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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Development of high Fe content squeeze cast 2A16 wrought Al alloys with enhanced mechanical properties at room and elevated temperatures

Highlights: • Applied pressure improved tensile properties at both room and elevated temperatures. • Experimental alloys meet the requirement of safety-critical component in automotive industry. • Increasing value of mechanical properties at elevated temperatures resulting from pressure decreases - Abstract: In this study, the evolution of iron-rich intermetallics and their effects on room and elevated-temperature tensile properties of gravity die cast and squeeze cast 2A16 wrought Al alloys with high Fe content of 0.5% after T7 heat treatment were investigated by various methods. Compared to gravity die-cast alloys, squeeze cast 2A16 wrought Al alloys showed superior tensile properties at both room and elevated temperatures, especially in terms of elongation. This can be attributed to refinement in grain size and iron-rich intermetallics, which decreased porosity and raised dispersoids in α(Al) matrix. However, the increase in mechanical properties at high temperature resulting from applied pressure was lower than that obtained at room temperature. The results were attributed to the refinement in grain size and the weakness of grain boundary at elevated temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Control on the homogeneity and crystallinity of Zn0.5Cd0.5S nanocomposite by different reaction conditions with high photocatalytic activity for hydrogen production from water

Highlights: • The effects of the various reaction conditions are investigated. • Different photocatalytic activities attributed to the different homogeneity and crystallinity of the nanoparticles. • Combination of good crystallinityand homogeneityresulted in an excellent photocatalytic activity. - Abstract: Zn{sub 0.5}Cd{sub 0.5}S nanoparticles with phase homojunctions were prepared by a one-step hydrothermal method with thioacetamide as sulfur source. The effects of the various reaction conditions, such as initial concentrations of Zn and Cd ions, initial content of sulfur source in the reaction mixture, and the temperature rising rate, are investigated. The photocatalytic activities for H{sub 2} evolution from water in the presence of sacrificial reagents of these Zn{sub 0.5}Cd{sub 0.5}S nanoparticles were significantly affected by the reaction conditions. These differences on the photocatalytic activities can be attributed to the different homogeneity and crystallinity of the nanoparticles prepared at different reaction conditions. A faster reaction rate leads to the formation of Zn{sub 0.5}Cd{sub 0.5}S nanoparticles with bad crystallinity, but good homogeneity. On the contrary, a slow reaction rate results in a bad homogeneity, but better crystallinity. Combination of good crystallinity and homogeneity in a Zn{sub 0.5}Cd{sub 0.5}S nanocomposite resulted in an excellent photocatalytic activity. The highest rate of H{sub 2} evolution achieved for these phase-homojunctions materials under visible-light irradiation (λ ≥ 420 nm) reached 1252.7 μmol h{sup −1} with an apparent quantum efficiency of 21.46% at 420 nm. The H{sub 2} evolution rate did not reduce distinctively in a continuous 15 hour test for H{sub 2} evolution, indicating an excellent stability for this material. This work not only demonstrates a facile method to produce highly active phase-homojunctions containing Zn{sub 0.5}Cd{sub 0.5}S solid solutions for photocatalytic hydrogen production from the perspective of controlling various reaction conditions, but also provides new insights into understanding the importance of the homogeneity and crystallinity for enhancing photocatalytic activity and stability of Zn{sub 0.5}Cd{sub 0.5}S solid solutions. It is expected that the strategies of modifying the homogeneity and crystallinity by controlling various reaction conditions can be extracted and used when designing other efficient and robust photocatalysts in the future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

The grain refinement mechanisms of various phases in shot-peened Nickel-Aluminum bronze (NAB) alloy

Highlights: • There exist two grain refinement mechanisms at the same time in the α phase. • The refinement of β' phase is attributed to the formation of dense and ordered nano twins. • The brittle strip-shape κ{sub iii} phases are fragmented after large deformation. • The κ{sub iv} and κ{sub ii} phases exhibit the twinning and dislocation deformation modes, separately. • The microhardness increases significantly owing to work hardening effect and grain refinement. - Abstract: In this study, coarse-grained Nickel-Aluminum bronze (NAB) alloy is subjected to shot-peening (SP) treatment, and the grain refinement mechanisms of various phases in shot-peened NAB alloy are investigated separately. The results show that severe deformation layers are produced on the surface. Meanwhile, refined grains with the average size below 100 nm are induced through SP treatment indicated by the results of X-ray diffraction (XRD) patterns. Various phases in NAB alloy including α, β' and three intermetallic phases (κ{sub ii}, κ{sub iii} and κ{sub iv}) display different grain refinement mechanisms. The grain refinement in the α phase involves dislocation segmentation in the precipitation-free zone and the twinning intersection in the precipitation zone. The formation of nanotwins by emitting partial dislocations at the grain boundary is found to be responsible for the grain refinement in the β' phase. As for the κ phases, the strip-shaped κ{sub iii} phases are fragmented after severe deformation, and the κ{sub iv} and κ{sub ii} phases exhibit the twinning and dislocation deformation modes, respectively. Also, the microhardness is significantly enhanced after SP treatment, which is mainly attributed to the work hardening effect and grain refinement.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Isothermal deformation and spheroidization mechanism of (TiB + La2O3)/Ti composites with different initial structures

Highlights: • Different initial microstructures were obtained through designed heat treatment. • Refined lamellar microstructures promoted dynamic recrystallization. • The spheroidization mechanism was attributed to dynamic recrystallization. • The micron TiB and submicron La{sub 2}O{sub 3} impeded dislocation movement. (TiB + La{sub 2}O{sub 3})/Ti composites with different initial structures were obtained through designed heat treatment. The isothermal deformation and spheroidization mechanisms of (TiB + La{sub 2}O{sub 3})/Ti composites with different initial structures were investigated. Initial structures were refined as the heat treatment temperature decreased. Simultaneously, the quenching and reheating resulted in finer α lamella colonies and α interlamellar spacing compared to the furnace cooling. The flow resistance of furnace cooled samples was lower than the quenched and reheated samples in terms of flow stress data. Following the deformation at 920 °C, the furnace cooled samples demonstrated lamellar α phase and partial spheroidized structure. Moreover, the spheroidization mechanism was similar to the boundary splitting model. Recrystallized grains of approximately 1 μm in diameter were obtained in the quenched and reheated sample following deformation at 920 °C. The spheroidization mechanism was attributed to the development of finer needles through quenching and reheating, as well as to subsequent dynamic recrystallization during the hot deformation. Additionally, the dislocation movement was blocked by the reinforcements on account of the composites with micron TiB and submicron La{sub 2}O{sub 3} during the hot deformation. Furthermore, the reinforcements could facilitate the dynamic recrystallization (DRX) of the α phase.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Observation of oxo-bridged yttrium in TiO2 nanostructures and their enhanced photocatalytic hydrogen generation under UV/Visible light irradiations

Highlights: • Synthesis of yttrium doped TiO{sub 2} nanoparticles (NPs) and nanorods (NRs) through a facile wet chemical method. • The doped Y ions are found to be oxo-bridged with the host TiO{sub 2} through Y-O-Ti like formation. • The NPs of Y:TiO{sub 2} showed increased photocatalytic hydrogen production efficiency. • The observed efficiency of NPs is attributed to their three-dimensional confinement. - Abstract: Yttrium doped TiO{sub 2} (Y:TiO{sub 2}) nanoparticles (NPs) and nanorods (NRs) are synthesized using facile wet chemical methods. Interestingly, the doped Y ions are found to be oxo-bridged with the host TiO{sub 2} through Y-O-Ti like formation as confirmed from their XRD and XPS studies. The photocatalytic hydrogen production efficiency of the synthesized nanostructures was studied under UV and visible light irradiations. The NPs of Y:TiO{sub 2} showed increased activity as compared to NRs. The observed efficiency of NPs is attributed to their three-dimensional confinement, where it facilitated a stronger oxo-bridging formation that improved the metal-to-metal charge transfer process, reducing the band gap and surface energies as compared to NRs. As investigated in this study, the oxo-bridging formation in the doped metal-oxide systems is relatively promising as this configuration largely favors the photocatalytic process by re-designing the charge separation and transfer processes as compare to the other conventional systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Highly stable and efficient hybrid perovskite solar cells improved with conductive polyanilines

Highlights: • MAPbI{sub 3} perovskite film has been fabricated and modified with polyanilines for highly stable and efficient solar cells. • For the C-PNAI modified perovskite solar cells, a PCE enhanced from 7.91% to 9.43% as the fill factor improved. • The C-PNAI surfaces of perovskite film assists in the hole transport to the conductive carbon in the device. • The improved stability is attributed to the –NH{sub 2}{sup +}– of C-PNAI cations on the surface of the perovskites. - Abstract: Methyl ammonium lead iodide (MAPbI{sub 3}) perovskite film has been fabricated and modified with conductive polyanilines (C- PANI) and demonstrated for highly stable and efficient solar cells. For the C-PANI modified perovskite solar cells (PSCs), the average short circuit current density increased by 13.8% compared with pristine perovskite film (i.e., from 15.9 to 18.1 mA/cm{sup 2}) and the fill factor also improved, eventually leading to a power conversion efficiency (PCE) enhancement from 7.91% to 9.43% with high reproducibility. The C-PANI acts as a scaffold for crystallization of the perovskite layer, and improves the perovskite photovoltaic performance and stability, attributed to the favorable interfacial interaction between –NH{sub 2}{sup +}– groups of C-PANI and I{sup −} of MAPbI{sub 3} perovskite. The C-PANI-rich surfaces of MAPbI{sub 3}/PNAI perovskite film may also assists in the hole transport to the conductive carbon in the device. This work demonstrates that C-PANI can enhance the PCE and stability of PSCs.

14 SOLAR ENERGY↗
DOE OSTI2018

In situ construction of conjugated polymer P3HT coupled hierarchical ZnO composite with Z-scheme enhanced visible-light photocatalytic activity

Highlights: • P3HT@H-ZnO photocatalysts were fabricated via a two-step solution method. • The P3HT@H-ZnO composite. exhibited high photodegredation of RhB under visible-light. • Enhanced photocatalytic activity attributed to the closely contacted interface between P3HT and H-ZnO and the matched band gap structure. • The fabricated P3HT@H-ZnO composite follow a Z-scheme mechanism rather than type II heterojunction. - Abstract: Conjugated polymer P3HT coupled with hierarchical ZnO (H-ZnO) photocatalysts were fabricated by a two-step solution method with assembling P3HT nanoparticles on the surface of H-ZnO micro-flowers. Optical properties revealed that the fabricated H-ZnO micro-flowers were rich in defects. The as-prepared P3HT@H-ZnO composite exhibited higher photocatalytic activity than H-ZnO for photocatalytic degradation of Rhodamine B (RhB) under visible light irradiation. The enhanced photocatalytic activity was attributed to the strengthened visible light absorption and the closely contacted interface between P3HT and H-ZnO. Based on the reactive species trapping experiments and band gap structure analysis, it can be identified that the effective separation and transfer of the photo-induced electron-hole pairs within the P3HT@H-ZnO composite follow a Z-scheme mechanism rather than type II heterojunction. The present work will provide a new insight to design Z-scheme photocatalysts with enhanced photocatalytic performance via metal-free polymers modification.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Intrinsic and extrinsic effects on the fracture toughness of ductile metallic glasses

The potential application of metallic glasses (MGs) as structural materials demands accurate measurements of their toughness and the understanding of the underlying factors affecting it. Currently, it is challenging to precisely measure the toughness of MGs, especially ductile MGs. Measured toughness values are widely scattered, even for MGs with identical compositions. That is attributed to the combined effect of intrinsic and extrinsic factors including processing, sample geometries, and loading conditions. A fundamental understanding of the influences of these elements is thus of great significance. In the present study, molecular dynamics simulations are performed to investigate the influence of intrinsic and extrinsic effects on the fracture toughness of CuZr MGs. In particular, focused is placed on the effects of cooling rate, notch shape and size, strain rate, and temperature. The results indicate that the fracture toughness of a MG scales with the cooling rate used to prepare it. This is attributed to increased free volume content generated at high cooling rates, which enhances plastic deformation and amplifies the associated energy dissipation during plastic deformation events. Fracture toughness also increases with the strain rate, arguably due to strain rate-induced crack extension delay. Overall, the results demonstrate that the largest fracture toughness are achieved when MG samples are fabricated at high cooling rates and subjected to high strain rate deformation. In addition, results suggest that the fracture toughness decreases with increasing temperature, due to the significant decrease in strength. Here, the correlations revealed between these crucial intrinsic and extrinsic parameters and the calculated MG fracture toughness support the development of a framework to understand the root of the discrepancies in the measurement of the toughness of MGs and provide insights into the design of tough MGs for structural applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Cryogenic mechanical behaviors of CrMnFeCoNi high-entropy alloy

The CrMnFeCoNi high-entropy alloy (HEA) exhibits higher yield strength, ultimate strength and ductility at lower temperature. To further clarify the effect of the testing temperature on microstructure evolution, in this study in-situ synchrotron-based high-energy X-ray diffraction tensile tests were carried out from 298 K down to 123 K. The enhanced yield strength of the alloy at cryogenic temperatures can be attributed to the greater lattice distortion prior to plastic deformation. Higher strain hardening rate leads to the simultaneously enhanced strength and ductility of the studied HEA below room temperature. Both dynamic Hall-Petch hardening (twinning) and dislocation hardening provide high work hardening capacity for this alloy during the plastic deformation at cryogenic temperatures. The increased dislocation density and nano-twins at cryogenic temperatures can be attributed to the decrease in the stacking fault energy as the deformation temperature decreases. These studies could provide an in-depth understanding for the strengthening mechanisms of the HEA in different temperature conditions and guide the exploration of HEAs with superb mechanical properties at cryogenic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Boron Nitride-Driven Strengthening of Aluminum Composites via Friction Stir Processing

Friction stir welding and processing (FSW/P) has emerged as an effective solid-state joining technique for fabricating metal matrix composites (MMCs), offering improved mechanical properties through refined microstructural evolution. In this study, an aluminum-boron nitride nanoparticle (Al-BNNP) composite was synthesized via FSW, and its indentation-based mechanical properties were systematically evaluated. Microhardness mapping across the weld cross-section revealed a progressive increase in hardness toward the stir zone (SZ), attributed to severe plastic deformation, dynamic recrystallization (DRX), and the reinforcing effect of BNNPs. Profilometry-based indentation plastometry (PIP) inferred yield strength (YS) demonstrates a 47.8% increase compared to the base metal (BM) and a 75% improvement compared to FSP pure aluminum reported in literature. This enhancement is attributed to strengthening mechanisms, including grain boundary pinning, load transfer, and increased dislocation density. The strain rate sensitivity (SRS) measurements at the nanoscale demonstrated a substantial decrease in the SZ, correlated with ultrafine grain structures and strong BNNP-matrix interactions. Activation volume analysis revealed a significant reduction in the SZ, suggesting that dislocation motion is increasingly restricted by dislocation-dislocation and dislocation-particle interactions. These findings suggest that incorporating BNNPs in FSW/P enables tailoring the microstructure without thermal degradation of the secondary particles, thereby significantly enhancing the mechanical performance of aluminum composites, particularly for structural applications in aerospace and automotive industries.

Aluminum↗
DOE OSTI2026

Influence of the as-built microstructure on the recrystallization of an additively manufactured Inconel939 Ni-based superalloy

This study investigates the influence of the as-built microstructure on the recrystallization (RX) behavior and mechanical properties of the Ni-based superalloy Inconel 939 produced by laser powder bed fusion (PBF-LB/M). Two distinct as-built microstructures were obtained by varying the hatch distance (h d ): a columnar, strongly textured condition (h d =50, termed h d 50) and an equiaxed, weakly textured condition (h d =70, termed h d 70)). Both were subjected to nine solution treatments combining three temperatures (1100, 1150, and 1200 °C) and three holding times (1, 4, and 8 h). Comprehensive microstructural characterization was conducted to assess grain morphology, texture, grain boundary character, dislocation density, and precipitate distribution. Recrystallization was found to be significantly slower than in cast counterparts, requiring higher temperatures and longer times for completion. The initial microstructure plays a decisive role: full RX was achieved only in hd70 specimens after treatment at 1200 °C for 8 h, whereas hd50 samples exhibited delayed and incomplete RX under identical conditions. This behavior is attributed to the finer grain size and higher fraction of high-angle grain boundaries in hd70, which promote recrystallization. Mechanical testing revealed that hd70 samples subjected to a 1200 °C/8 h treatment followed by standard double ageing show higher yield and tensile strengths across the investigated temperature range than both printed and cast Inconel939 processed under conventional conditions, albeit with slightly reduced ductility. The enhanced mechanical performance is attributed to the larger grain size, which limits grain boundary sliding. These results demonstrate the critical importance of controlling the as-built microstructure and tailoring post-processing strategies to optimize high-temperature performance of PBF-LB/M Inconel939.

Inconel939↗
DOE OSTI2022

Multicycle flash sintering of cubic Y 2 O 3 -stabilized ZrO 2 : An in situ energy dispersive synchrotron x-ray diffraction study with high temporal resolution

The current induced unit cell volume changes, (111) Bragg peak full width at half maximum (FWHM) and its integrated intensity in 8 % Y 2 O 3 stabilized ZrO 2 (8 %YSZ) solid state electrolyte was monitored during a triple-flash sintering experiment by in situ energy dispersive x-ray diffraction using a polychromatic synchrotron probe (max, photon energy 200 keV) with 2 second temporal resolution. The first spontaneous singularity in the unit cell volume (+0.54 %) was observed at 899 °C under 15 V/mm applied field intensity, which was associated with 13 mA/mm 2 current draw and an increase in density to 97 %. Following anelastic relaxation of the unit cell volume under open circuit conditions, the same applied field was applied twice in a row which resulted in additional induced singularities at 925 °C (+0.48 %) and 944 °C (+0.42 %). A floating baseline, which was above the thermal expansion baseline, was observed from 833 to 969 °C and was attributed to Joule heating. In conclusion, the singularity at 899 °C is associated with a sharp change in (111) FWHM and a 34 % decrease in integrated peak area that was attributed to changes in the distribution of oxygen vacancies and the changes in their concentration as induced by the applied field in the spontaneous transient stage of flash sintering.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic Diffusion, Segregation, and Grain Boundary Migration in Nickel-Based Alloys from Molecular Dynamics Simulations

Grain boundary diffusion and metal mobility in alloys control material performance in many applications and yet remain poorly understood at a mechanistic level. With advances in accessible time and length scales for computational molecular simulations, and recent force field developments, we now possess tools to help unravel those mechanisms. Using large-scale molecular dynamics simulations, here we examined vacancy-mediated diffusion processes in Ni-5Cr alloy with low and high-energy grain boundaries. We show that atomic diffusion inside the grain boundary plane is about four times higher than bulk diffusion, at any temperature, and exhibits a typical Arrhenius behavior with a very small energy barrier (0~.8 eV for Cr and 0.7 eV for Ni within 1300-1600 K). Additionally, the fastest diffusing species inverts; Cr diffusion was faster than Ni in the bulk but slower in the grain boundaries. This is attributed to the creation of high cohesive energy clusters of Cr at the grain boundary. Grain boundary migration was also observed to be temperature dependent and appears to be two times higher in the 5% Cr alloy than in pure Ni, highlighting the important role of the alloying element on grain boundary motion.

Simonnin, Pauline GN↗
DOE OSTI2022

Process and feedstock driven microstructure for laser powder bed fusion of 316L stainless steel

Here in the pursuit of improving additively manufactured (AM) component quality and reliability, fine-tuning critical process parameters such as laser power and scan speed is a great first step toward limiting defect formation and optimizing the microstructure. However, the synergistic effects between these process parameters, layer thickness, and feedstock attributes (e.g. powder size distribution) on part characteristics such as microstructure, density, hardness, and surface roughness are not as well-studied. In this work, we investigate 316L stainless steel density cubes built via laser powder bed fusion (L-PBF), emphasizing the significant microstructural changes that occur due to altering the volumetric energy density (VED) via laser power, scan speed, and layer thickness changes, coupled with different starting powder size distributions. This study demonstrates that there is not one ideal process set and powder size distribution for each machine. Instead, there are several combinations or feedstock/process parameter ‘recipes’ to achieve similar goals. This study also establishes that for equivalent VEDs, changing powder size can significantly alter part density, GND density, and hardness. Through proper parameter and feedstock control, part attributes such as density, grain size, texture, dislocation density, hardness, and surface roughness can be customized, thereby creating multiple high-performance regions in the AM process space.

316L stainless steel↗
DOE OSTI2018

Heat capacity of Mg 3 Sb 2 , Mg 3 Bi 2 , and their alloys at high temperature

The thermoelectric figure of merit reported for n-type Mg 3 (Sb,Bi) 2 compounds has made these materials of great engineering significance, increasing the need for accurate evaluations of their thermal conductivity. Thermal conductivity is typically derived from measurements of thermal diffusivity and determination of the specific heat capacity. The uncertainty in this method (often 10% or more) is frequently attributed to measurement of heat capacity such that estimated values are often more accurate. Inconsistencies between reported thermal conductivity of Mg 3 (Sb,Bi) 2 compounds may be attributed to the different values of heat capacity measured or used to calculate thermal conductivity. The high anharmonicity of these materials can lead to significant deviations at high temperatures from the Dulong-Petit heat capacity, which is often a reasonable substitute for measurements at high temperatures. Herein, a physics-based model is used to assess the magnitude of the heat capacity over the entire temperature range up to 800 K. The model agrees in magnitude with experimental low-temperature values and reproduces the linear slope observed in high-temperature data. Owing to the large scatter in experimental values of high-temperature heat capacity, the model is likely more accurate (within ±3%) than a measurement of a new sample even for doped or alloyed materials. It is found that heat capacity for the solid solution series can be simply described (for temperatures: 200K≤T≤800K ) by the polynomial equation: c p [Jg –1 K –1 ]=3NR/M W (1 + 1.3 × 10 –4 T – 4 × 10 3 T –2 ), where 3 NR = 124.71 J mol –1 K –1 , M W is the molecular weight [gmol –1 ] of the formula unit being considered, and T is temperature in K . This heat capacity is recommended to be a standard value for reporting and comparing the thermal conductivity of Mg 3 (Sb,Bi) 2 including doped or alloyed derivatives. Furthermore, a general form of the equation is given which can be used for other material systems

36 MATERIALS SCIENCE↗
DOE OSTI2020

In-situ measurement of irradiation behavior in LiNbO 3

In-situ measurement of LiNbO 3 based surface acoustic wave (SAW) crystal resonator device under irradiation was demonstrated and used to characterize the impact of radiation on physical properties of this material. The resonant frequency of the SAW device was monitored as the output power of the reactor was varied. Upon step increase of the reactor power, a gradual shift in the device’s resonant frequency was observed. This frequency shift initially exhibits a linear growth and eventually reaches an equilibrium value proportional to the reactor power. The observed behavior can be attributed to two competing processes: increase of temperature due to gamma heating or accumulation of irradiation induced defects. In both cases, the response is attributed to changes in the physical properties of LiNbO 3 , particularly the elastic constants. This demonstrated ability to measure materials properties under irradiation is attractive for development of sensors and performing materials science under irradiation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Chain flexibility and glass transition temperatures of poly(n-alkyl (meth)acrylate)s: Implications of tacticity and chain dynamics

The relationship between chain microstructure and glass transition temperature (T g ) is complicated for poly(alkyl methacrylate)s and poly(alkyl acrylate)s. Despite intensive studies, relationships between the structures of these polymers and their properties, including solution characteristics and T g , are still controversial. Solution properties, chain conformations, including Flory's characteristic ratio (C ∞ ), persistence length (l p ), and chain diameters, and T g are reported for series of poly(n-alkyl acrylate)s and poly(n-alkyl methacrylate)s having alkyl side chain lengths (n) ranging from 1 to 10 carbons in length, with uniform and well-characterized tacticities. Chain flexibilities of both series of polymers decrease as n increases, reflecting increased hindrances to rotation about backbone bonds as side chains become longer. Conversely, the T g s for both series of polymers decrease substantially as n increases, reflecting the greater side chain mobilities of long alkyl substituents. For shorter alkyl chain lengths, T g s for the poly(n-alkyl acrylate)s are much lower than for the corresponding poly(n-alkyl methacrylate)s, a difference which has been attributed in the past to the presumed reduced chain flexibility of polymethacrylates due to the presence of the α-methyl substituent. However, contrary to such expectations, C ∞ and l p values for these two series of polymers are nearly identical at a given n value, except for the longest n-alkyl substituents. Instead, the differences in T g may be attributed to the differences in tacticity of the two series – almost ideally atactic for the poly(n-alkyl acrylate)s but high in syndiotacticity for the poly(n-alkyl methacrylate)s. The T g s for the two series of polymers approach that of polyethylene at longer alkyl chain lengths. In addition, the effects of tacticity and chain dynamics on C ∞ , l p , and T g of poly(methyl methacrylate) is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dynamics of polymer segments, polymer chains, and nanoparticles in polymer nanocomposite melts: A review

The addition of nanoparticles (NPs) to a polymer matrix, forming a polymer nanocomposite (PNC), is known to alter the microscopic dynamic processes of both species which leads to unique macroscopic material properties of the PNC. Because the NPs and polymers have overlapping characteristic length, time, and energy scales, the interactions within these materials are complex and the dynamics are interrelated. In this review, we present an overview of experimental, simulation, and theoretical results that probe multi-scale polymer and nanoparticle dynamics in polymer nanocomposites and navigate the dense parameter space presented by these multicomponent systems. Although a variety of PNC systems are mentioned, we focus this discussion on linear thermoplastics filled with hard spherical or cylindrical NPs in the melt state. We begin by introducing PNCs, the dynamic processes within them, and the importance of dynamics for properties and processing. At the smallest length and time scales, we discuss segmental dynamics in PNCs, including the role of polymer attributes, NP attributes, and NP-polymer interactions. Then, we present measurements of collective motions and intermediate (Rouse) dynamics in various PNC materials. At longer length and time scales, we discuss polymer center-of-mass diffusion in PNCs with either spherical or anisotropic NPs. We then explore the dynamics of the NPs in PNCs and polymer melts, including theoretical predictions, simulation results, and experimental observations. Lastly, we note some of the remaining challenges in probing dynamics in PNC materials and fundamentally studying PNCs more generally.

36 MATERIALS SCIENCE↗