The Effect of Thin Film Adhesives on Mode II Interlaminar Fracture Toughness in Carbon Fiber Composites with Shape Memory Alloy Inserts.

A single sheet of nickel-titanium (NiTi) shape memory alloy (SMA) was introduced within an IM7/8552 polymer matrix composite (PMC) panel in conjunction with multiple thin film adhesives to promote the interfacial bond strength between the SMA and PMC. End notched flexure (ENF) testing was performed in accordance to ASTM D7905 method for evaluation of mode II interlaminar fracture toughness (GIIC) of unidirectional fiber-reinforced polymer matrix composites. Acoustic emissions (AE) were monitored during testing with two acoustic sensors attached to the specimens. The composite panels examined using scanning electron microscopy techniques after part failure. GIIC values for the control composite samples were found to be higher than those of samples with embedded SMA sheets. The presence of adhesives bonded to SMA sheets further diminished the GIIC values. AE values revealed poor bonding of the panels, with little to no signals during testing.

The Effects of Fiber Orientation and Adhesives on Tensile Properties of Carbon Fiber Reinforced Polymer Matrix Composite with Embedded Nickel-Titanium Shape Memory Alloys.

Tensile tests of Nickel-titanium (NiTi) shape memory alloys (SMA) embedded within carbon fiber reinforced polymer matrix composite (CFRP/PMC) laminates were evaluated with simultaneous monitoring of modal acoustic emissions (MAE). Three different layup configurations utilizing two different thin film adhesives were applied to bond the materials. Ultimate tensile strengths, strains, and moduli were obtained along with cumulative AE energy of events and specimen failure location. Scanning electron microscopy was used to examine the break areas of the specimens post-test. Microscopy was used to validate failure locations revealed from MAE analysis. 90° plies in the outer ply gave the strongest acoustic signals as well as the cleanest fracture of the specimens tested. Overlapping 0° ply layers surrounding the SMA was found to be the best scenario to prevent failure of the specimen itself.

Multiscale Progressive Failure Analysis of 3D Woven Composites.

Application of three-dimensional (3D) woven composites is growing as an alternative to the use of ply-based composite materials. However, the design, analysis, modeling, and optimization of these materials is more challenging due to their complex and inherently multiscale geometries. Herein, a multiscale modeling procedure, based on efficient, semi-analytical micromechanical theories rather than the traditional finite element approach, is presented and applied to a 3D woven carbon-epoxy composite. A crack-band progressive damage model was employed for the matrix constituent to capture the globally observed nonlinear response. Realistic microstructural dimensions and tow-fiber volume fractions were determined from detailed X-ray computed tomography (CT) and scanning electron microscopy data. Pre-existing binder-tow disbonds and weft-tow waviness, observed in X-ray CT scans of the composite, were also included in the model. The results were compared with experimental data for the in-plane tensile and shear behavior of the composite. The tensile predictions exhibited good correlations with the test data. While the model was able to capture the less brittle nature of the in-plane shear response, quantitative measures were underpredicted to some degree.

Polyimide aerogels for ballistic impact protection.

The ballistic performance of edge-clamped monolithic polyimide aerogel blocks (12 mm thickness) has been studied through a series of impact tests using a helium-filled gas gun connected to a vacuum chamber and a spherical steel projectile (approximately 3 mm diameter) with an impact velocity range of 150-1300 m s-1. The aerogels had an average bulk density of 0.17 g cm-3 with high porosity of approximately 88%. The ballistic limit velocity of the aerogels was estimated to be in the range of 175-179 m s-1. Moreover, the aerogels showed a robust ballistic energy absorption performance (e.g., at the impact velocity of 1283 m s-1 at least 18% of the impact energy was absorbed). At low impact velocities, the aerogels failed by ductile hole enlargement followed by a tensile failure. By contrast, at high impact velocities, the aerogels failed through an adiabatic shearing process. Given the substantially robust ballistic performance, the polyimide aerogels have a potential to combat multiple constraints such as cost, weight, and volume restrictions in aeronautical and aerospace applications with high blast resistance and ballistic performance requirements such as in stuffed Whipple shields for orbital debris containment application.

Flexible Polyimide Aerogels with Dodecane Links in the Backbone Structure.

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.

Toward Improved Optical Transparency of Polyimide Aerogels.

Highly translucent polyimide aerogels were prepared by combining equimolar amounts of pyromellitic dianhydride, 4,4'-hexafluoroisopropylidene di(phthalic anhydride) (6FDA), and 2,2'-dimethylbenzidine and cross-linking with 1,3,5-benzenetricarbonyl trichloride. A multivariable statistical design of experiments was used to perform a comparison study between three variables used to fabricate the aerogels: formulated repeat unit (n) of polyimide oligomers, 6FDA fraction of total dianhydride (0-50 mol %), and total polymer concentration in solution (7-10 wt %). Polymers with 25 mol % 6FDA in the backbone structure were found to produce polyimide aerogels with high optical transmission and low haze. These aerogels also possessed higher surface areas and very narrow nanoscale pore size distribution. Because of the decreased thermal conductivity with increasing amount of 6FDA in the backbone, these aerogels may find use where the combination of high optical transparency and thermal impedance is desired, such as insulated window panes. To this end, future efforts will focus on reducing the yellow color of the polyimide aerogels.

Polyimide Aerogels Using Triisocyanate as Cross-linker.

A family of polyimide (PI)-based aerogels is produced using Desmodur N3300A, an inexpensive triisocyanate, as the cross-linker. The aerogels are prepared by cross-linking amine end-capped polyimide oligomers with the triisocyanate. The polyimide oligomers are formulated using 2,2'-dimethylbenzidine, 4,4'-oxydianiline, or mixtures of both diamines, combined with 3,3',4,4'-biphenyltetracarboxylic dianhydride, and are chemically imidized at room temperature. Depending on the backbone chemistry, chain length, and polymer concentration, density of the aerogels ranged from 0.06 to 0.14 g/cm3 and Brunauer-Emmett-Teller surface areas ranged from 350 to 600 m2/g. Compressive moduli of these aerogels were as high as 225 MPa, which are comparable to, or higher than, those previously reported prepared with similar backbone structures but with other cross-linkers. Because of their lower cost and commercial availability as cross-linker, the aerogels may have further potential as insulation for building and construction, clothing, sporting goods, and automotive applications, although lower-temperature stability may limit their use in some aerospace applications.

Highly Porous, Rigid-Rod Polyamide Aerogels with Superior Mechanical Properties and Unusually High Thermal Conductivity.

We report here the fabrication of polyamide aerogels composed of poly-p-phenylene-terephthalamide, the same backbone chemistry as DuPont's Kevlar. The all-para-substituted polymers gel without the use of cross-linker and maintain their shape during processing-an improvement over the meta-substituted cross-linked polyamide aerogels reported previously. Solutions containing calcium chloride (CaCl2) and para-phenylenediamine (pPDA) in N-methylpyrrolidinone (NMP) at low temperature are reacted with terephthaloyl chloride (TPC). Polymerization proceeds over the course of 5 min resulting in gelation. Removal of the reaction solvent via solvent exchange followed by extraction with supercritical carbon dioxide provides aerogels with densities ranging from 0.1 to 0.3 g/cm3, depending on the concentration of calcium chloride, the formulated number of repeat units, n, and the concentration of polymer in the reaction mixture. These variables were assessed in a statistical experimental study to understand their effects on the properties of the aerogels. Aerogels made using at least 30 wt % CaCl2 had the best strength when compared to aerogels of similar density. Furthermore, aerogels made using 30 wt % CaCl2 exhibited the lowest shrinkage when aged at elevated temperatures. Notably, whereas most aerogel materials are highly insulating (thermal conductivities of 10-30 mW/m K), the polyamide aerogels produced here exhibit remarkably high thermal conductivities (50-80 mW/(m K)) at the same densities as other inorganic and polymer aerogels. These high thermal conductivities are attributed to efficient phonon transport by the rigid-rod polymer backbone. In conjunction with their low cost, ease of fabrication with respect to other polymer aerogels, low densities, and high mass-normalized strength and stiffness properties, these aerogels are uniquely valuable for applications such as lightweighting in consumer electronics, automobiles, and aerospace where weight reduction is desirable but trapping of heat may be undesirable-applications where other polymer aerogels have to date otherwise been unsuitable-creating new opportunities for commercialization of aerogels.

Moisture-Resistant Polyimide Aerogels Containing Propylene Oxide Links in the Backbone.

Polyimide aerogels made using anhydride-capped oligomers from 4,4'-oxydianiline (ODA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) cross-linked with 1,3,5-tri(aminophenoxy)benzene (TAB) have been reported with very good mechanical properties but poor resistance to moisture. Replacing 50 mol % of the ODA with poly(propylene glycol)bis(2-aminopropyl ether) (PPG) with an average molecular weight of 230 g/mol in the oligomer backbone gives aerogels with water contact angles of 80°. The aerogels also absorb very little moisture on soaking in water. The aerogels also shrink less with increasing PPG concentration and therefore have significantly lower density and higher porosity than those made without PPG. Mechanical properties of the aerogels increased with increasing density, regardless of the polymer backbone. Brunauer-Emmett-Teller (BET) surface area of the aerogels studied ranged from 300 to 400 m2/g, depending mainly on PPG concentration. The high moisture resistance makes them promising materials for substrates for lightweight antennas as well as insulation for a variety of applications.

Trade-off between the Mechanical Strength and Microwave Electrical Properties of Functionalized and Irradiated Carbon Nanotube Sheets.

Carbon nanotube (CNT) sheets represent a novel implementation of CNTs that enable the tailoring of electrical and mechanical properties for applications in the automotive and aerospace industries. Small molecule functionalization and postprocessing techniques, such as irradiation with high-energy particles, are methods that can enhance the mechanical properties of CNTs. However, the effect that these modifications have on the electrical conduction mechanisms has not been extensively explored. By characterizing the mechanical and electrical properties of multiwalled carbon nanotube (MWCNT) sheets with different functional groups and irradiation doses, we can expand our insights into the extent of the trade-off that exists between mechanical strength and electrical conductivity for commercially available CNT sheets. Such insights allow for the optimization of design pathways for engineering applications that require a balance of material property enhancements.

Polyimide aerogels with amide cross-links: a low cost alternative for mechanically strong polymer aerogels.

Polyimide aerogels combine high porosity, low thermal conductivity, flexibility, and low density with excellent mechanical properties. However, previously used cross-linkers, such as 1,3,5-triaminophenoxybenzene (TAB), 2,4,6-tris(4-aminophenyl)pyridine (TAPP), or octa(aminophenoxy)silsesquioxane (OAPS), either are not commercially available or are prohibitively expensive. Finding more cost efficient cross-linkers that are commercially available to synthesize these aerogels is crucial for making large scale manufacturing attractive. Herein, we describe an approach to making polyimide aerogels starting with amine capped oligomers that are cross-linked with 1,3,5-benzenetricarbonyl trichloride (BTC). BTC is a lower cost, commercially available alternative to TAB, TAPP, or OAPS. Aerogels made in this way have the same or higher modulus and higher surface area compared to those previously reported with either TAB or OAPS cross-links at the same density. While the cross-link structure is an amide, the thermal stability is not compromised most likely because the cross-link is only a small part of the composition of the aerogel. Onset of decomposition depends primarily on the backbone chemistry with 4,4'-oxidianiline (ODA) being more thermally stable than 2,2'-dimethylbenzidine (DMBZ), similar to those previously reported with other cross-links.

Increased tensile strength of carbon nanotube yarns and sheets through chemical modification and electron beam irradiation.

The inherent strength of individual carbon nanotubes (CNTs) offers considerable opportunity for the development of advanced, lightweight composite structures. Recent work in the fabrication and application of CNT forms such as yarns and sheets has addressed early nanocomposite limitations with respect to nanotube dispersion and loading and has pushed the technology toward structural composite applications. However, the high tensile strength of an individual CNT has not directly translated into that of sheets and yarns, where the bulk material strength is limited by intertube electrostatic attractions and slippage. The focus of this work was to assess postprocessing of CNT sheets and yarns to improve the macro-scale strength of these material forms. Both small-molecule functionalization and electron-beam irradiation were evaluated as means to enhance the tensile strength and Young's modulus of the bulk CNT materials. Mechanical testing revealed a 57% increase in tensile strength of CNT sheets upon functionalization compared with unfunctionalized sheets, while an additional 48% increase in tensile strength was observed when functionalized sheets were irradiated. Similarly, small-molecule functionalization increased tensile strength of yarn by up to 25%, whereas irradiation of the functionalized yarns pushed the tensile strength to 88% beyond that of the baseline yarn.

Tailoring properties of cross-linked polyimide aerogels for better moisture resistance, flexibility, and strength.

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.

Polyimide aerogels cross-linked through amine functionalized polyoligomeric silsesquioxane.

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.

Reinforced thermoplastic polyimide with dispersed functionalized single wall carbon nanotubes.

Molecular pi-complexes were formed from pristine HiPCO single- wall carbon nanotubes (SWCNTs) and 1-pyrene- N-(4-N'-(5-norbornene-2,3-dicarboxyimido)phenyl butanamide, 1. Polyimide films were prepared with these complexes as well as uncomplexed SWCNTs and the effects of nanoadditive addition on mechanical, thermal, and electrical properties of these films were evaluated. Although these properties were enhanced by both nanoadditives, larger increases in tensile strength and thermal and electrical conductivities were obtained when the SWCNT/1 complexes were used. At a loading level of 5.5 wt %, the T(g) of the polyimide increased from 169 to 197 degrees C and the storage modulus increased 20-fold (from 142 to 3045 MPa). The addition of 3.5 wt % SWCNT/1 complexes increased the tensile strength of the polyimide from 61.4 to 129 MPa; higher loading levels led to embrittlement and lower tensile strengths. The electrical conductivities (DC surface) of the polyimides increased to 1 x 10(-4) Scm(-1) (SWCNT/1 complexes loading level of 9 wt %). Details of the preparation of these complexes and their effects on polyimide film properties are discussed.

Elastic behavior of methyltrimethoxysilane based aerogels reinforced with tri-isocyanate.

The elastic properties and/or flexibility of polymer reinforced silica aerogels having methyltrimethoxysilane (MTMS) and bis(trimethoxysilylpropyl)amine (BTMSPA) making up the silica structure are examined. The dipropylamine spacer from BTMSPA is used both to provide a flexible linking group in the silica structure, and as a reactive site via its secondary amine for reaction with a tri-isocyanate, Desmodur N3300A. The tri-isocyanate provides an extended degree of branching or reinforcement, resulting in increased compressive strength of the aerogel monoliths while the overall flexibility arising from the underlying silica structure is maintained. The compressive moduli of the reinforced aerogel monoliths in this study range from 0.001 to 158 MPa. Interestingly, formulations across this entire range of modulus recover nearly all of their length after two compressions to 25% strain. Differences in pore structure of the aerogels due to processing conditions and solvent are also discussed.

Tailoring elastic properties of silica aerogels cross-linked with polystyrene.

The effect of incorporating an organic linking group, 1,6-bis(trimethoxysilyl)hexane (BTMSH), into the underlying silica structure of a styrene cross-linked silica aerogel is examined. Vinyltrimethoxysilane (VTMS) is used to provide a reactive site on the silica backbone for styrene polymerization. Replacement of up to 88 mol % of the silicon from tetramethoxyorthosilicate with silicon derived from BTMSH and VTMS during the making of silica gels improves the elastic behavior in some formulations of the cross-linked aerogels, as evidenced by measurement of the recovered length after compression of samples to 25% strain. This is especially true for some higher density formulations, which recover nearly 100% of their length after compression to 25% strain twice. The compressive modulus of the more elastic monoliths ranged from 0.2 to 3 MPa. Although some of these monoliths had greatly reduced surface areas, changing the solvent used to produce the gels from methanol to ethanol increased the surface area in one instance from 6 to 220 m(2)/g with little affect on the modulus, elastic recovery, porosity, or density.

Structure-property relationships in porous 3D nanostructures: epoxy-cross-linked silica aerogels produced using ethanol as the solvent.

Cross-linking silica aerogels with organic groups has been shown to improve the strength over un-cross-linked aerogels by as much as 2 orders of magnitude. Previous cross-linking chemistry has been developed using solvents specifically chosen to dissolve the monomers and accommodate the reaction temperature. Because the process of making the aerogels requires so much solvent, it is of interest to consider less toxic solvents such as ethanol to increase safety and enhance scale up. To this end, two different epoxy precursors with suitable solubility in ethanol were evaluated as cross-linkers for silica gels prepared from (3-aminopropyl)triethoxysilane and tetraethylorthosilicate. In addition, 1,6-bis(trimethoxysilyl)hexane (BTMSH) was used as an additive in the underlying silica structure to add flexibility to the aerogels. It was found that the ethanol-derived aerogels exhibited more shrinkage than those prepared from other solvents but that including BTMSH in the aerogels significantly reduced this shrinkage. Inclusion of BTMSH also imparted the ability of the aerogel monoliths to recover elastically when compressed up to 50% strain. In addition, optimized cross-linked aerogels prepared in this study have mechanical properties comparable to those using other more undesirable solvents and cross-linkers.