Preparation and Characterization of Light-Colored Polyimide Nanocomposite Films Derived from a Fluoro-Containing Semi-Alicyclic Polyimide Matrix and Colloidal Silica with Enhanced High-Temperature Dimensionally Stability.

Light-colored and transparent polyimide (PI) films with good high-temperature dimensional stability are highly desired for advanced optoelectronic applications. However, in practice, the simultaneous achievement of good optical and thermal properties in one PI film is usually difficult due to the inter-conflicting molecular design of the polymers. In the present work, a series of PI-SiO2 nanocomposite films (ABTFCPI) were developed based on the PI matrix derived from hydrogenated pyromellitic anhydride (HPMDA) and an aromatic diamine containing benzanilide and trifluoromethyl substituents in the structure, 2,2'-bis(trifluoromethyl)-4,4'-bis [4-(4-aminobenzamide)]biphenyl (ABTFMB). The inorganic SiO2 fillers were incorporated into the nanocomposite films in the form of colloidal nanoparticles dispersed in the good solvent of N,N-dimethylacetamide (DMAc) for the PI matrix. The derived ABTFCPI nanocomposite films showed good film-forming ability, flexible and tough nature, good optical transparency, and good thermal properties with loading amounts of SiO2 up to 30 wt% in the system. The ABTFCPI-30 film with a SiO2 content of 30 wt% in the film showed an optical transmittance of 79.6% at the wavelength of 400 nm (T400) with a thickness of 25 µm, yellow index (b*) of 2.15, and 5% weight loss temperatures (T5%) of 491 °C, which are all comparable to those the pristine ABTFCPI-0 matrix without filler (T400 = 81.8%; b* = 1.77; T5% = 492 °C). Meanwhile, the ABTFCPI-30 film exhibited obviously enhanced high-temperature dimensional stability with linear coefficients of thermal expansion (CTE) of 25.4 × 10-6/K in the temperature range of 50 to 250 °C, which is much lower than that of the AMTFCPI-0 film (CTE = 32.7 × 10-6/K).

Thermomechanical characterisation data of 30 g/m2 and 150 g/m2 cured unidirectional carbon/epoxy tape prepreg TP 402/T700S.

With the aim to calculate through the Classical Laminate Theory the most reliable stress value generated in the 90° layer of cross-ply laminates tested under fatigue loading [1], the mechanical and thermal properties were measured for a novel composite material TP402/T700S 12K/35% using two different unidirectional tape prepregs, 30 and 150 g/m2. 0° unidirectional (UD-0), 90° unidirectional (UD-90), ±45°, 10° off-axis and samples for thermal properties measurements were manufactured in an autoclave. Tensile and thermal tests were performed in an Instron 4482 and in an oven, respectively, using strain gauges for all of them. Data collected was analysed following technical standards. The values of the mechanical properties, i.e., elastic and shear stiffness and strength, and the coefficients of thermal expansion (CTEs), α 1 and α 2 , were calculated also obtaining the corresponding statistics.

Intrinsically Negative Photosensitive Polyimides with Enhanced High-Temperature Dimensional Stability and Optical Transparency for Advanced Optical Applications via Simultaneous Incorporation of Trifluoromethyl and Benzanilide Units: Preparation and Properties.

Negative photosensitive polyimides (PSPIs) with the photo-patterned ability via the photocrosslinking reactions induced by the i-line (365 nm) and h-line (426 nm) emitting wavelengths in high-pressure mercury lamps have been paid increasing attention in semiconductor fabrication, optical fiber communications, and other advanced optoelectronic areas. In the current work, in view of the optical and thermo-mechanical disadvantages of the currently used negative PSPIs, such as the intrinsically photosensitive or auto-photosensitive systems derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and the ortho-alkyl- substituted aromatic diamines, a series of modified negative PSPIs with the enhanced optical transparency in the wavelength of 365~436 nm and apparently reduced coefficients of linear thermal expansion (CTE) were developed. For this purpose, a specific aromatic diamine with both of trifluoromethyl and benzanilide units in the molecular structures, 2,2'-bis(trifluoromethyl)-4,4'-bis[4-(4-amino-3-methyl)benzamide]biphenyl (MABTFMB) was copolymerized with BTDA and the standard 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane (TMMDA) diamine via a two-step chemical imidization procedure. As compared with the pristine PI-1 (BTDA-TMMDA) system, the new-developed fluoro-containing PSPI systems (FPI-2~FPI-7) exhibited the same-level solubility in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N- dimethylacetamide (DMAc). The FPI films cast from the corresponding FPI solutions in NMP showed the optical transmittances of 78.3-81.3% at the wavelength of 436 nm (T436, h-line), which were much higher than that of the PI-1 (T436 = 60.9%). The FPI films showed the CTE values in the range of 40.7 × 10-6/K to 54.0 × 10-6/K in the temperature range of 50 to 250 °C, which were obviously lower than that of PI-1 (CTE = 56.5 × 10-6/K). At last, the photosensitivity of the FPI systems was maintained and the micro-pattern with the line width of 10 µm could be clearly obtained via the standard photolithography process of FPI-7 with the molar ratio of 50% for MABTFMB in the diamine moiety.

Preparation and Properties of Inherently Black Polyimide Films with Extremely Low Coefficients of Thermal Expansion and Potential Applications for Black Flexible Copper Clad Laminates.

In the current work, a series of black polyimide (PI) films with excellent thermal and dimensional stability at elevated temperatures were successfully developed. For this purpose, two aromatic diamines including 4,4'-iminodianline (NDA) and 2-(4-aminophenyl)-5- aminobenzimidazole (APBI) were copolymerized with pyromellitic dianhydride (PMDA) to afford PIs containing imino groups (-NH-) in the molecular structures. The referenced PI film, PI-ref, was simultaneously prepared from PMDA and 4,4'-oxydianiline (ODA). The introduction of imino groups endowed the PI films with excellent blackness and opaqueness with the optical transmittance lower than 2% at the wavelength of 600 nm at a thickness of 25 µm and lightness (L*) below 10 for the CIE (Commission International Eclairage) Lab optical parameters. Meanwhile, the introduction of rigid benzimidazole units apparently improved the thermal and dimensional stability of the PI films. The PI-d film based on PMDA and mixed diamines (NDA:APBI = 70:30, molar ratio) showed a glass transition temperature (Tg) of 445.5 °C and a coefficient of thermal expansion (CTE) of 8.9 × 10-6/K in the temperature range of 50 to 250 °C, respectively. It is obviously superior to those of the PI-a (PMDA-NDA, Tg = 431.6 °C; CTE = 18.8 × 10-6/K) and PI-ref (PMDA-ODA, Tg = 418.8 °C; CTE: 29.5 × 10-6/K) films.

Reduced Coefficients of Linear Thermal Expansion of Colorless and Transparent Semi-Alicyclic Polyimide Films via Incorporation of Rigid-Rod Amide Moiety: Preparation and Properties.

Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3',4,4'-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4'-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4'-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-Ia (HPMDA-MeDABA) and PI-IIa (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-Ib and PI-IIb). PI-Ia and PI-IIa showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 µm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10-6/K for PI-Ia and 27.7 × 10-6/K for PI-Ib in the temperature range of 50-250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures (T5%) higher than 430 °C and glass transition temperatures (Tg) in the range of 349-351 °C.

Effect of slow-cooling protocol on biaxial flexural strengths of bilayered porcelain-ceria-stabilized zirconia/alumina nanocomposite (Ce-TZP/A) disks.

OBJECTIVE: The present study investigated the biaxial flexural strengths of bilayered ceria-stabilized zirconia/alumina nanocomposite (Ce-TZP/A) disks with various layering porcelains veneered using a slow-cooling protocol. METHODS: Five porcelain materials (VITA VM9, Cercon Ceram Kiss, and Vintage ZR with experimental coefficient of thermal expansions; CTEs of 8.45, 9.04, and 9.61ppm/°C) were veneered on Ce-TZP/A disks and slow-cooled after firing to fabricate bilayered specimens (core-to-porcelain thickness: 0.8mm/1.5mm). Biaxial flexural strengths of the specimens with the porcelain layer in tension were tested based on the piston-on-three-ball method (ISO 6872:2008). The data were statistically analyzed using Weibull distribution and Fisher's exact test. RESULTS: Tensile stresses were observed in the entire porcelain layer while compressive stress at the surface of the Ce-TZP/A layer shifted to tensile stress at the interface between the materials. The cases of small CTE mismatches between the materials showed high Weibull characteristic strengths at the internal and external surfaces of the specimens, except the VM9 group (CTE: 9.0-9.2ppm/°C). The maximum tensile stress was observed on the surface of the porcelain layer, where cracks originated and continuously propagated into the Ce-TZP layer. The Ce-TZP/A fractured into two pieces for large CTE mismatches between the materials, resulting in significantly lower flexural strengths than those fracturing into three pieces for small CTE mismatches. SIGNIFICANCE: Flexural strengths and fracture behaviors of bilayered porcelain-Ce-TZP/A disks were influenced by the CTE mismatches, and a small CTE mismatch between the materials was preferred when using a slow-cooling protocol.

Biaxial flexural strength of the bilayered disk composed of ceria-stabilized zirconia/alumina nanocomposite (Ce-TZP/A) and veneering porcelain.

OBJECTIVE: Herein we investigated the flexural strengths of bilayered ceria-stabilized zirconia/alumina nanocomposite (Ce-TZP/A) disks using different veneering porcelains. METHODS: Commercial (VITA VM9, Cercon Ceram Kiss, and IPS e.max Ceram) and experimental porcelains (Vintage ZR with coefficient of thermal expansions: CTEs of 8.45, 9.04, and 9.61ppm/°C) with various layer thicknesses (1.0, 1.5, and 2.0mm) were applied to Ce-TZP/A disks (0.8mm thickness, n=180). Biaxial flexural tests of the specimens with the porcelain layer in tension were evaluated based on the piston-on-three-ball method (ISO 6872: 2008). The calculated strengths were statistically analyzed using the two-parameter Weibull distribution with the maximum likelihood estimation. RESULTS: Although no significant differences were observed among the experimental porcelains, most specimens with the thinner layer of commercial porcelain showed higher Weibull characteristic strengths at the external surfaces than those with the thicker layer. Irrespective of the porcelain material, the thinner porcelain layer showed significantly higher strengths at the interface between the layers. Fracture origins were always observed at the bottom surface and continuously propagated into Ce-TZP/A substrates. The maximum tensile stress was located at the interface in specimens with the 1.0mm porcelain layer, except for IPS e.max Ceram. Porcelain delamination was dominant in the case of the higher CTE value and thicker layer thickness of the porcelain. SIGNIFICANCE: The calculated biaxial flexural strengths and the stress distributions for bilayered Ce-TZP/A disks were dependent on the porcelain materials. Optimum behavior was observed for a combination of a small CTE mismatch between the materials and a low core-to-porcelain thickness ratio.

Mixed Rigid and Flexible Component Design for High-Performance Polyimide Films.

To develop the polyimide (PI) which is closely matched to the coefficient of the thermal expansion (CTE) of copper, a series of PIs are prepared from 5,4'-diamino-2-phenyl benzimidazole (DAPBI), 4,4'-diaminodiphenyl ether (ODA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) using a sequential copolymerization, blade coating, and thermal imidization process. The physical properties of the PIs are effectively regulated and optimized by adjusting the ratio of the rigid DAPBI and flexible ODA components. By increasing the DAPBI content, thermal stability, dimensional stability, and mechanical properties, the resultant polymer is enhanced. PI-80 exhibits an excellent comprehensive performance, a glass transition temperature of 370 °C, and a tensile strength of 210 MPa. Furthermore, the CTE as calculated in the range 50⁻250 °C is ca. 19 ppm/K, which is equal to that of copper. A highly dimensionally stable, curl-free, and high T-style peel strength (6.4 N/cm) of copper/PI laminate was obtained by casting the polyamic acid onto copper foil (13 µm) and thermally curing at 360 °C, which indicates that it has the potential to be applied as an electronic film for flexible displays and flexible printed circuit boards. A structural rationalization for these remarkable properties is also presented.