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At least 163 records · Page 9

Damage-Tolerant Composites Made By Stitching Carbon Fabrics

Work conducted at NASA Langley Research Center to investigate stitching combined with resin transfer molding to make composites more tolerant of damage and potentially cost competitive with metals. Composite materials tailored for damage tolerance by stitching layers of dry carbon fabric with closely spaced threads to provide reinforcement through thickness. Epoxy resin then infused into stitched preforms, and epoxy was cured. Various stitching patterns and thread materials evaluated by use of flat plate specimens. Also, blade-stiffened structural elements fabricated and tested. Stitched flat laminates showed outstanding damage tolerance, excellent compression strength in notched specimens, and acceptable fatigue behavior. Development of particular interest to aircraft and automotive industries.

Dow, Marvin B.↗

Carbon Fiber and Polymer Composites

Tooling is an integral part of composites manufacturing. Composite tools, also called ‘soft’ tools, are more easily constructed than ‘hard’ metal tools and, because they are made from materials similar to the manufactured composite part, they can be made in-house and have a good co-efficient of thermal expansion match. However, as the ‘soft’ designation suggests, they are more vulnerable to wear and typically find application in relatively low-volume production. Additive manufacturing of thermoplastics has proven to be a lucrative option that can help improve the tooling functionalities, as it offers more design flexibility. Owing to the inherent nature of additive manufacturing, the possibility of printing sensors within the tool material and at proximity to otherwise inaccessible areas of the tool become a reality. Continuous carbon fiber (CCF)-reinforced three-dimensional (3D) printing of engineering thermoplastics has proven to be a viable option to strengthen a part well beyond the ideal moduli of unmodified thermoplastic. Furthermore, adding nanotubes or graphene to the thermoplastic matrix will also improve both the thermal conductivity and interlaminar shear strength within the tool. Carbon nanotubes (CNTs) and carbon fibers (CFs) are microwave susceptors; exploiting the physics of Joule heating to increase the energy efficiency of tool hardening and cure rates is a core goal of this project. Because of the rapid volumetric heating enabled by the absorption of microwave or radio frequency energy and electromagnetic (EM) annealing presents an attractive opportunity to significantly reduce manufacturing cycle times while improving part performance.

Craps, Matthew G.↗

Elucidating Norrish type I reactive pathways by ultrafast X-ray absorption spectroscopy

Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.

Graßl, Martin [SLAC National Accelerator Laborator↗

Fabrication of Polyimide-Matrix/Carbon and Boron-Fiber Tape

The term HYCARB denotes a hybrid composite of polyimide matrices reinforced with carbon and boron fibers. HYCARB and an improved process for fabricating dry HYCARB tapes have been invented in a continuing effort to develop lightweight, strong composite materials for aerospace vehicles. Like other composite tapes in this line of development, HYCARB tapes are intended to be used to build up laminated structures having possibly complex shapes by means of automated tow placement (ATP) - a process in which a computer-controlled multiaxis machine lays down prepreg tape or tows. The special significance of the present process for making dry HYCARB for ATP is that it contributes to the reduction of the overall cost of manufacturing boron-reinforced composite-material structures while making it possible to realize increased compression strengths. The present process for making HYCARB tapes incorporates a "wet to dry" process developed previously at Langley Research Center. In the "wet to dry" process, a flattened bundle of carbon fiber tows, pulled along a continuous production line between pairs of rollers, is impregnated with a solution of a poly(amide acid) in N-methyl-2-pyrrolidinone (NMP), then most of the NMP is removed by evaporation in hot air. In the present case, the polyamide acid is, more specifically, that of LaRC. IAX (or equivalent) thermoplastic polyimide, and the fibers are, more specifically, Manganite IM7 (or equivalent) polyacrylonitrile- based carbon filaments that have a diameter of 5.2 m and are supplied in 12,000-filament tows. The present process stands in contrast to a prior process in which HYCARB tape was made by pressing boron fibers into the face of a wet carbon-fiber/ poly(amide acid) prepreg tape . that is, a prepreg tape from which the NMP solvent had not been removed. In the present process, one or more layer(s) of side-by-side boron fibers are pressed between dry prepreg tapes that have been prepared by the aforementioned gwet to dry h process. The multilayer tape is then heated to imidize the matrix material and remove most of the remaining solvent, and is pressed to consolidate the multiple layers into a dense tape. For tests, specimens of HYCARB tapes and laminated composite panels made from HYCARB tape were prepared as follows: HYCARB tapes were fabricated as described above. Each panel was made by laying down ten layers of tape, containing, variously, one, two, or three boron-fiber plies and the remainder carbon- fiber-only plies (see figure). Each panel was made by laying down ten layers of tape. Each panel was then cured by heating to a temperature of 225 C for 15 minutes, then pressing at 200 psi (A1.4 MPa) while heating to 371 C, holding at 371 C for 1 hour, then continuing to hold pressure during cooling. Control specimens that were otherwise identical except that they did not contain boron fibers also were prepared. In room-temperature flexural tests, the HYCARB specimens performed comparably to the control specimens; in room-temperature, open-hole compression tests, the HYCARB specimens performed slightly better, by amounts that increased with boron content.

Belvin, Harry L.↗

Process Development and Testing for Lunar Habitats

Non-metallic composites are appealing for Lunar habitats due to their low specific weight and contribution to passive radiation shielding. This application of composite materials presents notable challenges, however: flammability risks are higher due to elevated oxygen levels expected in habitat structures and absorbed radiation can cause damage long-term. The Materials and Processes Laboratory at Marshall Space Flight Center awarded funding for an internal research and development study which included fabrication and testing of composite materials for Lunar habitats. Composite layups used carbon fiber or ultra-high molecular weight polyethylene reinforcement and a variety of polymer matrices. Pre-impregnated fabric was autoclave cured; however, novel coatings were incorporated during select layups. Samples from each panel were used for screening-level flammability testing (ASTM D 2863) and combined vacuum ultraviolet and electron irradiation followed by tension testing (ASTM D5766). Two of the tested composite materials exceeded a 37% limiting oxygen index. Material property degradation for a 10 year simulated radiation dose was minimal in most cases.

manufacturing↗

Controlled Pyrolysis: A Robust Scalable Composite Recycling Technology

The reinforced composites industry is facing significant challenges in handling the scrap composite material from automobile manufacturing, the wind turbine industry, and others. The fibers in the material, whether they be carbon, glass, or other materials have commercial value if they can be recovered successfully. Successfully means the fibers are clean with no sizing or other binders and have adequate strength and physical properties that would allow them to be economically reprocessed into valuable product. The composites recycling project was an industry-collaborative effort to develop a composite recycling technology using controlled pyrolysis. Through the recycling of scrap and end-of-life (EOL) cured composite materials, this pilot study was intended to create a business case by realizing a cost-effective means for recycling EOL and production scrap composite materials, ultimately reducing the volume of composite materials destined for landfill. The project was led by the Institute for Advanced Composites Manufacturing Innovation (IACMI), the American Composites Manufacturers Association (ACMA), Oak Ridge National Laboratory (ORNL), Continental Structural Plastics (CSP) a Teijin Group Company, CHZ Technologies, and A. Schulman with support from Owens Corning, John Deere, General Electric (GE), Ashland LLC, and Plastics Europe (CEFIC). The team studied and tested CHZ Technologies’ controlled pyrolysis system, known as the Thermolyzer TM , which operates on a scalable basis to convert organic polymer materials into a clean synthesis gas and char containing the recoverable carbon and glass fiber reinforcement. The recoverable energy contained in the input polymers creates the synthesis gas that can be used to provide heat to the Thermolyzer TM primary reactor in a sustainable manner. That is, once the Thermolyzer TM is started with a small amount of external natural gas, the synthesis gas that is created from the polymers will continue to operate the burners so long as feedstock is supplied. The reinforcing fiber materials remaining in the solid phase char were separated and cleaned for re-use in other polymer systems based on the retained properties of the fibers. The study created reports (attached in the appendix) on the Mass and Energy Balances, syngas analytics, VOC assessment, yield analysis and other analytics necessary for a Techno-Economic Analysis (TEA) to quantify the economic impact of the recovery and sustainable re-use of the carbon and glass fibers. The process consisted of 4 steps: Selection of 4 samples of cured composite waste materials from project partners interested in materials recycling and recovering the reinforcing fibers for best case re-use. The materials included glass fiber (GF) polyester/vinyl ester automotive SMC from CSP, GF epoxy balsa/PVC foam wind blades from GE, carbon fiber (CF) epoxy wind blade laminated spar caps from GE, and GF/CF epoxy hybrid assembly from John Deere. Processing the waste composite samples into 1-2” shreds. Packaging the shredded composites into bulk sacks on international shipping pallets for shipment to KUG in Forst (Lausitz), Germany. Pyrolysis of the shredded composites under controlled conditions designed for each polymer system. Collecting samples of the gas and char for analysis. Shipping the char containing the CF/GF back to the US for the next steps of testing the fibers and developing protocols for sustainable re-use of the fibers in composite applications.

36 MATERIALS SCIENCE↗

Characterization of micro-sandwich structures via direct ink writing epoxy based cores

Sandwich structured (SS) composites demonstrate considerable flexural stiffness and high strength-to-weight ratios and can be tailored as functional materials. Historically they have been constrained to specific material types and geometry due to limitations in manufacturing methods. However, employing additive manufacturing (AM), specifically direct ink writing (DIW), can provide an alternative method for making SS composites with complex and controllable micro and mesostructures with multifunctionality targeted at desired mechanical, thermal, and electrical properties. DIW, an extrusion-based AM technique, uses a viscous and thixotropic ink with desired components that, once printed, is cured to obtain the final complex net shape parts. In this paper, a novel hybrid AM technique is employed to manufacture SS composite materials containing bisphenol A-based epoxy core and carbon fiber reinforced polymer (CFRP) face sheets that are fabricated via DIW and vacuum infusion process (VIP), respectfully. We demonstrate that the fabrication of these SS composites can be tailored from a thermosetting material, from which additives and/or various lattice structures can be manufactured to achieve enhanced and desirable mechanical integrity with functional properties. Surface topology and mechanical testing techniques are used to characterize the fabricated hybrid SS composites to study and assess mechanical stability. A rheo-kinetic cure model was developed for the core material to allow for additive manufacturing process requirements while ensuring complete cross-linking for the thermoset-based core material. Because of the ability to obtain relatively small core-thickness and controlled architecture, this method now allows for fabricating layered micro-sandwich structures for realizing further light-weighting in relevant applications.

36 MATERIALS SCIENCE↗

Ultrahigh areal number density solid-state on-chip microsupercapacitors via electrohydrodynamic jet printing

Microsupercapacitors (MSCs) have garnered considerable attention as a promising power source for microelectronics and miniaturized portable/wearable devices. However, their practical application has been hindered by the manufacturing complexity and dimensional limits. Here, we develop a new class of ultrahigh areal number density solid-state MSCs (UHD SS–MSCs) on a chip via electrohydrodynamic (EHD) jet printing. This is, to the best of our knowledge, the first study to exploit EHD jet printing in the MSCs. The activated carbon-based electrode inks are EHD jet-printed, creating interdigitated electrodes with fine feature sizes. Subsequently, a drying-free, ultraviolet-cured solid-state gel electrolyte is introduced to ensure electrochemical isolation between the SS–MSCs, enabling dense SS–MSC integration with on-demand (in-series/in-parallel) cell connection on a chip. The resulting on-chip UHD SS–MSCs exhibit exceptional areal number density [36 unit cells integrated on a chip (area = 8.0 mm x 8.2 mm), 54.9 cells cm -2 ] and areal operating voltage (65.9 V cm -2 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AERoBOND Project Summary

Under NASA’s Convergent Aeronautics Solutions (CAS) project, the Adhesive-Free Bonding of Complex Composites (AERoBOND) project investigated off-stoichiometric epoxy polymers for fast, reliable assembly of epoxy matrix composite structures. The project goal was to demonstrate feasibility of the AERoBOND joining method by demonstrating mechanical properties greater than 80% of conventional co-cured materials while reducing structure weight by 1%. The project consisted of three convergent research areas: material and process development, systems analysis, and material and process modeling. Material and process development was the largest component of AERoBOND with approximately 6 FTE and 1WYE of support to formulate and characterize new resins, prepare carbon fiber prepregs, fabricate laminates, measure mechanical properties, analyze failure results, and select material and process improvements. The systems analysis activity estimated the potential reduction in part count and aircraft weight by comparing models of composite wing boxes with no fasteners (co-cured structure), fasteners in major joints (co-cured stringers), and fasteners in all joints. The materials and process modeling activity included a molecular model of the AERoBOND materials system to predict mechanical properties of resins with offset stoichiometry and a process model to predict the effect of resin formulation and processing conditions on the extent of mixing and degree of cure in a finished joint. As the number of airline passenger trips doubles in the next 20 years (IATA/Tourism Economics Air Passenger Forecasts, April 2019), the increased demand for new commercial aircraft is now the single greatest technical challenge to the airframe manufacturing industry. To meet efficiency requirements, new aircraft must be fabricated primarily from high performance structural composites, but manufacturing processes are inherently slow with the largest bottleneck attributed to assembly and installation of fasteners (NASA/TM–2019-220428). Manufactures of commercial transport aircraft are compelled to install more than 100,000 redundant fasteners into bonded joints to prevent failures due to unpredictable weak bonds. In structural adhesive bonds, the interface between adherend and adhesive is nearly two-dimensional making it susceptible to minute quantities of contamination, which can cause weak bonds. Currently, bond strength assessment is only possible through destructive testing (i.e., breaking the joint). For these reasons, regulatory organizations such as the Federal Aviation Administration (FAA) often require redundant load paths in secondary-bonded, primary-structures to alleviate concerns with bond performance. The AERoBOND process enables reflow of matrix resin during assembly to eliminate the material discontinuity at the interface, thereby eliminating the dependence of mechanical performance on interfacial adhesion. The AERoBOND joint is equivalent to the interlaminar region obtained during a co-cure process, so joint performance depends on the cohesive properties of the matrix resin. Conventional co-cured structures, although too costly and complex for large-scale manufacturing, are trusted by manufacturers and regulators, and are certified for flight with few or no redundant fasteners.Systems analysis performed on a composite wing model at the scale of a single-aisle commercial transport aircraft indicated that >20,000 redundant fasteners per wing could be eliminated by implementing the AERoBOND joining method. A total weight reduction of 15% was predicted in a wing box by eliminating fasteners and thinning components that must no longer support localized fastener loads and accommodate fastener dimensions. Interlaminar shear fracture toughness measured by the end-notched flexure test was greater than 1 kJ/m2 (nearly 140% of the co-cured benchmark property), which is greatly in excess of the project goals for mechanical properties. Testing was planned to measure interlaminar tensile fracture toughness as well as interlaminar tensile and shear strengths using the same AERoBOND configuration, but was delayed due to closure of LaRC facilities during the COVID-19 pandemic. The AERoBOND process model is partially validated and available for experimental use. It allows the user to input AERoBOND process parameters such as material composition, laminate configuration, and cure cycle to predict the final cure state of the AERoBOND joint. A preliminary, multi-scale material model was developed to predict AERoBOND joint mechanical properties (stiffness and strength) based on the cure state of the joint provided by the process model. The timing for transition of this technology within NASA is excellent as NASA initiates new enduring projects to address composites manufacturing rate challenges. AERoBOND technology is well suited to AAVP/AATT objectives for rapid manufacturing of a composite wing. A minimal effort (1 FTE/$15k procurement/0 WYE) is proposed in FY21 to continue a minor mechanical testing effort and maintain a SAA with ASX composites to develop commercial quality prepreg material. An RFI with the composites industry is suggested to quantify the technology gap between the current TRL and the TRL needed for transition to industry. A moderate effort [3-4 FTE/$150k/1 WYE (~$115k)] is proposed in FY22 for the “high rate composites manufacturing” project currently in planning. The partnership with ASX Composites will be expanded to produce material for sub-element/element-scale “panel-off” activities. Industry partnerships with airframe manufacturers is an expected component to explore damage tolerance and environmental stability. Further development of multi-scale modeling tools (process model, meso-scale model, and molecular model) is planned to enhance and deliver tools for rapid manufacturing infusion.

Frank Louis Palmieri↗

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗

Optimized Carbon Fiber Intermediate Development to Enable High-Volume Manufacturing of Lightweight Automotive Composites

The ongoing pursuit of improved fuel economy and reduced greenhouse gas emissions has resulted in sustained interest for lightweight materials technologies. In this context, carbon fiber composites have captured the imagination of automotive engineers due to the potential to achieve substantial mass reduction when compared to traditional steel construction. That stated, the use of carbon fiber composites in automotive has been limited for the most part to premium supercars and other derivative platforms. In these cases, manufacturing costs are less of an obstacle to implementation, and the performance benefits of carbon fiber have enabled production of structures offering more than 50% weight savings. In practice, translating these low-volume demonstrations onto high-volume vehicle platforms has remained challenging. This can be attributed to several factors, with the absence of suitable high throughput production methodologies being a key impediment. To date, structural, crash critical components have relied upon manufacturing techniques born out of the aerospace industry. This has created a disconnect between automotive production systems that are accustomed to manufacturing multiple parts per minute and the aerospace technologies that have cycle times in the order of hours. Consequently, the focus of this project is the development of manufacturing process technology for carbon fiber composites that can support a mainstream vehicle program at an assumed throughput of 100,000 vehicles per year. In practice, this translates to a part-to-part cycle time of less than 3 minutes. Project participation included contributions from a broad range of academic, industrial and national lab partners. The primary scope of work, being the development of new carbon fiber epoxy compounds that are stable at room temperature and suited to high throughput automated processing. For project management, the work streams were divided into six key areas, with the lead organization in parentheses. • Carbon fiber/epoxy materials formulation development and scale up (Dow) • Simulation of discontinuous near isotropic meso-structure intermediates (Purdue) • Simulation of mechanical performance of compression molded components (Purdue) • Meso-Scale morphological analysis and correlation with structural performance (UTK) • Paint and adhesion durability analysis (MSU) • Demonstrator part design, prototype production, and validation testing (Ford). The primary goal at the commencement of the project was development of a chopped carbon fiber sheet molding compound (SMC) that offered a three times improvement in tensile modulus over a comparable glass-based SMC. In addition to meeting mechanical performance targets, the resin kinetics were modified to achieve a processing cycle time of less than 3 minutes. Other critical-to-quality (CTQ) specifications were also stipulated to account for a broad range of materials and processing characteristics. To achieve the above, staff scientists at Dow Chemical created an extensive series of new epoxy blends for testing and validation. Throughout this development, a key challenge was attaining material performance goals without impacting processing behavior and paintability of finished components. The latter required a new internal mold release system being developed by Dow that was designed to complement the kinetics of the rapid cure epoxy. As a complement to work studies at the industrial partners, the teams from academia executed a series of analytical and experimental studies to investigate potential factors influencing CF-SMC performance. Unit cell models were developed to capture the meso-scale representations of the fiber matrix architecture. Results of this analysis and subsequent morphological investigations led to the design of a novel composite derivative comprising carbon fiber platelets embedded in an epoxy matrix; the platelet size and aspect ratio playing significant role in final composite properties. This approach was a departure from previous research in CF-SMC development whereby bulk filamentization or disassembly of the carbon fiber rovings had been considered the most effective means of achieving both fiber wet through and wet-out. As the course of the academia studies progressed, the aspect ratio of the fiber constituents was further optimized before finalizing material attributes and processing conditions. For the purposes of technology validation, the Ford team led a work stream devoted to the design, fabrication and testing of demonstration components. The carbon fiber SMC material has the potential to displace numerous stampings and castings on an automotive structure but ultimately vehicle closure applications were selected to showcase the abilities of the CF-SMC to achieve both mass reduction and business case for large complex structures. Using target properties established by the Dow staff scientists, the complete closure system for a full-size sedan decklid and a mid-size wagon liftgate were engineered. Prototypes for both applications were fabricated using production representative processing methods to allow for physical testing and performance validation of the CF-SMC structures. Following completion of a testing program that concluded with a FMVSS301 55 mph offset rear crash, the CF-SMC formulation was declared by the Ford team to have met all engineering requirements. To summarize, the joint development activities during this project led to significant technical breakthroughs and achievement of all milestones. The result was the development of a novel, tack-free carbon fiber molding compound that is suited to automated processing. This combined room temperature stability, fast cure kinetics, and internal mold release system facilitates cycle times that are conducive to high-volume production. The VORAFUSE M6400 successfully passed technology validation at Ford and is now eligible for consideration on future production commercial vehicle programs.

36 MATERIALS SCIENCE↗

An infiltration/cure model for manufacture of fabric composites by the resin infusion process

A 1-D infiltration/cure model was developed to simulate fabrication of advanced textile composites by the resin film infusion process. The simulation model relates the applied temperature and pressure processing cycles, along with the experimentally measured compaction and permeability characteristics of the fabric preforms, to the temperature distribution, the resin degree of cure and viscosity, and the infiltration flow front position as a function of time. The model also predicts the final panel thickness, fiber volume fraction, and resin mass for full saturation as a function of compaction pressure. Composite panels were fabricated using the RTM (Resin Transfer Molding) film infusion technique from knitted, knitted/stitched, and 2-D woven carbon preforms and Hercules 3501-6 resin. Fabric composites were fabricated at different compaction pressures and temperature cycles to determine the effects of the processing on the properties. The composites were C-scanned and micrographed to determine the quality of each panel. Advanced cure cycles, developed from the RTM simulation model, were used to reduce the total cure cycle times by a factor of 3 and the total infiltration times by a factor of 2.

Weideman, Mark H.↗

Infusion Processing of Phenylethynyl Terminated Imides by High Temperature RTM and VARTM

Fabrication of composite structures using infusion processes such as resin transfer molding (RTM) and vacuum assisted resin transfer molding (VARTM) is generally more affordable than conventional autoclave techniques. Recent efforts have focused on adapting both technologies for the fabrication of high temperature (HT) resistant composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using these high temperature out-of-autoclave processes. In the current study, two PETI resins, LARC(TradeMark) PETI-330 and LARC(TradeMark) PETI-8 have been used to make test specimens using both RTM and VARTM. For aerospace applications, a void fraction of less than 2% is desired. Traditionally, RTM has had the advantage over VARTM for generating composites with low void content. However, the process is limited in terms of size. Work at NASA LaRC has incorporated modifications to the thermal cycle used in laminate fabrication that have reduced the void content significantly (typically 1-3%) using the current HT-VARTM process. For composite fabrication by both RTM and VARTM, the resins were infused into three carbon fiber preforms (T650-35-3k 5HS, IM7-6k 5HS, and IM7-6k Uniweave) at 316 C and 260 C respectively and cured up to 371 C. The details of the RTM processing carried out at the University of Akron are discussed in this work along with a brief description of the HT-VARTM processing carried out at NASA-LaRC. Photomicrographs of the panels were taken and void contents were determined by acid digestion. Mechanical properties (short beam shear, SBS) of the panels fabricated by both infusion processes were determined at room temperature as well as at various elevated temperatures. The results of this work are presented herein.

Ghose, Sayata↗

TPS Materials and Costs for Future Reusable Launch Vehicles

There is considerable interest in developing new reusable launch vehicles (RLVs) for reducing the cost of transporting payload to and from orbit. This work reviews thirteen candidate thermal protection system (TPS) options currently available for RLVs. It is useful to begin with the current Shuttle TPS layout as a reference. The nose cap and wing leading edge , which reach the highest temperatures, are made of reinforced carbon-carbon (RCC) that is protected from oxidation by an external coating (about 0.020" thick) of silicon-carbide. Most of the windward surface is 9 lb/cubic ft ceramic tiles (LI-900) with a thin (about 0.012") coating of Reaction Cured Glass (RCG). The leeward side of the vehicle is covered largely by AFRSI, a quilted ceramic blanket, and FRSI, a polyamide felt. These four materials can be considered first generation reusable TPS. Since the time of the Shuttle design, considerable progress has been made advancing TPS technologies in terms of thermal performance, robustness, and cost. For each of the major systems, a second generation ceramic TPS has been developed, tested, and characterized. Metallic-based systems have also been developed. For applications requiring RCC in the past, advanced carbon-carbon (ACC) is now available. This material has better mechanical properties, somewhat higher temperature capability to 2900F and greatly increased oxidation resistance. New carbon fiber reinforced silicon-carbide matrix composites (C/SiCs) have shown additional improvement in properties over ACC with use temperatures to 3000F and above. For rigid tiles, NASA Ames has made two significant advancements. The first is a tile substrate called Alumina Enhanced Thermal Barrier, or AETB, that incorporates alumina fibers for improved dimensional stability at high temperatures, to 2600F and above. This material can be made to densities as low as 8 lb/cubic ft. The second is a coating preparation called Toughened Uni-piece Fibrous Insulation, or TUFT, that penetrates about 0.1 in. into the tile substrate. The resulting composite, with a functionally gradient density near the surface, provides orders of magnitude increased damage resistance compared with RCG coated LI-900, with only a small weight increase. The TPS that combines these two developments is called AETB-8/TUFI and has been adopted for high damage areas on the Shuttles. Two notable developments have occur-red in flexible ceramic blanket technology. The first is aluminoborosilicate-based fibers with use temperatures of 2200F and above," in comparison to quartz and silica fiber used in AFRSI which have multi-use temperature limits of 1200 to 1400F. Blankets incorporating these new high temperature fibers are referred to as AFRSI-HT. The second is an integral weaving techniques that produces a fluted core blanket with a smoother surface and greater resistance to aero-acoustic noise, to levels as high as 170 dB. This Ames innovation is called Tailorable Advanced Blanket Insulation, or TABI. Finally, for felt-based TPS, Boeing is developing Polybenzimidazole Blanket Insulation, or PBI, with a multi-use temperature limit of 1000F and above, in contrast to Shuttle FRSI which has a multi-use temperature limit of about 700F. 1.6 NASA Langley and BF Goodrich (formerly Rohr Corp.) have led the development of metallic-based TPS. This activity uses essentially three approaches: metallic tiles which encase a fibrous ceramic batting in a box fabricated largely from metallic honeycombs, typically Nickel based alloys; metallic honeycomb sheets, made of Nickel-based alloys, incorporating a fibrous back-side insulation encapsulated in a metallic foil bag, providing reduced weight; and metallic multi-wall, which is comprised of dimpled Titanium metal sheets, which are stacked and then diffusion bonded at contact points to form the TPS. The Nickel-based systems can be used up to temperatures of about 1800F, and the Titanium system to about 100F. These thirteen TPS materials have pros and cons to their usage in terms of temperature capability, weight, initial cost, and maintenance. Carbon-carbon and C/SiC systems have the highest temperature capability but are relatively expensive and heavy, requiring significant time, expertise, and costly facilities and tools for design and fabrication. Second generation ceramic tiles are relatively light, durable, simple to fabricate and easy to install; however, waterproofing is a concern. Blankets and felts are light, simple, inexpensive, and easy to install over curved vehicle surfaces, but durability and waterproofing are concerns. Metallics are robust and appear to have eliminated waterproofing, but they tend to be heavy and relatively expensive, requiring costly facilities and tools. If thin metal sheets are used to reduce weights, then issues arise from possible metal fatigue and corrosion caused by thermal cycling, pressure oscillations, and environmental exposure. For application to future RLVs, system analyses show that a significant component of the vehicle life cycle cost is from the TPS; however, it is difficult to quantify and to compare the potential savings of advanced systems without performing full vehicle designs using each of the different options. Because this entails a considerable effort and also tends to submerge TPS cost impacts under unrelated vehicle design assumptions, there is a clear need for a simpler quantitative method to evaluate the cost impact of different TPS options. To this end, this work introduces a TPS life-cycle cost parameter which is easily computed and applicable to generic RLVs.

Rasky, Dan J.↗

Sequestration of Single-Walled Carbon Nanotubes in a Polymer

Sequestration of single-walled carbon nanotubes (SWCNs) in a suitably chosen polymer is under investigation as a means of promoting the dissolution of the nanotubes into epoxies. The purpose of this investigation is to make it possible to utilize SWCNs as the reinforcing fibers in strong, lightweight epoxy-matrix/carbon-fiber composite materials. SWCNs are especially attractive for use as reinforcing fibers because of their stiffness and strength-to-weight ratio: Their Young s modulus has been calculated to be 1.2 TPa, their strength has been calculated to be as much as 100 times that of steel, and their mass density is only one-sixth that of steel. Bare SWCNs cannot be incorporated directly into composite materials of the types envisioned because they are not soluble in epoxies. Heretofore, SWCNS have been rendered soluble by chemically attaching various molecular chains to them, but such chemical attachments compromise their structural integrity. In the method now under investigation, carbon nanotubes are sequestered in molecules of poly(m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene) [PmPV]. The strength of the carbon nanotubes is preserved because they are not chemically bonded to the PmPV. This method exploits the tendency of PmPV molecules to wrap themselves around carbon nanotubes: the wrapping occurs partly because there exists a favorable interface between the conjugated face of a nanotube and the conjugated backbone of the polymer and partly because of the helical molecular structure of PmPV. The constituents attached to the polymer backbones (the side chains) render the PmPV-wrapped carbon nanotubes PmPV soluble in organic materials that, in turn, could be used to suspend the carbon nanotubes in epoxy precursors. At present, this method is being optimized: The side chains on the currently available form of PmPV are very nonpolar and unable to react with the epoxy resins and/or hardeners; as a consequence, SWCN/PmPV composites have been observed to precipitate out of epoxies while the epoxies were being cured. If the side chains of the PmPV molecules were functionalized to make them capable of reacting with the epoxy matrices, it might be possible to make progress toward practical applications. By bonding the side chains of the PmPV molecules to an epoxy matrix, one would form an PmPV conduit between the epoxy matrix and the carbon nanotubes sequestered in the PmPV. This conduit would transfer stresses from the epoxy matrix to the nanotubes. This proposed load-transfer mode is similar to that of the current practice in which silane groups are chemically bonded to both the epoxy matrices and the fibers (often glass fibers) in epoxymatrix/fiber composites.

Bley, Richard A.↗

Tuning the Mechanical Properties of Crosslinked Copolymers via Sequence and Solvent‐Selective Swelling for Vat Photopolymerization

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

additive manufacturing↗

Removal of surface loop from stitched composites can improve compression and compression-after-impact strengths

Stitching through-the-thickness (TTT) of composite materials produces a surface loop of yarn between successive penetrations. The surface loop is pressed into the surface layers of the composite material during the curing of the laminate, kinking the in-plane fibers near the surface of the material. The compression strength and compression-after-impact (CAI) strengths of carbon-epoxy specimens were measured with and without the surface loop. Removal of the surface loop had no influence on failure mode or failure mechanism, but did significantly increase the compression and CAI strengths.

Farley, Gary L.↗

Structural Health Monitoring of Composite Wound Pressure Vessels

The increasing use of advanced composite materials in the wide range of applications including Space Structures is a great impetus to the development of smart materials. Incorporating these FBG sensors for monitoring the integrity of structures during their life cycle will provide valuable information about viability of the usage of such material. The use of these sensors by surface bonding or embedding in this composite will measure internal strain and temperature, and hence the integrity of the assembled engineering structures. This paper focuses on such a structure, called a composite wound pressure vessel. This vessel was fabricated from the composite material: TRH50 (a Mitsubishi carbon fiber with a 710-ksi tensile strength and a 37 Msi modulus) impregnated with an epoxy resin from NEWPORT composites (WDE-3D-1). This epoxy resin in water dispersed system without any solvents and it cures in the 240-310 degrees F range. This is a toughened resin system specifically designed for pressure applications. These materials are a natural fit for fiber sensors since the polyimide outer buffer coating of fiber can be integrated into the polymer matrix of the composite material with negligible residual stress. The tank was wound with two helical patterns and 4 hoop wraps. The order of winding is: two hoops, two helical and two hoops. The wall thickness of the composite should be about 80 mil or less. The tank should burst near 3,000 psi or less. We can measure the actual wall thickness by ultrasonic or we can burst the tank and measure the pieces. Figure 1 shows a cylinder fabricated out of carbon-epoxy composite material. The strain in different directions is measured with a surface bonded fiber Bragg gratings and with embedded fiber Bragg gratings as the cylinder is pressurized to burst pressures. Figure 2 shows the strain as a function of pressure of carbon-epoxy cylinder as it is pressurized with water. Strain is measured in different directions by multiple gratings oriented in both axial and hoops directions.

Joseph Grant↗