in sputtered TiN thin films

Residual stress in thin films and coatings strongly affects their properties and behavior in service. Comprehensive understanding and precise measurements of residual stress are prerequisites for preparing high quality films and coatings. Residual stresses in TiN films with different thickness were measured by X-ray diffraction (XRD) employing the cos²α sin²ψ method with certain optimization. Grazing incidence parallel beam optics was combined with side-inclination geometry using in-house designed sample stage to ensure results accuracy. To validate this method, TiN films with thickness ranging from 1 to 3 µm were deposited on (100) Si single crystal substrates at 300 °C by RF magnetron sputtering. High compressive −2 GPa residual stress was present in the 0.9 µm thick film and decreased with film thickness. Tensile stress of less than 0.3 GPa was present in 2 µm TiN film. Compressive-to-tensile residual stress transition was observed with the film thickness increase. Microstructure change with growth, annihilation of grain boudaries, atomic peening and recovery mechanisms are responsible for the reported stress sign transition.     

Effect of thermal history during drying and curing process on the chain orientation of rod-shaped polyimide

Chain orientation in polyimide (PI) film is influenced by the thermal history during drying and curing process. The amount of residual solvent and the degree of imidization, among other factors, play a major role in determining the chain orientation during the process. In the present study, poly(amic acid), the precursor of PI, coated on the glass substrate was imidized to PI through different drying and curing protocols. On the way of complete imidization, the residual solvent concentration and the degree of imidization were characterized using confocal Raman spectroscopy. The poly(amic acid) began to imidize quickly while retaining more solvent in the film as the initial drying temperature increased. The degree of in-plane chain orientation in fully imidized PI film made by different process protocols was compared using polarized Raman spectroscopy. The fully imidized PI showed the lowest degree of in-plane chain orientation when it was processed by the protocol with the highest drying temperature. The difference in the degree of in-plane chain orientation among different PI films significantly influenced the in-plane thermal expansion coefficient, while no significant change in crystallinity or glass transition temperature was observed.     

涂层材料与几何尺寸对等离子喷涂残余应力的影响

在等离子喷涂过程中,由于基体与涂层的热膨胀系数的不匹配,在它们共同冷却的过程中,产生了不同的热变形。本文采用有限元瞬态热分析方法对等离子喷涂过程的温度场进行了分析。在此基础上,进一步计算了常用的Al2O3涂层与16MnR基体组成的喷涂系统的残余应力分布,并对计算结果进行了讨论。然后,针对不同的涂层尺寸、不同涂层材料(a相Al2O3、Al2O3、ZrO2、TiO2、Al2O3-ZrO3)进行了残余应力计算,对涂层与基体内部的应力进行了分析,并且比较了不同的涂层尺寸以及材料性能对应力状态及分布的影响,对实际喷涂工艺有一定的指导意义。     

Structure–property correlation for thin films of semi-interpenetrating polyimide networks. I. Miscibility,curing, and morphology studies

Three different semi-interpenetrating polymer network (semi-IPN) polyimide systems were prepared through blending in solution by using 2 different polyimides, BPDA–PDA and PMDA–ODA (E), and 2 different oligomers, bismaleimide (MDAB) and phenylthynyl-terminated BPDA–PDA (BPDA–PDA–PEPA) oligomers. The oligomers are used as crosslinkers to modify the morphology of polyimides. The results show that both MDAB and PEPA are miscible with BPDA–PDA, but MDAB is immiscible with PMDA–ODA (E). Fourier transform infrared spectrum, dynamic mechanical thermal analysis data, and calculated crosslinking density indicate that there are crosslinking networks in these semi-IPN polyimide systems. In addition, the density and wide-angle X-ray diffraction results confirm that the molecular ordering and packing order are reduced by the addition of oligomers for these semi-IPN polyimide systems. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 261–272, 1998     

Surface topography effect on fibroblasts population on epiclon-based polyimide films

A polyimide based on alicyclic units, such as epiclon (5-(2,5-dioxotetrahydrofurfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride), was investigated from the point of view of its surface features to check their suitability for cell culture applications. Atomic force microscopy data revealed fractal and isotropic surfaces with nanoscale roughness and peaks placed at much smaller distances comparing to the cell size scale, favoring a good compatibility of the synthesized material with the biological medium, particularly after plasma treatment. Surface tension properties were determined in order to evaluate the interactions at the bio-interface affecting the adherence behavior of cell-binding proteins to the sample surface. In vitro experiments regarding the cytocompatibility and population tendency reveal that polyimide allows cells to adhere and to proliferate onto the surface. These tests indicate that the studied epiclon-based polyimide is not cytotoxic and can be recommended as good candidate for cell culture substrate in tissue engineering, especially after plasma treatment.     

UV exposure and temperature effects on curing mechanisms in thin linseed oil films: Spectroscopic and chromatographic studies

The influence of thermal and photochemical treatment in the curing mechanisms of thin linseed oil films is studied. The role of copper acetate pigments is also investigated under the above conditions. UV and FTIR absorption spectroscopy and chromatographic product analysis are used as the main analytical techniques, which allowed the identification of significant changes in the curing mechanism in each case. Yellowing, crosslinking, and fragmentation inside the film material proceed to a different extent according to the conditions. Peroxide destruction is induced by UV exposure at early curing stages and affects the course of the yellowing process. Yellow product formation is also favored by curing at elevated temperatures, which is accompanied in this case by decreased crosslinking in the cured film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 936–949, 2002; DOI 10.1002/app.10117     

硫化温度及硫化程度对全钢载重子午线轮胎胎面胶性能的影响

研究硫化温度和硫化程度对全钢载重子午线轮胎胎面胶性能的影响。结果表明：硫化温度、硫化程度越低,对胶料物理性能、耐磨性,滚动阻力越有利;硫化温度与滞后损耗值tanδ(60℃)呈强相关性,硫化程度与硫化胶阿克隆磨耗量呈强相关性;S/Si/促进剂组合的平衡硫化体系可有效减缓因硫化程度增加导致滞后损耗增加的趋势。     

Solvent effect on the curing of polyimide resins

The effect of the solvent 1-methyl-2-pyrrolidinone (NMP) on the curing of polyimide resins synthesized from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) has been investigated. Three polyimide precursors, i.e., the polyamic acid (PAA), with controlled amount of NMP were prepared. The study was aimed first to independently investigate the decomplexation process, which involved the evolution of hydrogen-bonded NMP from PAA, without interference from imidization. This was accomplished by TGA at varying heating rates using different solvent content in PAA. The observed one-stage decomplexation process suggested that the complex formation of NMP and PAA was not the same as the model compound studied by others. An average value of 150 kJ/mol for the activation energy of the decomplexation process was obtained. The study then sought to identify the effect of the decomplexation on the imidization kinetics by employing DSC at several drying temperatures and also varying heating rates. This allowed one to control the extent of plasticization that occurred to facilitate the imidization process. Our DSC data showed that over-drying PAA resulted in prolonged imidization due mainly to the lack of plasticization by decomplexed NMP. The estimated enthalpy of imidization and that of decomplexation were 114 KJ/mol and 53 kJ/mol NMP, respectively. Finally, the imidization kinetics was independently investigated using FTIR, without the interference from decomplexation process. The results indicated that there were four stages during the entire imidization process. Up to a temperature of 150°C, less than 20% of amide groups had reacted to give imide groups and the reaction was slow. Most of the imidization took place between 150 and 180°C with conversion as high as 90%. The imidization process was completed after the temperature was further raised to 250°C. Above 250°C, the reverse reaction became more significant (due probably to configurational and packing preference) and resulted in a lowering of final conversion back to 80%. © 1992 John Wiley & Sons, Inc.     

FT‐IR studies on the curing behavior of polycardanol from naturally renewable resources

In the present study, the curing behavior of polycardanol prepared by enzymatic oxidative polymerization of thermally treated cashew nut shell liquid, which can be available from naturally renewable resources, was explored in the presence of methyl ethyl ketone peroxide (MEKP) and cobalt naphthenate (Co‐Naph). The curing behavior was monitored varying Co‐Naph concentration and curing temperature by means of Fourier transform infrared (FT‐IR) spectroscopy. The result revealed that the characteristic absorption bands were significantly affected by the given curing condition, resulting mainly from the unsaturated moiety in the polycardanol molecule. The extent of curing of polycardanol strongly depended on curing temperature, showing a typically sigmoidal curve reaching almost 1.0 upon processing at 200°C for 120 min. The thermal curing conditions for preparing polycardanol with an optimal state of cure were provided in the work. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of microencapsulated curing agents on the curing behavior for diglycidyl ether of bisphenol A epoxy resin systems

Microcapsules containing a curing agent, 2‐phenyl imidazole (2PZ), for a diglycidyl ether of bisphenol A (DGEBA) epoxy resin were prepared by a solid‐in‐oil‐in‐water emulsion solvent evaporation technique with poly(methyl methacrylate) (PMMA) as a polymeric wall. The mean particle size of the microcapsules and the concentration of 2PZ were about 10 μm and nearly 10 wt %, respectively. The onset cure temperature and peak temperature of the DGEBA/2PZ–PMMA microcapsule system appeared to increase by nearly 30 and 10°C, respectively, versus those of the DGEBA/2PZ system because of the increased reaction energy of curing. The former could take more than 3 months at room temperature, whereas the latter was cured after only a week. The values of the reaction order (a curing kinetic parameter) for DGEBA/2PZ and DGEBA/2PZ–PMMA microcapsules were quite close, and this showed that the curing reactions of the two samples proceeded conformably. The curing mechanism was investigated, and a two‐step initiation mechanism was considered: the first was assigned to adduct formation, whereas the second was due to alkoxide‐initiated polymerization. The glass‐transition temperature of DGEBA/2PZ was 165.2°C, nearly 20°C higher than the glass‐transition temperatures of DGEBA/2PZ–PMMA microcapsules and DGEBA/2PZ/PMMA microspheres, as determined by differential scanning calorimetry measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on the thermal and curing behavior of polyimide blends

Blends of thermosetting (Thermid MC-600 and Thermid FA-700) and thermoplastic (UL-TEM 1000) polyimide resins with different compositions were prepared. Curing and thermal behavior of the blends were investigated using differential scanning calorimetry and dynamic thermogravimetry in a nitrogen atmosphere. The peak exotherm temperature increased with increasing amount of thermoplastic resin, whereas the heat of polymerization decreased. The electrical characteristics of the blends were also investigated using a dielectric analyzer. Dynamic as well as isothermal scans were recorded. Ionic conductivity, permittivity, and the loss factor were measured as a function of temperature at various frequencies. These results showed the complete curing of the resins having 50% Ultem at 225°C in 1 h, whereas Thermid MC-600 required a postcuring step to observe fully cured resins. A marginal decrease in thermal stability was observed on blending. © 1994 John Wiley & Sons, Inc.     

Local residual stress evolution of highly irregular thermally grown oxide layer in thermal barrier coatings

Local residual stress in thermally grown oxide (TGO) layers is the primary cause of failure of thermal barrier coating (TBC) systems, especially TBCs prepared by air plasma spray (APS) with a highly irregular TGO. Herein, the distribution of residual stress and the evolution of the irregular TGO layer in APS TBCs were investigated as a function of oxidation time. The stress was measured from cross-sectional micrographs and converted to the actual stress inside the coatings before sectioning. The TGO exhibited significant inhomogeneity at different locations. Stress conversion occurred across the TGO thickness; the layer near the yttria-stabilised zirconia (YSZ) component exhibited compressive stress, whereas that along the bond coat was under tensile stress. The evolution of the compressive stress is also discussed. These analyses may provide a better understanding of the mechanism of APS TBCs.     

聚酰亚胺改性环氧树脂/酸酐体系固化动力学研究

采用非等温差示扫描量热(DSC)法研究了聚酰亚胺(PI)改性环氧树脂(EP)/酸酐体系的固化反应动力学及其固化工艺。通过Kissinger法、Ozawa法和Crane法计算出该体系的动力学参数。结果表明:该固化体系具有较高的活性,其固化工艺条件为"80℃/2 h→120℃/2 h",后处理工艺为150℃/2 h;采用Kissinger法和Ozawa法计算出该体系的平均表观活化能为8.24 kJ/mol;结合Crane方程计算出该体系的反应级数为0.95,近似一级反应。     

烯丙基酚醛树脂固化行为的研究

利用酚醛树脂与氯丙烯反应,合成出了烯丙基酚醛树脂（APF）,并对其固化过程进行了研究。结果表明,烯丙基酚醛树脂不仅能溶于极性溶剂,还能溶于非极性溶剂,其起始固化温度为180℃,比普通的酚醛树脂高。烯丙基酚醛树脂的固化窗口为44℃,其固化是通过双键的加成反应来实现的,固化后树脂为连续相结构。     

硫化体系对再生胶性能影响的实验研究

考察了硫化体系中硫磺、促进剂M,促进剂TMTD,活性剂硬脂酸用量对再生胶制品拉伸强度以及断裂伸长率的影响.结果表明:适当提高硫化温度能减少硫磺的用量;在硫化温度为140℃,硫化时间为5min的条件下,当硫磺,促进剂M,促进剂TMTD和硬脂酸用量分别为1.5份,0.5份,0.5份,1.5份以及再生胶为100份时,再生胶硫...     

Effect of wood on the curing behavior of commercial phenolic resin systems

Differential scanning calorimetry (DSC) was used to study the effect of wood on the curing behavior of two types of commercial oriented‐strand‐board phenolic resins. DSC analysis showed that the curing behavior of the core resin differed significantly from that of the face resin in terms of the peak shape, peak temperature, and activation energy. The addition of wood to the resins moved the two separated peaks in the DSC curves of the core resin adjacent to each other. It also accelerated the addition reactions in the curing processes of both the core and face resins. The two peaks in the DSC curves were the result of the high pH values of the resins. These two peaks became either jointed together or overlapped when the pH value of the resin was reduced. Wood also reduced the activation energies for both the core and face resins by decreasing the pH values of the curing systems. Moreover, the effects of wood on the curing behavior of the resins among the five species studied were similar. The lowest activation energy for a phenolic resin probably appeared at pH 10–11 under alkaline conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 185–192, 2005