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.     

Effects of reactive end-capper on mechanical properties of chemical amplified photosensitive polyimide

Photosensitive polyimide (PSPI) was synthesized and characterized to replace the conventional polyimide buffer layer because direct patterning with PSPI could reduce the processing procedure to the half. Since PSPI should be dissolved in alkaline aqueous solution and have good mechanical properties after imidization, low molecular weight of PSPI was synthesized with reactive end-capper, which could extend the chain length of PSPI during imidization. Therefore norbornene end-capped PSPI precursor was synthesized with various 5-norbornene-2,3-dicarboxylic anhydride (NDA) content.Although molecular weight of PSPI decrease with increasing NDA content, the elongation at break and the glass transition temperature (T_g) of PSPI films imidized at 300 °C increased with increasing NDA content. On the other hand, elongation at break of PSPI films imidized at 350 °C decreased but T_g of those increased with increasing NDA content. Above T_g, thermal expansion coefficient decreased dramatically by introducing NDA end-capper. From mechanical and thermal properties of PSPI, it appears that low molecular weight of PSPI can be chain-extended and crosslinked during imidization.     

Ion beam-induced positive imaging of polyimide via two step imidization

The preparation of ion track membranes of thermally stable polyimide films has been performed by ion beam irradiation of partially imidized polyamic acid (PAA) films followed by alkaline etching and final imidization. No discernible positive hole patterns were observed on the irradiated films of partially imidized PAA containing sulfonyl linkages, although sulfonyl group is known to be highly sensitive to ion beams. In contrast, positive hole patterns appeared on the irradiated films of the partially imidized PAA with 68-89% imidization degrees that contains sulfonyl linkages along with a methylene group in the main chain. The most contrasty hole patterns with 0.3 μm diameter were observed on the irradiated PAA films of 89% imidization degree. The irradiated PAA film with the hole patterns was then transformed to the corresponding polyimide film with curing at 350 °C for 1 h. From the structural comparison of the polyimides, the possible mechanism for the hole pattern formation is suggested.     

The effects of varied imidization conditions on rubbed polyimide film surface morphology

The thermal histories of polyimide films were varied to study the effect of the extent of imidization on the response of films to rubbing. Films rubbed prior to imidization formed tears that extended to the substrate; tears in these films formed at smaller film thicknesses than in films imidized prior to rubbing. Aligned nanoscopic islands were also seen. The alignment of these islands disappeared upon imidization. Films imidized at a low temperature showed less alignment of islands than conventionally prepared films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1192–1197, 2004     

The effect of curing history on the residual stress behavior of polyimide thin films

The effect of curing history on the residual stress behaviors in semiflexible structure poly(4,4′‐oxydiphenylene pyromellitimide) (PMDA–ODA) and rigid structure poly(p‐phenylene biphenyltetracarboximide) (BPDA–PDA) polyimide was investigated. Depending upon the curing history and different structures of polyimide, the residual stress behaviors and the morphology of polyimide thin films were detected in situ by using a wafer bending technique and wide angle X‐ray diffraction (WAXD), respectively. For the rigid structure BPDA–PDA polyimide, the residual stress and the slope decreased from 11.7 MPa and 0.058 MPa/°C to 4.2 MPa and 0.007 MPa/°C as the curing temperature increased, and the annealing process is done. However, for the semiflexible structure PMDA–ODA, the change of the residual stress and the slope was relatively not significant. In addition, it was found that the cured polyimide prepared at a higher temperature with a multistep curing process showed a higher order of chain in‐plain orientation and packing order than does the polyimide film prepared at a lower temperature with a one‐step curing process. These residual stress behaviors of polyimide thin films show good agreement with WAXD results, such as polyimide chain order, orientation, and intermolecular packing order, due to curing history. Specifically, it shows that the effect of curing history on residual stress as well as morphological change was significant in rigid BPDA–PDA polyimide but, not in semiflexible PMDA–ODA polyimide. Therefore, it suggests that the morphological structure depends upon curing history, and the polyimide backbone structure might be one of important factors to lead the low residual stress in polyimide thin films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3287–3298, 1999     

Molecular mechanism of temporal physico/chemical changes that take place during imidization of polyamic acid: Coupled real-time rheo-optical and IR dichroism measurements

Multiple overlapping physical and chemical changes often take place during casting/drying and imidization from PMDA-ODA polyamic acid precursors from cast solutions. To shed light into details of these complex phenomena, we designed a unique real time measurement system that combines true stress, true strain, in-plane birefringence and temperature with polarized ultra-rapid scan FT-IR spectrometry (URS-FT-IR). At the early stages of heating (21°C–130 °C), initially isotropic solution cast film was observed to develop stress and birefringence as the solvent decomplexed and evaporated without showing any imidization as it was held in uniaxially constrained state. At a temperature around 130 °C, the onset of imidization reaction was detected while the stress went through a maximum. Beyond this stage, the evaporation of bound solvent and chemical conversion was observed to take place simultaneously and this is accompanied by a steady increase in birefringence. As the majority of the bound solvent evaporated, the stress and birefringence values started leveling off at long times.     

Synthesis,miscibility, and properties of rodlike/flexible polymer composites via in-situ rod chain formation

Summary Flexible, soluble poly(amic diethyl ester) precursors of rodlike poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA) and poly(4,4-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA), which are more stable than the respective poly(amic acid)s and are not in the equiliration with the constituent anhydride and amine monomers so that chemical exchange reactions are prevented in their solution blending, were synthesized. Homogeneous precursor/precursor solutions with various compositions were obtained in N-methyl-2-pyrrolidinone with appreciably high solid contents. The dried precursor blend films and resultive polyimide composite films thermally imidized were optically transparent, regardless of compositions and film process conditions. The composites showed single T_g behavior. Conclusively, rodlike BPDA-PDA/flexible BPDA-ODA molecular composites were achieved from the blend of the respective flexible poly(amic diethyl ester) precursors through conventional drying and imidization process. In addition, film properties of composites were characterized.     

Residual stress and thermal expansion of spun-on polyimide films

The residual stress in spin coated films and the effect of heat treatments on this stress were determined by the Fizeau interference method. Three types of spin coated polyimide (PI) films have been studied. Two of them were prepared by thermal conversion of their poly(amic acid)s (PAAs) and the third one by solvent evaporation of the soluble preimidized PI. For the imidized PI films the residual stress vs. bake temperature shows an inclined steplike behavior while this function for soluble PI is approximately linear. The room temperature stress relative to silicon substrates in fully baked films (400°C) is between 40 and 70 MPa and nearly independent of the film thickness. From the stress measurement, the thermal expansion coefficient and Young's moduli have also been obtained. The thermal expansion coefficient and the Young's modulus are in the order of 9.0 × 10^?6°C^?1 and 10 GPa, respectively. These values deviate from those published for bulk material which is explained by the in-plane orientation of the molecular chains in spun-on PI films.     

Novel soluble polyimides derived from 2,2′-bis[4-(5-amino-2-pyridinoxy)phenyl]hexafluoropropane: Preparation,characterization, and optical,dielectric properties

Two novel aromatic diamine monomer, 2,2′-bis[4-(5-amino-2-pyridinoxy)phenyl] hexafluoropropane (6FBAPDP) and 2,2′-bis[4-(5-amino-2-pyridinoxy)phenyl] propane (BAPDP), were successfully synthesized. Aimed at clarifying the structure-property relationships of pyridine-containing high-performance polymers, a series of novel fluorinated polyimides PI-(1–4) were prepared from 6FBAPDP with various commercially aromatic anhydrides, and polyimide (PI-5) was synthesized derived from BAPDP and 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) via a two-stage process with heating imidization method. The fluorinated polyimides PI-(1–4) exhibited good solubility in strong polar solvents, such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, m-cresol, and could afford flexible, tough and transparent films with an UV–visible absorption cut-off wavelength at 342–393 nm. The glass transition temperatures of these polyimides were recorded between 239 and 306 °C by differential scanning calorimetry, and the 5% weight loss occurred at temperatures above 498 and 490 °C, in nitrogen and air, respectively. The polyimide films had the in-plane coefficients of thermal expansion (CTE) that ranged from 54 to 74 ppm °C⁻¹. Moreover, the fluorinated polyimide films showed low moisture absorptions of 0.51–0.82% and outstanding mechanical properties with the tensile strengths of 75–100 MPa, tensile moduli of 3.2–4.0 GPa and elongation at break of 5.5–10.3%, good dielectric properties with low dielectric constants of 2.71–2.92 at 1 MHz.     

The effect of preparation process of PMDA–ODA–DR1 polyimide on its second harmonic generation characteristics

In situ second harmonic generation (SHG) observation of PMDA–ODA–DR1 polyimide films prepared by different preparative procedures were studied to understand the effects of the residual acid and the imidization byproduct and the extent of imidization on the SHG characteristics of the PMDA–ODA–DR1 polyimides. PMDA–ODA–DR1 polyimides with or without removal of salt were also investigated to study the influence of remaining triethyl hydrogen ammonium chloride salt on the SHG characteristics and reliability of the polymers. A blue shift in the UV/vis spectrum during poling was observed for the low temperature-baked film, but did not occur for the high-temperature-baked film. Both high temperature imidization and removal of the byproduct organic salt did not only improve the poling efficiency of PMDA–ODA–DR1 polyimide as a SHG material, but also slowed down the relaxation of the film and made the film more reliable. © 1995 John Wiley & Sons, Inc.     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Comparison of one-pot and two-step polymerization of polyimide from BPDA/ODA

The one-pot method polymerization of polyimide was carried out from 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) by the use of p-chloro-phenol as the solvent. The behavior of the polymerization was compared with that of the two-step method. The imidization reaction in the one-pot method proceeds completely in this system at even a low temperature such as 100°C. In the course of the film preparation from the solution, the embrittlement occurs when the film is prepared from polyamic acid solution, while it does not occur in the case of that from the solution of the one-pot method. A molecular weight of polyimide film is almost the same as that of precursor polyimide in the solution. In the same way, that of polyimide film is almost the same as that of precursor polyamic acid. The mechanical properties of the polyimide film prepared by the one-pot method are similar to those by the two-step method. © 1996 John Wiley & Sons, Inc.     

Carbonization and graphitization of polyimide films: Effect of size of leaving group at imidization

Polyamide acid was prepared from pyromellitic dianhydride and p-phenylenediamine and was then reacted with NaH and various kinds of alkyl halides to transform into alkyl esters. The cast films were imidized as fixed on glass substrate to give polyimide films and were then carbonized by heating to 900°C. The electrical conductivity of the carbonized films decreased with the increase of the size of the leaving group at the imidization step. The carbonized films were further heated to 2800°C for graphitization. Their degrees of graphitization and orientation of the graphite crystallite as a function of weight loss at imidization were studied by X-ray diffraction measurement at room temperature and magnetoresistance measurement at liquid nitrogen temperature. Both measurements clearly indicate that the graphitized films prepared from polyamide acid alkyl ester have high degrees of graphitization. It was also made clear that the orientation of the graphitized films increased with the increase of the size of the leaving group at the imidization step. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci John Wiley & Sons, Inc.J Appl Polym Sci 68: 1613–1620, 1998     

High-performance polymer films. III. Preparation and characterization

A series of polyimide and copolyimide films were prepared by film casting, drying, and thermal imidization from the respective precursor poly(amic acid) (PAA) and copoly(amic acid) solutions derived from two dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and two diamines, 4,4′-oxydianiline (ODA) and a proprietary aromatic diamine (PD) as monomers. Depending on the solution's inherent viscosity value (molecular weight) and the nature of the polymer chains (derived from rigid or flexible monomers), precursor poly(amic acid) and copoly(amic acid) solution concentrations of 8–12% (w/w) were found to be suitable for the preparation of good quality polyimide/copolyimide films. The recovery of film toughness and creasability from the brittleness at the intermediate temperature of the cure cycle depended not only on the molecular weight of the precursor poly(amic acids)/copoly(amic acids) but also on their chain flexibility. The poly(amic acid) derived from both rigid dianhydride and diamine practically gave rise to a brittle film of polyimide even after curing to 360°C. The resulting polyimide and copolyimide films were compared with Du Pont's Kapton H film. The density of the films was in the range 1.39–1.42 g/cm³. The thickness of most of the films was in the range 20–30 μm. The HPF 3 film, based on PMDA–PD, appeared to be highly colored (reddish brown), and the HPF 2 film, based on BTDA–ODA, had the lightest yellow coloring among the films in this investigation, including Kapton H film. HPF 2, HPF 6, and HPF 8 films were more amorphous than the other films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 976–988, 2001     

A chemically amplified positive-working photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) and poly(amic acid)

We prepared a novel chemically amplified photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) (PAAE) and poly(amic acid); this blend produces polyimide (PI) films with improved mechanical properties after imidization with photoacid generator (PAG). PAAE and poly(amic acid) were end-capped with 5-norbornene-2,3-dicarboxylic dianhydride and 2,3-dimethyl maleic anhydride, respectively, to lower their molecular weights without compromising the properties of the resulting PI films. As a result of the blending of these PI precursors, the mechanical properties of the PI films were found to be less affected by the strong acid generated from the PAG than PI films fabricated by imidization of PAAE alone. The relatively high solubility of the blended PI precursor film in basic aqueous solutions was found to be effectively controlled by the use of a high-temperature post-exposure bake process to partially imidize the end-capped PAA. It was found that a 10-μm-thick film of the PSPI precursor system containing 13 wt% PAGs exhibits a sensitivity (D⁰) of 700 mJ/cm² when developed with 2.38 wt% aqueous tetramethyl ammonium hydroxide solution at room temperature. A fine positive pattern was fabricated in a 12 μm thick film with 1000 mJ/cm² of i-line exposure. The resultant PI film was also found to exhibit excellent mechanical and thermal properties, which are critical to its practical use as a stress buffer layer in semiconductor packaging.     

Relationship between microstructure of lamellar graphene sheets and properties of polyimide/graphene nanocomposites film under different imidization stages

Herein, polyimide/graphene sheets (PI/GS) nanocomposite films with different GS distribution structures have been successfully obtained by controlling the imidization degrees, and the effect of the lamellar structure on the properties of PI film has been investigated. The results show that GS are gradually parallel to the surface of PI nanocomposite film with the increase of the imidization temperature, and 150 °C is the critical temperature, where the imidization rate is the fastest and the lamellar structure begins to form. Furthermore, with the drying temperature increasing, the corresponding thermal, electrical and mechanical properties of PI/GS nanocomposite films are significantly improved compared with that of pure PI films, which are ascribed to both the higher imidization degree and the lamellar GS structure. It is noteworthy that the formation process of the lamellar structure at different imidization stages can be directly observed by scanning electron microscope. Based on these results, a model has been proposed to explain the relationship between the lamellar structure and properties of PI composite film under different imidization stages, and the confinement of the thickness may be the most important factor for the formation of lamellar GS structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43575.     

Negative in-plane CTE of benzimidazole-based polyimide film and its thermal expansion behavior

Non-stretched polyimide films based on 5,4′-diamino-2-phenyl benzimidazole (DAPBI) show curious thermal expansion properties: the in-plane CTE value of PI film is negative when cured at 350 °C (contract upon heating). However, the value of CTE turns positive when cured at 400 °C. In-plane and out-of-plane CTE of PI films annealed at various temperatures have been measured to study the annealing effect on thermal expansion feature. The in-plane CTE value increases from negative to positive as the raise of the annealing temperatures (T_anneal), while the out-of-plane CTE decreases as a function of T_anneal. Morphologies of PI films change from amorphous to semi-crystalline accompanied with the change of in-plane CTE from negative to positive. Mechanism of the thermal expansion behavior of DAPBI-based PI films is proposed: negative in-plane CTE is generated under the combination of the more preferential thermal expansion in the out-of-plane direction and the amorphous structure when the films are cured at lower temperatures; while thermal expansion in the in-plane and out-of-plane directions are both available for semi-crystallized PI films, affording positive in-plane CTE values.     

Characterization of alicyclic polyimides based on cyclobutane ring dianhydride and aromatic diamine

Films of alicyclic polyamic acid and polyimide containing cyclobutane ring in dianhydride moiety and aromatic ring with p- or m-linkages in diamine moiety were characterized by infrared (IR) spectroscopy, dynamic viscoelasticity, differential-scanning calorimetry (DSC), density, and wide-angle X-ray diffraction analyses. Partially and fully imidized polyimides were obtained by varying the imidization temperature, e.g., 150°C, 250°C, and 350°C. It was found from the results of IR spectra, dynamic viscoelasticity, and DSC measurements that the imidization of alicyclic polyamic acid was reduced at about 150°C and needed a higher imidization temperature than aromatic polyamic acid. Alicyclic polyimide with m-linkage in the diamine moiety had a higher density and a much more ordered structure than with p-linkage. © 1994 John Wiley & Sons, Inc.     

Carbonization and graphitization of polyimide films: Polyamide acid methyl ester of PMDA/PDA as a precursor

Polyamide acid was prepared from pyromellitic dianhydride (PMDA) and p-phenylene-diamine (PDA) and was then reacted with NaH and methyl iodide to transform into methyl ester having various degrees of esterification. Polyamide acid methyl ester was also prepared by the polymerization between PDA and acid chloride of half-ester of PMDA. The cast films were imidized as fixed on glass substrate to give polyimide films having slightly higher tensile moduli than those from polyamide acid, suggesting that higher orientation along the film surface was achieved. It should be noted that the polyimide films prepared by the latter method from the meta-rich configuration had considerably low modulus. The polyimide films were then carbonized by heating to 900°C, and the electrical conductivity of the carbonized films was measured at room temperature. It was shown that the carbonized films from methyl ester have higher electrical conductivity than the films from corresponding polyamide acid. The carbonized films were further heated to 2800°C for graphitization, and their degrees of graphitization and orientation of the graphite crystallite as a function of esterification ratio were studied by x-ray diffraction measurement at room temperature and magnetoresistance measurement at liquid nitrogen temperature. Both measurements clearly indicate that the graphite films prepared from polyamide acid methyl ester have high degrees of graphitization and orientation. © 1996 John Wiley & Sons, Inc.     

An ellipsometric study of polymer film curing: 2,6-Bis(3-aminophenoxy) benzonitrile/4,4′oxidiphthalic anhydride poly(amic acid)

The curing of 2,6-bis(3-aminophenoxy)benzonitrile/4,4′oxidiphthalic anhydride ((β-CN) APB/ODPA) has been investigated using spectroscopic ellipsometry on films with various degrees of imidization. Results indicate that much of the film imidization is accomplished at 200 °C and above. Three absorption peaks have been observed (4.1, 5, and 6 eV) which correspond to intra- and inter-molecular optical transitions. A comparison of the film optical constants for the pristine poly(amic acid) and the fully cured polyimide shows film densification upon imidization. A curing timeline has been obtained using in situ real-time spectroscopic ellipsometry, and ellipsometry is shown to serve as a general technique for studying organic film curing.