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At least 73 records · Page 4

Effects of a composite flame retardant system on the flame retardancy and mechanical performance of epoxy resin adhesive

Abstract A flame‐retarded epoxy resin (ER) adhesive with strong flame retardancy and adhesion performance was prepared. The coated ammonium polyphosphate (MFAPP), melamine (MEL), and organic montmorillonite (OMMT) were mixed to prepare a composite flame retardant. It was subsequently blended with a toughened ER thoroughly and then the mixture was cured with polyamide. The resultant ER adhesive thermosets achieved UL‐94 V‐0 rating during vertical burning test, and the limiting oxygen index value was as high as 31.6%. The shear strength of the ER adhesive was 27.9 MPa when 25 wt% MFAPP/MEL/OMMT was introduced. Compared with the pure adhesive, the flame retardant epoxy adhesive maintained outstanding adhesion performance because of the good compatibility between the composite flame retardant additives and the toughened ER adhesive. Cone calorimetry tests indicated that the release of heat and smoke were obviously declined with the incorporation of the composite flame retardant system in comparison to pure ER adhesive thermoset. The investigation of flame retardant mechanism revealed that the composite MFAPP/MEL/OMMT flame retardant system stimulated the generation of highly expanded, integral, and strong char layer and the formed char layer exerted superior insulation effect during combusiton. The present work provided an alternative approach to prepare flame retardant ER adhesive with the similar excellent adhesive performance.

Li, Sheng↗

All-polymer nanocomposites having superior strength, toughness and ultralow energy dissipation

Toughening polymers has attracted significant interest. Traditionally, polymer toughness is enhanced by constructing polymer networks or introducing sacrificial bonds into the chains between crosslink points. These strategies, though, introduce pronounced energy dissipation and associated heat, both of which are undesirable under long-term cyclic loading, for example at the interface of implants in the human body. By incorporating single-chain nanoparticles (SCNPs) into linear polymer chains to generate all-polymer nanocomposites (APNCs), we have been able to achieve high strength, high toughness with low energy dissipation. Using a combination of simulation and experimental results, we are advancing a “SCNPs effect” where tightly cross-linked SCNPs produce a modulus contrast to achieve strengthening and toughening. Benefitting from the soft interface, the penetrable and deformable SCNPs cause the surrounding polymer chains to move in concert, significantly reducing the interfacial friction to achieve low energy dissipation. The intramolecular cross-linking of the SCNPs and adhesion between the SCNPs and polymer matrix are critical for realizing such high-performance systems. Based on a Gaussian regression model and back propagation (BP) neural network, the mechanical strength can be predicted and is supported by simulations. Finally, the APNC concept described can be applied to elastomers and gels, broadening its utilization in high-cycle and low-dissipation applications, like soft robots, flexible sensors and cartilage replacements, and artificial heart valves.

36 MATERIALS SCIENCE↗

Tuneable phase behaviour and glass transition via polymerization-induced phase separation in crosslinked step-growth polymers

We report once limited to chain-growth polymerizations, fine control over polymerization-induced phase separation (PIPS) has recently been demonstrated in rubber-toughened thermoset materials formed through step-growth polymerizations. The domain length scales of these thermoset materials can be elegantly tuned by utilizing a binary mixture of curing agents (CAs) that individually yield disparate morphologies. Importantly, varying the composition of the binary mixture affects characteristics of the materials such as glass transition temperature and tensile behavior. Here, we establish a full phase diagram of PIPS in a rubber-toughened epoxy system tuned by a binary CA mixture to provide a robust framework of phase behaviour. X-Ray scattering in situ and post-PIPS is employed to elucidate the PIPS mechanism whereby an initial polymerization-induced compositional fluctuation causes nanoscale phase separation of rubber and epoxy components prior to local chain crosslinking and potential macrophase separation. We further demonstrate the universality of this approach by alternatively employing binary epoxy or binary rubber mixtures to achieve broad variations in morphology and glass transitions.

59 BASIC BIOLOGICAL SCIENCES↗

Structural and mechanical properties of monolayer amorphous carbon and boron nitride

Amorphous materials exhibit various characteristics that are not featured by crystals and can sometimes be tuned by their degree of disorder (DOD). Here, we report results on the mechanical properties of monolayer amorphous carbon (MAC) and monolayer amorphous boron nitride (maBN) with different DOD. The pertinent structures are obtained by kinetic-Monte-Carlo (kMC) simulations using machine-learning potentials (MLP) with density-functional-theory (DFT)-level accuracy. An intuitive order parameter, namely the areal fraction F x occupied by crystallites within the continuous random network, is proposed to describe the DOD. We find that F x captures the essence of the DOD: Samples with the same F x but different sizes and arrangements of crystallites, obtained using two distinct kMC procedures, have virtually identical radial distributions functions as well as bond-length and bond-angle distributions. Furthermore, by simulating the fracture process with molecular dynamics, we found that the mechanical responses of MAC and maBN before fracture are mainly determined by F x and are insensitive to the sizes and specific arrangements and to some extent the numbers and area distributions of the crystallites. The behavior of cracks in the two materials is analyzed and found to mainly propagate in meandering paths in the CRN region and to be influenced by crystallites in distinct ways that toughen the material. Furthermore, the present results reveal the relation between structure and mechanical properties in amorphous monolayers and may provide a universal toughening strategy for 2D materials.

2-dimensional systems↗

Making ultrastrong steel tough by grain-boundary delamination

Developing ultrahigh-strength steels that are ductile, fracture resistant, and cost effective would be attractive for a variety of structural applications. We show that improved fracture resistance in a steel with an ultrahigh yield strength of nearly 2 gigapascals can be achieved by activating delamination toughening coupled with transformation-induced plasticity. Delamination toughening associated with intensive but controlled cracking at manganese-enriched prior-austenite grain boundaries normal to the primary fracture surface dramatically improves the overall fracture resistance. As a result, fracture under plane-strain conditions is automatically transformed into a series of fracture processes in “parallel” plane-stress conditions through the thickness. The present “high-strength induced multidelamination” strategy offers a different pathway to develop engineering materials with ultrahigh strength and superior toughness at economical materials cost.

36 MATERIALS SCIENCE↗

On the strength and fracture toughness of an additive manufactured CrCoNi medium-entropy alloy

An additively manufactured (nominally equiatomic) CrCoNi alloy was processed by laser powder bed fusion (LPBF). At ambient temperatures (298 K), this medium-entropy alloy displayed a yield strength, σ y of ~691 ± 9 MPa, and an ultimate tensile strength, σ u of ~926 ± 15.2 MPa; at cryogenic temperatures (77 K), yield and tensile strengths increased respectively to σ y ~ 944 ± 6 MPa and σ u ~ 1382 ± 11 MPa. These strength levels are 57 and 44% higher than that of the wrought alloy, due to strengthening from the solidification cellular structures intertwined with dislocations in the LPBF CrCoNi. The crack-initiation fracture toughness, K JIc was measured to be ~183.7 ± 28 MPa√m at 298 K; this value marginally decreased by ~4% to ~176 ± 11 MPa√m at 77 K. These K JIc values of the LPBF CrCoNi were 11% and 35% lower than the wrought CrCoNi alloy at 298 K and 77 K, respectively. Here, the resistance to crack growth of the LPBF CrCoNi from its hierarchical micro- and meso-structures was evaluated using nonlinear-elastic fracture mechanics by measuring R-curve behavior in the form of the J-integral as a function of crack extension. The specific features of the hierarchical microstructures at different length-scales provide a basis for the strengthening and toughening properties of this additively manufactured medium-entropy alloy. This correlation between the deformation and the hierarchical microstructures at different length-scales may provide future guidance for improving the fracture toughness properties of medium-entropy alloys.

36 MATERIALS SCIENCE↗

3D Printable All-Polymer Epoxy Composites

Herein, 3D printable polymer-toughened epoxy resin composites are reported. Epoxy resins are widely used due to their excellent properties, such as thermal and chemical stability. However, their applications are limited by traditional mold-based manufacturing and their high brittleness. Mixtures of homopolymers, diblock copolymers, and triblock copolymers composed of poly(phenylene ether), poly(styrene), poly(methyl methacrylate), and poly(ethylene oxide) that self-assemble into micelles in the uncured resin are employed, providing a balance of structure, creep resistance, and flowability that enables 3D printing processing techniques and a retention of dimensional fidelity from the time of printing throughout the cured state. The precured ink is solid at room temperature and has strong shear-thinning behavior at elevated temperature for printing. As the printed parts cure, the polymer morphology evolves via reaction induced phase separation to yield finished composites with enhanced mechanical properties, including a 40% increase in the impact strength compared to the neat epoxy, without compromising thermal properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here, in this work, we discover that heterogeneous Ag + doping dramatically affects lithium intrusion into Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZO), a brittle solid electrolyte. Nanoscale Ag + doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag–Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag + incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag + -doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag + -doped LLZO surface exhibits improved lithium plating at >250 mA cm −2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

36 MATERIALS SCIENCE↗

Improving the Fracture Toughness and Ductility of Liquid-Phase Sintered WNiFe Tungsten Heavy Alloys by High-Temperature Annealing

Tungsten heavy alloys (WHAs) are candidates for use in fusion reactor divertors. Here, we characterize liquid-phase sintered WHAs with 90, 92.5, 95, and 97 (wt.%) tungsten (W), with a balance of a 0.7Ni–0.3Fe ductile phase. These WHAs show remarkable room temperature (RT) fracture toughness at the maximum load, K Jm , ranging from ≈ 38 to 107 MPa√m, compared to a monolithic W toughness of ≈ 8 MPa√m. In most cases, the fracture of WHAs occurs through stable crack tearing. However, the 97W WHA has the lowest toughness and fracture elastically in all but the smallest specimens. As lower Ni contents are desirable for fusion application, we explore the potential for improving the ductility and K Jm of WHAs using vacuum annealing at 1300 °C for 24 h. The microstructural observations reveal negligible changes in the WHA microstructure and constituent compositions. While annealing reduces the Vickers microhardness (HV), it does not significantly change the RT yield (σ y ) and ultimate (σ u ) strengths but results in beneficial increases in total elongation in the 95 and 97W WHAs by a factor of 2. RT tests on the precracked three-point-bend (3PB) bars show that annealing increases the K Jm of these WHAs, and in the case of the 97W WHA, the increase is from 42 to 92%, depending on the size of the specimen. Toughening is due to enhanced crack tip process zone microcracking and dilatation.

36 MATERIALS SCIENCE↗

Formation of Composite SiC/SiC Joints by Embedded Wire Chemical Vapor Deposition

The joining of ceramic monoliths or composites to date has primarily been limited to the formation of brittle monolithic joints using heterogeneous (dissimilar) materials, similar to brazing in metals. The development of a damage-tolerant joint layer by SiC fiber reinforcements is demonstrated here. Tube workpieces made of SiC fiber-SiC matrix composite are joined using a nonwoven SiC fiber mat densified by embedded wire chemical vapor deposition (EWCVD), creating a fiber-reinforced weld-like joint by homogeneous joining. EWCVD uses a localized heating method to target deposition and growth to the joint region specifically, while minimizing thermal damage to the surrounding composite tube material. X-ray computed tomography (XCT) is used to nondestructively characterize as-made joints for relative density, adhesion, and composition. In situ XCT analysis during mechanical testing revealed crack deflections in the bonding layer, which indicates a toughening mechanism typical of ceramic matrix composite phase. Gas permeation testing of these proof-of-concept composite joints identified relatively high leak rates in comparison to fully coated SiC/SiC composite tube workpieces. In conclusion, the novelty of the composite joining method and current technology challenges, including gas permeability, are discussed in comparison with traditional ceramic joints and materials.

SiC↗

Grain Boundary and Lattice Fracture Toughness of UO 2 Measured Using Small-Scale Mechanics

Small-scale mechanical testing has been used to isolate the properties of individual grain boundaries and regions of the lattice in undoped UO 2 polycrystals. Notched microcantilever specimens were prepared by focused ion beam milling and tested in bending. Fracture toughness values were calculated from finite element analysis of the sample geometry at fracture load using the J-integral method. Lattice and grain boundary fracture toughness values of 1.17 ± 0.16 MPa m 1/2 and 1.08 ± 0.08 MPa m 1/2 , respectively, were obtained. The similarity between the lattice and grain boundary fracture toughness values is consistent with the preference for transgranular room-temperature fracture in UO 2 . The grain boundary and lattice fracture toughness values also agree well with the toughness of dense polycrystals, which suggests that microstructural-scale toughening mechanisms are limited in such samples.

36 MATERIALS SCIENCE↗

Evading strength and ductility trade-off in an inverse nacre structured magnesium matrix nanocomposite

Mimicking nacre structure is an often-used strategy for developing materials which combine high strength and high toughness. Here, a novel strategy, named inverse nacre structure, is proposed where elongated and curled soft constituents are embedded in a matrix of hard constituent to form an ordered brick-and-mortar arrangement. This strategy is demonstrated in a particle reinforced metal matrix composite, using pure Mg as the soft phase and SiC nanoparticle reinforced Mg as the hard phase. In this work, the resulting nanocomposite yields high strength, and especially high tensile elongation which is five times that of the homogeneous counterpart. The superior comprehensive strengthening-toughening effect originates from the tailored inverse nacre structure which enables a stable microcrack-multiplication process by sufficiently promoting strain hardening so as to avoid any significant decrease in post-ultimate tensile strength. This strategy, while demonstrated here for the specific case of particle reinforced Mg, is not restricted to any particular material system but constitutes a generic pathway for the development of high-performance materials for engineering applications.

36 MATERIALS SCIENCE↗

Enhanced flexibility and thermal conductivity of HfC decorated carbon nanofiber mats

Future-generation spacecraft components allude discovery of novel materials that can withstand extreme environments (>2000 °C). The combined effect of ultra-high temperature ceramics (UHTCs) and carbon fibers (C f ) can satisfy the demanding requirements of aerospace applications. A novel, hybrid, and flexible hafnium carbide (HfC)-decorated carbon nanofiber (C nf ) mat was fabricated via electrospinning. Enhanced thermal stability of the flexible HfC decorated C nf over C nf can be elucidated from the 20-fold increment in thermal conductivity and the onset of degradation at higher temperatures (840 °C). Successful integration of multi-layered sandwich lattice using in-housed fabricated HfC decorated C nf showed retention of the fibrous structure even after extreme spark plasma sintering (SPS) process at 1850 °C. Fabricating a similar multi-layered structure using procured C f was unsuccessful due to bundled agglomeration and micron-sized fibers. High-load indentation suggests that HfC decorated C nf interlayer is stronger (~2.3 times) than the parent UHTC with no cracking at the interface. Compared with the HfC matrix, the indentation-damaged area at the interface reduced up to ~56% due to toughening mechanisms such as C nf , fiber pull-out and bridging. The synthesized HfC decorated Cnf mat is proposed as an ultra-thin filler material for joining similar or dissimilar UHTCs while maintaining similar chemistry and better mechanical integrity at the interface. Furthermore, the findings insinuate a new paradigm in designing hybrid and flexible ceramic-containing materials for thermal protection systems (TPS) of future-generation spacecraft components that can mitigate failure in extreme environments (>2000 °C).

36 MATERIALS SCIENCE↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain hardening magnesium-silicate-hydrate composites (SHMSHC) reinforced with short and randomly oriented polyvinyl alcohol microfibers

Magnesium-silicate-hydrate (M-S-H) cement has emerged as an alternative binder with potentially lower energy requirements and emissions. Due to the intrinsically low pH values of its matrix, however, normal steel reinforcement is not appropriate for M-S-H system. To toughen the matrix and to overcome the brittle nature of the material, a new strain hardening magnesium-silicate-hydrate composite (SHMSHC) is developed for the first time by incorporating 2 vol% short and randomly oriented polyvinyl alcohol (PVA) microfibers. The resulting SHMSHC exhibits significant strain hardening with a tensile strain capacity of more than 3%, a compressive strength beyond 50 MPa and a tensile strength of around 3 MPa. Remarkably, saturated multiple cracking with a tight crack width less than 10 μm invisible to the human naked eyes was observed. The newly developed SHMSHC addresses the fundamental challenge of M-S-H binder and is expected to widen possible application areas of M-S-H system.

36 MATERIALS SCIENCE↗

3D-printable engineered cementitious composites (3DP-ECC): Fresh and hardened properties

3D printing (3DP) is an emerging digital construction method for concrete materials. A major impediment to efficient 3D concrete printing (3DCP) is the need for steel reinforcement, the placement of which is incompatible with the 3DP process. Unlike plain concrete, ductile self-reinforced engineered cementitious composite (ECC) holds promise to remove the dependence on steel reinforcement. The objective of this research is to develop a 3D-printable ECC (3DP-ECC). The fresh rheological and hardened mechanical properties of 3DP-ECC are investigated. The robotically printed tensile specimens demonstrated the familiar multiple microcracking and strain-hardening behavior of conventionally cast ECC. Significant orthotropy is revealed in the compressive properties. The interface between printed layers is found to be toughened by a printed groove-tongue joint. The developed 3DP-ECC was used to print a twisted column with 150 layers, reaching a height of 1.5 m. This research lays the groundwork for efficient robotically 3D-printed structures of complex shapes.

36 MATERIALS SCIENCE↗

The effect of loading direction on the fracture behaviors of cortical bone at a dynamic loading rate

Here, the dynamic cracking processes in porcine cortical bone were visualized in real-time using the high-speed synchrotron X-ray phase-contrast imaging (PCI) technique in three osteon orientations: in-plane transverse, out-of-plane transverse and in-plane longitudinal. The dynamic flexural loading applied on the pre-notched bone specimens was introduced by a modified Kolsky compression bar. High-speed X-ray images of the entire loading events were documented with a high-speed camera. Three-dimensional X-ray micro-computed tomography was conducted to examine the intact microstructures and obtain the basic material properties of the bone material used for mechanical characterizations. The onset location, where crack initiated, and the subsequent direction, along which the incipient crack propagated, were measured quantitatively using the high-speed X-ray images and the latter was found dependent on the osteon direction significantly. The crack propagation velocities were dependent on crack extension over the entire crack path significantly for all the three directions while the initial velocity for in-plane longitudinal direction was lower than the other two directions. Straight-through crack paths were observed for in-plane longitudinal specimens while the cracks were deflected and twisted in the in-plane transverse direction. For out-of-plane transverse direction, the cracks follow paths with tortuosity fall in between the other two directions, showing a mixed mode of fractures of the former two extreme cases. The toughening mechanisms, visualized by the high-speed X-ray images, and the corresponding fracture toughness, evaluated in terms of fracture initiation toughness and crack growth resistance curve (R-curve), were also found significantly different among the three osteon directions, suggesting an overall transition from brittle to ductile-like fracture behaviors at the dynamic displacement rate (5.4 m/s) as the osteon orientation varies from in-plane longitudinal to out-of-plane transverse, and to in-plane transverse eventually.

42 ENGINEERING↗

Through-thickness fracture behavior of neutron-irradiated nuclear graphite NBG-17 Using X-ray micro-CT

Achieving precise control over crack propagation in nuclear graphite and conducting quantitative analysis remain challenging. In this study, the through-thickness fracture behavior of pristine and neutron-irradiated (700 °C, ∼7 dpa) NBG-17 nuclear graphite was investigated using split-disc testing coupled with micro-computed tomography (micro-CT). A notably lower number of micropores was observed in the neutron-irradiated specimen. The fracture toughness of neutron-irradiated NBG-17 was measured to be 1.45 MPa√m, compared to 1.17 ± 0.05 MPa√m for the pristine specimen. In both materials, cracks were found to initiate at the filler–binder interface, and often correlated with microstructural features such as pores and thermal cracks. Crack bridging and deflections emerged as the primary toughening mechanisms in both unirradiated and irradiated NBG-17. However, compared with the pristine specimen, the cracks in the neutron-irradiated specimen were more likely to grow trans granularly, resulting in less deflected crack paths. The reduced micro-porosity and strengthened filler–binder boundaries were considered to be the cause of the observed differences in crack morphologies. In conclusion, this study provides a qualitative analysis of the fracture behavior of neutron-irradiated nuclear graphite in the absence of radiolytic oxidation.

36 - MATERIALS SCIENCE↗