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Cryogenic Mixed Mode I – Mode II Fracture Toughness of Various Polymer Composite Materials

The present study investigates the mixed mode interlaminar fracture toughness of six polymer matrix composite materials at both room temperature and cryogenic liquid nitrogen temperature. The single leg bending test employed gives a mix of Mode I (opening) and Mode II (in-plane shearing) cracking. The tested thermoplastic-matrix composites were shown to have total mixed mode toughnesses 3.1–4.3 times higher than those of representative thermoset resin composites.

Carbon fiber

Influence of microstructure and temperature on impact toughness of H13 steel produced by binder jet additive manufacturing

Binder Jet Additive Manufacturing (BJAM) is a promising manufacturing pathway to produce H13 steel dies and tooling with complex geometries for applications in high pressure aluminum die casting, hot stamping, and injection molding. While fully dense H13 coupons produced using BJAM have been subjected to detailed microstructure characterization, properties which are critical and relevant to the aforementioned applications, such as impact toughness, have not been reported. Here, this work evaluated the influence of microstructural characteristics and test temperature on the impact toughness of H13 produced by BJAM. Coupons were produced from three different powder size distributions (PSDs), with nominal powder size ranges of −22 μm, 10-32 μm, and 15-53 μm. Coupons were printed, sintered, hot isostatically pressed (HIPed), and heat treated by quenching and tempering. After HIPing, the measured porosities of the different PSDs were all less than 0.015 vol%. The −22 μm PSD BJAM material exhibited the best impact toughness of all three PSDs across the entire test temperature range from 25 to 400 °C, and also exhibited an ambient temperature impact toughness of 10.9 J at a hardness of 46 HRC, equivalent to minimum threshold requirements for premium grade H13. However, all three BJAM PSDs exhibited moderately lower impact toughness than premium grade wrought H13 from RT to 400 °C. We attribute this in part due to the very large prior-austenite grain (PAG) sizes near 400 μm and segregation from former liquid channels leading to greater amounts of carbide precipitation on PAG boundaries. Technical pathways for optimizing processing and chemistry of BJAM H13 to further improve impact toughness are discussed.

Binder jet additive manufacturing

Atomic faulting drives exceptional toughness in low thermal expansion chromium alloys

Endowing functional properties with mechanical responses in traditional metals has been a frontier topic, akin to transforming base metal into gold. Chromium and its alloys, with their functional deficiencies and limited ductility, serve as typical examples. Herein, we report a Cr96Fe4Ge1.3B1 alloy that unifies low thermal expansion (LTE, αl = 1.79 × 10-6 K-1, 200 − 315 K) with exceptional toughness (240.2 J·cm-3). The enhancement in mechanical responses is primarily attributed to layered Cr2B intermetallic precipitates, which ameliorate interfacial cohesion and simultaneously refine the grain structure. The weakened interlayer interactions within the Cr-B layers facilitate the nucleation and movement of numerous tiny stacking faults in precipitates, efficiently alleviating strain energy and resulting in marked work-hardening ability. Additionally, antiferromagnetic fluctuations in the BCC matrix contribute to the unique LTE behavior. This paves the way for the design of high-performance alloys featuring layered-symmetry precipitates.

Yu, Chengyi [University of Science and Technology

Polymer Composite Material Screening for a Cryotank Application

Composite cryotanks will play a key role in enabling the next generation of efficient aircraft. Carbon fiber reinforced polymer (CFRP) composites have the benefits of reduced weight and potentially higher structural strength compared to traditional metallic fuel tanks. A material screening study was conducted to inform material selection for liquid hydrogen (LH2) fuel storage. Three composite materials were considered because of their aerospace grade toughness, strength, and existing data to compare against. These materials were a thermoplastic low-melt polyaryletherketone (LM-PAEK)/carbon fiber (CF), thermoset/CF, and hybrid thermoset/thermoplastic polyurethane (TPU) veil/CF composite. Mechanical screening tests included tension, compression, in-plane shear (IPS), and tensile-tensile fatigue (TTF). Each material was tested at both a baseline (no liquid nitrogen/LN2 cycling) and 100 LN2-cycled conditions to determine the knockdown factor, if any, of each material when exposed to environmental loading effects in a cryotank. Results show minimal effects of the LN2-cycling compared against baseline values. The three materials behaved similarly in tension; however, the thermoplastic/CF had the highest IPS toughness. The hybrid thermoset/TPU/CF composite had the lowest IPS strength, compressive strength, and toughness. LN2-cycling had minimal effects on tensile-tensile fatigue performance of the thermoplastic/CF material. Mechanical data was captured to guide material down selection for future commercially viable hydrogen aircraft design.

Composites

Polymer Composite Material Testing for a Cryotank Application

Composite cryotanks will play a key role in enabling the next generation of efficient aircraft. Carbon fiber reinforced polymer (CFRP) composites have the benefits of reduced weight and potentially higher structural strength compared to traditional metallic fuel tanks. A material screening study was conducted to inform material selection for liquid hydrogen (LH2) fuel storage. Three composite materials were considered because of their aerospace grade toughness, strength, and existing data to compare against. These materials were a thermoplastic low-melt polyaryletherketone (LM-PAEK)/carbon fiber (CF), thermoset/CF, and hybrid thermoset/thermoplastic polyurethane (TPU) veil/CF composite. Mechanical screening tests included tension, compression, in-plane shear (IPS), and tensile-tensile fatigue (TTF). Each material was tested at both a baseline (no liquid nitrogen/LN2 cycling) and 100 LN2-cycled conditions to determine the knockdown factor, if any, of each material when exposed to environmental loading effects in a cryotank. Results show minimal effects of the LN2-cycling compared against baseline values. The three materials behaved similarly in tension; however, the thermoplastic/CF had the highest IPS toughness. The hybrid thermoset/TPU/CF composite had the lowest IPS strength, compressive strength, and toughness. LN2-cycling had minimal effects on tensile-tensile fatigue performance of the thermoplastic/CF material. Mechanical data was captured to guide material down selection for future commercially viable hydrogen aircraft design. In its current state, there does not exist a consolidated, publicly available database for CFRP composite material performance data at cryogenic temperatures. The next step in this work is to test the thermoplastic and thermoset CFRP composites, as well as the neat resins, at LH2 relevant temperature (20 K) to capture this crucial material property data. These results are essential to inform cryotank design and modeling efforts. The process to start this next round of testing has begun. Planned mechanical tests include toughness (single-edge notched beam), tension (unidirectional and quasi-isotropic), thermal expansion, and thermal conductivity. Some tests will also be conducted at an intermediate temperature of 111 K relevant to liquid natural gas (LNG), another attractive fuel choice. The ultimate goal is to manufacture a sub-scale cryotank part that can pass relevant burst, fatigue, permeation, and thermal cycling tests. This work is a part of NASA’s Commercially viable Hydrogen Aircraft for Robust Growth in Efficiency (CHARGE) Project under the larger NASA Subsonic Vehicle Technologies and Tools (SVTT) Project.

composites

Molecular origin of anisotropic shear elastoplasticity in chitin

Chitin nano- and mesoscale structures present in the exoskeleton of crustaceans exhibit exceptional longitudinal stiffness and toughness, rivaling or even exceeding that of many synthetic polymer architectures. Here, we reveal the origin of the asymmetric shear response in chitin multiscale architectures, marked by pronounced anisotropy in deformation. Under shear aligned with the molecular axis, chitin accommodates strain through coherent atomic rearrangements that enable elastic recovery. In contrast, shear applied perpendicular to this axis induces liquid-like plasticity via localized sliding. These results demonstrate the intrinsic mechanical anisotropy of chitin, underpinning a dual function in resisting repetitive loading while dissipating internal stress during high-strain events. Our findings establish the molecular basis of shear elastoplasticity in multiscale chitin structures, wherein axial elasticity supports energy storage in load-bearing regions, whereas transverse plasticity enables controlled energy dissipation. These atomic-scale insights lay a foundation for the predictive design of chitin-based materials with tunable strength-toughness profiles.

Wan, Zhangmin [University of British Columbia, Van

Up-and-Coming IMCs

While the good oxidation and environmental resistance, high melting points, and comparatively low densities of such ordered intermetallics as Ti 3 Al, NiAl, FeAl, and NbAl 3 render them good candidates for advanced aerospace structures, their poor toughness at low temperatures and low strength at elevated temperatures have prompted the development of fiber-reinforced intermetallic-matrix composites (IMCs) with more balanced characteristics. Fabrication methods for continuous-fiber IMCs under development include the P/M 'powder cloth' method, the foil/fiber method, and thermal spraying. The ultimate success of IMCs depends on fibers truly compatible with the matrix materials.

Randy Bowman

3D Printing ofThermally Responsive Shape Memory LiquidCrystalline Epoxy Networks

Abstract A two-component liquid crystalline epoxy network (LCEN) with shape memory behavior was developed and evaluated as a candidate material for 3D printing. The cure kinetics of the uncured material and the shape memory properties of the cured LCEN were investigated by using parallel plate rheology and dynamic mechanical analysis, respectively. A commercially available fumed silica additive was introduced to the neat, uncured material to improve the rheological properties for 3D printing. The addition of fumed silica was found to increase the yield stress, shear-thinning behavior, and toughness of the uncured epoxy ink. Polarized light microscopy, differential scanning calorimetry, and wide-angle X-ray scattering measurements between the neat and additive-modified LCEN suggested a reduction in liquid crystalline alignment in the modified LCEN, owing to interactions between crystalline domains and fumed silica, which in turn influenced the mechanical behavior. Overall, the additive was found to be successful in preserving the shape memory properties of LCEN while improving its printability.

Chemistry

CRADA 2022-03 Final Report: Advanced Bearing Materials for Harsh Service Conditions

Develop advanced bearing materials for hydrogen gas turbines and wind turbines. Two candidate materials have been selected based on Ames lab’s recent work on high entropy alloys and shape memory alloys. These materials are designed to exhibit a balance of hardness, strength, toughness, and corrosion resistance. The hydrogen diffusion coefficient in the NiTi based shape memory alloy is two order of magnitude lower than that of the conventional case hardened bearing steel. We plan to atomize these materials into powders, additive manufacture cylindrical bearings, then test these bearing for rolling-contact fatigue, corrosion properties, and hydrogen embrittlement. We are a vertically integrated team comprises of national labs, bearing manufacturers, raw material powders makers, and aircraft gas turbine manufacturer.

Argibay, Nicolas [Ames Laboratory (AMES), Ames, IA

High Temperature Pressure (HTP) Boron Nitride Nanotube (BNNT): Discovery and Commercialization

Future NASA missions for space exploration require key technological elements that must provide sustainability, survivability and operational envelope in extreme environments, such as the high and low extremes in pressures and temperatures, ionizing radiations, chemical and/or physical corrosion, and hypervelocity particles. Advanced multifunctional materials enable revolutionary design schemes for future aerospace vehicles and structures for the extreme environments of NASA missions. Recent studies of nanocomposite materials have shown the potential for both structural integrity and multifunctional capabilities, such as sensing, actuating, health monitoring, radiation shielding, energy harvesting, thermal management, and thermal protection in extreme environments. After the advent of carbon nanotube (CNT) in 1991, scientists predicted that boron and nitrogen, carbons immediate neighbors on the periodic chart, might also form perfect nanotubes, namely boron nitride nanotubes (BNNTs). The discovery and progress of a new catalyst-free method for synthesizing highly crystalline, very long, and small diameter BNNTs under a high temperature and pressure (HTP) environment have enabled new applications for multifunctional materials. The white color BNNTs offer extraordinary properties including neutron radiation shielding, piezoelectricity, electrostriction, high thermal oxidative stability (>800C in air), not present in CNTs, as well as excellent mechanical strength and toughness, equivalent to CNTs. The characteristics of the BNNTs and their composites along with CNT composites are discussed in this presentation along with their potential aerospace applications in extreme environments.

Cheol Park

In-Situ Visualization of a Growing Brittle Crack in Aluminum Oxynitride Using Synchrotron X-Rays and the Double-Cleavage Drilled Compression Geometry

Brittle fracture is difficult to study in situ due to the speed of a growing crack and the often-catastrophic nature of failure in brittle materials. As a result, the influence of microstructural considerations, such as orientation, grain boundary locations, and strain field, on the crack path remains poorly understood. Presented in this study is a method addressing this knowledge gap, which utilizes the double-cleavage drilled compression geometry to achieve quasi-stable fracture in aluminum oxynitride (AlON). Synchrotron X-ray micro-computed tomography is used to characterize the crack shape and length, while high-energy diffraction microscopy provides information on the strains, orientations, and shapes of grains in the microstructure surrounding the crack tip. During testing, the crack grew in discrete and irregular jumps while the fracture toughness falls within reported ranges. The crack in AlON is found to have no greater tendency to crack intergranularly as compared to transgranularly, and grains which are cracked transgranularly do not display a trend in orientation or stress when compared to those around which the crack followed a grain boundary. The high resolution of the crack path and microstructural data provides a path forward for modeling and understanding 3D brittle fracture.

Gorske, Sara F.

Evaluating Fracture Behavior of Bioinspired Alumina-YSZ Composites through Static and Dynamic Mechanical Testing

Ceramic materials are known for their high hardness and strength but are limited by low toughness and sudden failure. Inspired by the microstructure of dental enamel, which features undulating rods that promote crack deflection and energy absorption, architected specimens were designed and manufactured. A bespoke ball-on-ring (BoR) testing apparatus measured the static biaxial rupture strength of these bioinspired materials. Additionally, impact testing with spherical steel projectiles assessed their behavior under dynamic conditions. Monolithic alumina specimens were compared to architected alumina reinforced with yttria-stabilized zirconia (YSZ) rods produced via direct ink write 3D printing. BoR tests revealed that monolithic alumina had a Weibull modulus of 10.53 and a characteristic strength of 372.3 MPa, while the composite specimens showed a Weibull modulus of 5.46 and a characteristic strength of 213.3 MPa. Although the composite failed at lower stresses and projectile velocities, it exhibited notable crack deflection and fracture resistance, with cracks being effectively interrupted by the rod inclusions. The composite specimens also resulted in fewer and larger fragments upon impact. Finite element simulations confirmed the effectiveness of the rod structures in enhancing fracture resistance.

Bioinspired materials

Erosion Behavior of Ti-hBN Multifunctional Coatings in A Custom-Made Planetary Test Rig at Extreme Lunar Temperatures

Spacecraft landings and takeoffs on the lunar surface, along with extreme temperature variations between day and night (-196 to 150° C), cause high-velocity dust impacts and erosion, resulting in the premature failure of structures. Ti/2 vol% hBN coatings were deposited using atmospheric (APS) and vacuum plasma spray (VPS) using cryo-milled powder feedstock to protect the structural components. The erosion performance of coatings at extreme lunar temperature regimes (-150 to 150° C) was evaluated in a custom-made planetary erosion test rig (PETR) at low (50 mph) and high impact velocities (250 mph). The mass loss of VPS coatings was reduced by 50% compared to the APS coatings and 40% compared to the Ti6Al4V substrate. The cryogenic temperature induces brittleness in the material, rendering it susceptible to extreme conditions of material loss. The particle impact-deformation behavior was captured using a high-speed camera to study the erosion mechanism. This analysis revealed chipping in substrates and brittle APS coatings, while particles rebounding and embedding were observed in VPS coatings. Energy calculations, aided by particle trajectory tracking from the high-speed camera, have conclusively shown that VPS coatings absorb 5–10% more energy than APS coatings during erosion tests. A modified erosion index was developed incorporating the fracture toughness and temperatures. New erosion models for brittle and ductile target materials are proposed for developing erosion-resistant material systems.

Abhijith Kunneparambil Sukumaran

Fracture Analysis of Cohesive Zone Models for Modeling Residual Stress Induced Delamination in Composite Structures

A fracture study of coupon-scale composite cylinders with embedded defects was conducted with an objective to assess and validate a modeling approach using two available cohesive material models. The study included experimental and simulation evaluations of initiation of crack growth and progression. Interrupted thermal experiments used acoustic emissions monitoring to identify the onset of crack progression during each cooling interval and ultrasonic scanning provided images of defect growth. Verification, validation, and uncertainty quantification (VVUQ) processes were performed in the assessment of the simulation predicted temperature at which crack propagation begins (quantity of interest). The Sobol sensitivity analysis identified the hoop direction elastic modulus in the carbon fiber reinforced polymer (CFRP) plies as the most influential parameter for simulations using both cohesive models, accounting for at least 70% of the variation in the temperature at crack propagation. The UQ temperature range for the Tvergaard-Hutchinson model was higher (more conservative) than the experimental acoustic measurement indicators of crack progression, while the temperature range for the Thouless-Parmigiani model enveloped the experimental data points for the primary defect size of 0.75 x 1 in. The simulations could not capture the stable crack growth indicated in the experiments. This is likely due to the models’ inability to represent anisotropic fracture toughness attributed to the structure of the orthotropic fiber weave in a woven composite laminate.

42 ENGINEERING

Microstructure, mechanical, and thermal properties of compositionally complex (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 ceramics

Novel compositionally complex borides, (Hf,Zr,Nb,Ti)B 2 and (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 , were fabricated using spark plasma sintering process. (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 exhibits a dual-phase microstructure, in which (Hf,Zr,Nb,Ti)B 2 is a primary phase with the hexagonal structure and LaB 6 is a secondary phase with a cubic structure. The mechanical properties of both (Hf,Zr,Nb,Ti)B 2 and (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 are comparable, with a combination of high hardness and moderate fracture toughness. Thermal diffusivity and conductivity of (Hf,Zr,Nb,Ti)B 2 are much lower than the individual transition metal borides but are significantly increased by the addition of LaB 6 . Herein, it is implied that the thermal properties of boride ceramics can be controlled through the appropriate design of principal metal element compositions.

borides

Review of European Microgravity Measurements

AA In a French/Russion cooperation, CNES developed a microgravity detection system for analyzing the Mir space station micro-g-environment for the first time. European efforts to characterize the microgravity (1/9) environment within a space laboratory began in the late seventies with the design of the First Spacelab Mission SL-1. Its Material Science Double Rack was the first payload element to carry its own tri-axial acceleration package. Even though incapable for any frequency analysis, the data provided a wealth of novel information for optimal experiment and hardware design and operations for missions to come. Theoretical investigations under ESA contract demonstrated the significance of the detailed knowledge of micro-g data for a thorough experiment analysis. They especially revealed the high sensitivity of numerous phenomena to low frequency acceleration. Accordingly, the payloads of the Spacelab missions D-1 and D-2 were furnished with state-of-the-art detection systems to ensure frequency analysis between 0.1 and 100 Hz. The Microgravity Measurement Assembly (MMA) of D-2 was a centralized system comprising fixed installed as well as mobile tri-axial packages showing real-time data processing and transmission to ground. ESA's free flyer EURECA carried a system for continuous measurement over the entire mission. All EURECA subsystems and experimental facilities had to meet tough requirements defining the upper acceleration limits. In a French/Russion cooperation, CNES developed a mi crogravity detection system for analyzing the Mir space station micro-g-environment for the first time. An approach to get access to low frequency acceleration between 0 and 0.02 Hz will be realized by QSAM (Quasi-steady Acceleration Measurement) on IML-2, complementary to the NASA system Spacelab Acceleration Measurement System SAMS. A second flight of QSAM is planned for the Russian free flyer FOTON.

H Hamacher

A Self‐Healing System for Polydicyclopentadiene Thermosets

Self-healing offers promise for addressing structural failures, increasing lifespan, and improving durability in polymeric materials. Implementing self-healing in thermoset polymers faces significant manufacturing challenges, especially due to the elevated temperature requirements of thermoset processing. To introduce self-healing into structural thermosets, the self-healing system must be thermally stable and compatible with the thermoset chemistry. This article demonstrates a self-healing microcapsule-based system stable to frontal polymerization (FP), a rapid and energy-efficient manufacturing process with a self-propagating exothermic reaction (≈200 °C). A thermally latent Grubbs-type complex bearing two N-heterocyclic carbene ligands addresses limitations in conventional G2-based self-healing approaches. Under FP's elevated temperatures, the catalyst remains dormant until activated by a Cu(I) co-reagent, ensuring efficient polymerization of the dicyclopentadiene (DCPD) upon damage to the polyDCPD matrix. The two-part microcapsule system consists of one capsule containing the thermally latent Grubbs-type catalyst dissolved in the solvent, and another capsule containing a Cu(I) coagent blended with liquid DCPD monomer. Using the same chemistry for both matrix fabrication and healing results in strong interfaces as demonstrated by lap-shear tests. In an optimized system, the self-healing system restores the mechanical properties of the tough polyDCPD thermoset. Self-healing efficiencies greater than 90% via tapered double cantilever beam tests are observed.

36 MATERIALS SCIENCE