Authors:Z. Wu, A. Zhang, D. Shen, M. Leland, F. W. Harris, and S. Z. D. Cheng
Three aromatic polyimides based on 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA) and three different diamines 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), 2,2′-dimethyl-4, 4′-diaminophenyl (DMB) or 3,3′-dimethylbenzidine (OTOL) have been synthesized. These polyimides are soluble in hotp-chlorophenol,m-cresol or other phenolic solvents. Fibers have been spun from isotropic solutions using a dry-jet wet spinning method. The as-spun fibers generally exhibit low tensile properties, and can be drawn at elevated temperatures (>380° C) up to a draw ratio of 10 times. Remarkable increases in tensile strength and modulus are achieved after drawing and annealing. The crystal structures of highly drawn fibers were determinedvia wide angle X-ray diffraction (WAXD). The crystal unit cell lattices have been determined to be monoclinic for BPDA-PFMB and triclinic for both BPDA-DMB and BPDA-OTOL. Thermomechanical analysis (TMA) was used to measure thermal shrinkage stress and strain. A selfelongation has been found in the temperature region around 450°C. This phenomenon can be explained as resulting from the structural development in the fibers as evidencedvia WAXD observations.
Authors:Young Ho Kim, Bong Seok Moon, F. W. Harris, and S. Z. D. Cheng
A new high molecular weight polyimide based on 4,4′-oxidiphthalic anhydride (ODPA) dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl (DMB) diamine has been synthesizedvia a one-step polymerization method. This polyimide is soluble in phenolic solvents. Films from 7 to 30 μm thick were cast from the polymer solution and show in-plane orientation on a molecular scale detected by Fourier transform infrared spectroscopy experiments. This anisotropic structure leads to anisotropic optical properties arising from two different refractive indices along the inplane and out-of-plane directions. ODPA DMB possesses high thermal and thermo-oxidative stability. The glass transition temperature has been determined to be 298 °C. Dynamic mechanical analyses show two relaxation processes appearing above room temperature: the β- and the α-relaxation processes. The α-relaxation corresponds to the glass transition while the β-relaxation is a secondary relaxation process associated with the non-cooperative subsegmental motion.
Authors:Mariana Cristea, Daniela Ionita, Maria Bruma, and B. Simionescu
Two aromatic polyimides and the corresponding poly(amic acid)s, with oxadiazole and para/meta phenoxyphenylene rings in the backbone, were synthesized and the structure — thermal properties correlation was followed
by dynamic mechanical analysis. Concerning the poly(amic acid)s, the glass transition domain was emphasized only for the compound
with meta-oriented rings because the process of imidization takes place with increasing temperature. A multiplex experiment was performed
to calculate the activation energy of the transition localized under 200°C. Consecutive heating-cooling-heating cycles were
accomplished. All phenomena are discussed by cross-examination of the storage modulus (E′), loss modulus (E″) and loss factor tanδ variation with temperature.
Pyrolysis of normally insulating aromatic polyimide is known to impart electrical conductivity to the polymer due to the formation
of carbonized regions in an insulating matrix with a concomitant change in the polymer’s structural arrangement. The wholly
pyrolyzed polyimide is potentially useful for specific applications in certain types of semiconductor devices because of the
polyimide’s insulator/conductor transition which creates a barrier type conduction. Pyrolysis, however, degrades the required
mechanical integrity of the polyimide for construction of such devices. In order to evaluate the fundamental aspects of barrier
conduction by high voltage electron transfer from metal contact that can still produce measurable current in thermally treated
non-pyrolyzed polyimide, the nature of depolarization in Kapton was assessed by the thermally stimulated depolarization current
(TSDC) technique. The results show that thermal treatment of polyimide without pyrolysis and therefore without loss of mechanical
integrity offers a viable means of steady electron conduction for semiconductor operation.
Authors:Z. Wu, F. Li, L. Huang, Y. Shi, X. Jin, S. Fang, K. Chuang, R. Lyon, F. Harris, and S. Cheng
The thermal mechanical properties and degradation behaviors were studied on fibers prepared from two high-performance, heterocyclic polymers, poly(p-phenylenebenzobisthiazole) (PBZT) and poly(p-phenylenebenzobisoxazole) (PBZO). Our research demonstrated that these two fibers exhibited excellent mechanical properties and outstanding thermal and thermo-oxidative stability. Their long-term mechanical tensile performance at high temperatures was found to be critically associated with the stability of the C—O or C—S linkage at the heterocyclic rings on these polymers' backbones. PBZO fibers with the C—O linkages displayed substantially higher thermal stability compared to PBZT containing C—S linkages. High resolution pyrolysis-gas chromatography/mass spectrometry provided the information of the pyrolyzates' compositions and distributions as well as their relationships with the structures of PBZT and PBZO. Based on the analysis of the compositions and distributions of all pyrolyzates at different temperatures, it was found that the thermal degradation mechanisms for both of these heterocyclic polymers were identical. Kevlar®-49 fibers were also studied under the same experimental conditions in order to make a comparison of thermo-oxidative stability and long-term mechanical performance at high temperatures with PBZO and PBZT fibers. The data of two high-performance aromatic polyimide fibers were also included as references.
Three different thermoanalytical methods are introduced as significant time-saving techniques in conventional life tests of some organic electrical insulating materials. DTA in cyclically alternated atmospheres of nitrogen and oxygen according to Randino and Andreotti, and TG analysis methods at different heating rates according to Flynn and Wall and to Broido were applied to two electrical insulations based on aromatic poly-imide and epoxy resin. The activation energies obtained are compared with those derived from the slopes of the life-lines produced via conventional life tests. The assumptions necessary for applying the thermal analyses in these cases are discussed.
Authors:Ion Sava, Ştefan Chişcă, Maria Brumă, and Gabriela Lisa
Aromaticpolyimides generally have excellent thermal, mechanical, and electrical properties primarily because of their heterocyclic structure [ 1 – 6 ]. However, even higher thermal stability and mechanical
Authors:Muhammad Bisyrul Hafi Othman, Rafiza Ramli, Zulkifli Mohamad Ariff, Hazizan Md Akil, and Zulkifli Ahmad
In the last 80 years, the synthesis of aromaticpolyimides (PIs) has seen a tremendous increase within a wide range of applications, particularly in insulation materials [ 1 , 2 ] and high performance polymers [ 3
Authors:Chinnaswamy Thangavel Vijayakumar, Rajendran Surender, Kumaraswamy Rajakumar, and Sarfaraz Alam
Recently, polyimides especially aromaticpolyimides have more and more applications in microelectronics, automotive, and aerospace sector because of their high thermal stability, mechanical strength, and excellent