Polyimide gels are produced by cross-linking anhydride capped polyamic acid oligomers with aromatic triamine in solution and chemically imidizing. The gels are then supercritically dried to form nanoporous polyimide aerogels with densities as low as 0.14 g/cm(3) and surface areas as high as 512 m(2)/g. To understand the effect of the polyimide backbone on properties, aerogels from several combinations of diamine and dianhydride, and formulated oligomer chain length are examined. Formulations made from 2,2'-dimethylbenzidine as the diamine shrink the least but have among the highest compressive modulus. Formulations made using 4,4'-oxydianiline or 2,2'dimethylbenzidine can be fabricated into continuous thin films using a roll to roll casting process. The films are flexible enough to be rolled or folded back on themselves and recover completely without cracking or flaking, and have tensile strengths of 4-9 MPa. Finally, the highest onset of decomposition (above 600 °C) of the polyimide aerogels was obtained using p-phenylene diamine as the backbone diamine with either dianhydride studied. All of the aerogels are suitable candidates for high-temperature insulation with glass transition temperatures ranging from 270-340 °C and onsets of decomposition from 460-610 °C.
We report the first synthesis of polyimide aerogels cross-linked through a polyhedral oligomeric silsesquioxane, octa(aminophenyl)silsesquioxane (OAPS). Gels formed from polyamic acid solutions of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), bisaniline-p-xylidene (BAX) and OAPS were chemically imidized and dried using supercritical CO(2) extraction to give aerogels having density around 0.1 g/cm(3). The aerogels are greater than 90 % porous, have high surface areas (230 to 280 m(2)/g) and low thermal conductivity (14 mW/m-K at room temperature). Notably, the polyimide aerogels cross-linked with OAPS have higher modulus than polymer reinforced silica aerogels of similar density and can be fabricated as both monoliths and thin films. Thin films of the aerogel are flexible and foldable making them an ideal insulation for space suits, and inflatable structures for habitats or decelerators for planetary re-entry, as well as more down to earth applications.
Combinations of rigid and flexible aromatic diamines were used to tailor the properties of octa(aminophenyl)-silsesquioxane (OAPS) cross-linked polyimide aerogels. 2,2'-Dimethylbenzidine (DMBZ) or p-phenylenediamine (PPDA) was used in combination with the more-flexible diamine, 4,4'-oxydianiline (ODA). The amount of rigid diamine was varied from 0% to 100% of the total diamines in the backbone. The resulting aerogels vary in density, shrinkage, porosity, surface area, mechanical and thermal properties (depending on the type of diamine and the proportions of rigid diamine to flexible diamine used). Replacing ODA with PPDA increases shrinkage that occurs during gelation and processing, while increasing the DMBZ fraction decreases shrinkage. Replacing ODA with 50 mol% of DMBZ maintains the flexibility of thin films, while the moisture resistance of the aerogels is greatly improved.
A novel class of high performance polymer porous aerogel film‐based triboelectric nanogenerators (A‐NGs) is demonstrated. The A‐NGs, made of a pair of highly porous polymer films, exhibit much higher triboelectric outputs than the corresponding dense polymer film‐based triboelectric nanogenerators (D‐NGs) under the same mechanical stress. The triboelectric outputs of the A‐NGs increase significantly with increasing porosity, which can be attributed to the increase in contact area and the electrostatic induction in the porous structure, thereby leading to additional charges on the porous surface. Remarkably, the A‐NG fabricated using porous chitosan aerogel film paired with the most porous polyimide (with a porosity of 92%) aerogel film demonstrates a very high voltage of 60.6 V and current of 7.7 µA, corresponding to a power density of 2.33 W m−2, which is sufficient to power 22 blue light‐emitting‐diodes (LEDs). This is the first report on triboelectric nanogenerators (TENGs) employing porous polymer aerogel films as both positive and negative materials to enhance triboelectric outputs. Furthermore, enhancing the tribopositive polarity of the cellulose aerogel film via silanization using aminosilane can dramatically improve the triboelectric performance. Therefore, this study provides new insights into investigating porous materials with tunable triboelectric polarities for high performance TENGs.
Triboelectric nanogenerators (TENGs) have been attracting a tremendous amount of attention since their discovery in 2012. Finding new means to enhance energy output is an ongoing pursuit. Herein, we introduce a new type of high-performance TENG composed of highly porous polyamide (PA) nanofiber mats and polyimide aerogel films. We have demonstrated that the thickness of the porous triboelectric materials, which is attained by stacking multiple layers of triboelectric materials, has a profound effect on the triboelectric output performance of TENGs. The triboelectric output increased when PA increased from one layer to six layers. However, it decreased when PA was further increased to 12 layers. With an optimum material thickness, a TENG with only a 2 cm effective device size achieved a high output voltage of 115 V and a current of 9.5 μA under a small compressive pressure (30 kPa). A peak power density of 1.84 W/m was achieved on a 4.7 MΩ external load. The TENG was able to light 60 light-emitting diodes easily and quickly charge capacitors with different capacitance to 6 V, indicating an outstanding energy harvesting ability. In addition, the performance of multiple TENGs connected in different ways, as well as the performance of TENGs in resistive/inductive/capacitive circuits, were investigated. These findings provide new insight into the working principles of TENGs in complex circuits.
Polyimide
aerogels using 1,12-dodecyldiamine (DADD), 3,3′-dimethylbenzidine
(DMBZ), and 3,3′,4,4′-biphenyltetracarboxylic dianhydride
(BPDA) and cross linked using 1,3,5-triaminophenoxybenzene (TAB) were
synthesized. Substitution of the aromatic diamine, DMBZ, with varying
amounts of the aliphatic diamine, DADD, increases the flexibility
in the backbone structure of the prepared aerogel. These aerogels
are also lightweight, low density, have a low dielectric constant,
and high modulus. Their overall properties (density, shrinkage, porosity,
dielectric constant, water uptake, and modulus) and potential use
as a conformal substrate for lightweight, high-performance antennas
are discussed.
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