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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 109 records · Page 6

Theory of activated penetrant diffusion in viscous fluids and colloidal suspensions

We heuristically formulate a microscopic, force level, self-consistent nonlinear Langevin equation theory for activated barrier hopping and non-hydrodynamic diffusion of a hard sphere penetrant in very dense hard sphere fluid matrices. Penetrant dynamics is controlled by a rich competition between force relaxation due to penetrant self-motion and collective matrix structural (alpha) relaxation. In the absence of penetrant-matrix attraction, three activated dynamical regimes are predicted as a function of penetrant-matrix size ratio which are physically distinguished by penetrant jump distance and the nature of matrix motion required to facilitate its hopping. The penetrant diffusion constant decreases the fastest with size ratio for relatively small penetrants where the matrix effectively acts as a vibrating amorphous solid. Increasing penetrant-matrix attraction strength reduces penetrant diffusivity due to physical bonding. For size ratios approaching unity, a distinct dynamical regime emerges associated with strong slaving of penetrant hopping to matrix structural relaxation. A crossover regime at intermediate penetrant-matrix size ratio connects the two limiting behaviors for hard penetrants, but essentially disappears if there are strong attractions with the matrix. Activated penetrant diffusivity decreases strongly with matrix volume fraction in a manner that intensifies as the size ratio increases. We propose and implement a quasi-universal approach for activated diffusion of a rigid atomic/molecular penetrant in a supercooled liquid based on a mapping between the hard sphere system and thermal liquids. Calculations for specific systems agree reasonably well with experiments over a wide range of temperature, covering more than 10 orders of magnitude of variation of the penetrant diffusion constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules with a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. The present studies opened a viable route to achieve designer functional composite thin films via kinetic control.

36 MATERIALS SCIENCE↗

Lumping Techniques for Mixed Finite Element Diffusion Discretizations

We are interested in positivity preserving spatial discretizations applicable to arbitrary order mixed finite element spatial discretizations of the radiative diffusion equations. Though not guaranteed to yield strict positivity, matrix lumping is appealing as a method of increasing solution positivity because unlike ad hoc fixups or strictly non-negative, non-linear solution representations, matrix lumping keeps the mixed finite element diffusion equations as a linear system of equations. Self-lumping schemes have previously been shown to be a generalization of more traditional matrix lumping techniques. Self-lumping schemes restrict integration quadrature points to the interpolation points used to define interpolatory finite element basis functions. As shown previously, the positivity and order of accuracy of self-lumping schemes are directly related to the choice of finite element interpolation point. Here, we develop self-lumping schemes for arbitrary order, mixed finite element spatial discretizations of the diffusion equation in Cartesian geometry. After introducing several possible self-lumping schemes appropriate for mixed finite elements, we test the ability of each scheme to increase solution positivity relative to an unlumped discretization using a simple test problem designed to induce negative solutions, evaluating efficacy as a function of finite element order and finite element interpolation point type. The method of manufactured solutions is then used to evaluate order of convergence for promising self-lumping schemes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Xenon adsorption on geological media and implications for radionuclide signatures

Here, the detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isotherm measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures.

58 GEOSCIENCES↗

Silver photo-diffusion and photo-induced macroscopic surface deformation of Ge{sub 33}S{sub 67}/Ag/Si substrate

Ge-chalcogenide films show various photo-induced changes, and silver photo-diffusion is one of them which attracts lots of interest. In this paper, we report how silver and Ge-chalcogenide layers in Ge{sub 33}S{sub 67}/Ag/Si substrate stacks change under light exposure in the depth by measuring time-resolved neutron reflectivity. It was found from the measurement that Ag ions diffuse all over the matrix Ge{sub 33}S{sub 67} layer once Ag dissolves into the layer. We also found that the surface was macroscopically deformed by the extended light exposure. Its structural origin was investigated by a scanning electron microscopy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Predicting Fluid Flow Regime, Permeability, and Diffusivity in Mudrocks from Multiscale Pore Characterisation

In geoenergy applications, mudrocks prevent fluids to leak from temporary (H 2 , CH 4 ) or permanent (CO 2 , radioactive waste) storage/disposal sites and serve as a source and reservoir for unconventional oil and gas. Understanding transport properties integrated with dominant fluid flow mechanisms in mudrocks is essential to better predict the performance of mudrocks within these applications. In this study, small-angle neutron scattering (SANS) experiments were conducted on 71 samples from 13 different sets of mudrocks across the globe to capture the pore structure of nearly the full pore size spectrum (2 nm–5 μm). We develop fractal models to predict transport properties (permeability and diffusivity) based on the SANS-derived pore size distributions. The results indicate that transport phenomena in mudrocks are intrinsically pore size-dependent. Depending on hydrostatic pore pressures, transition flow develops in micropores, slip flow in meso- and macropores, and continuum flow in larger macropores. Fluid flow regimes progress towards larger pore sizes during reservoir depletion or smaller pore sizes during fluid storage, so when pressure is decreased or increased, respectively. Capturing the heterogeneity of mudrocks by considering fractal dimension and tortuosity fractal dimension for defined pore size ranges, fractal models integrate apparent permeability with slip flow, Darcy permeability with continuum flow, and gas diffusivity with diffusion flow in the matrix. This new model of pore size-dependent transport and integrated transport properties using fractal models yields a systematic approach that can also inform multiscale multi-physics models to better understand fluid flow and transport phenomena in mudrocks on the reservoir and basin scale.

36 MATERIALS SCIENCE↗

Repairing large cracks and reversing fatigue damage in structural metals

Self-healing materials represent a paradigm shift from traditional materials development, enabling intrinsic repair of functionality (such as strength) after a catastrophic failure as opposed to part replacement. Several healing mechanisms have been demonstrated in polymeric and ceramic materials, but few in metallic systems. This study demonstrates a novel liquid-assisted self-healing metal-matrix composite (MMC) designed to be capable of over 90% strength recovery after a healing cycle. The aluminum (Al)-based matrix is reinforced with continuous nickel-titanium (NiTi) shape-memory alloy (SMA) reinforcements. Using a tailored heat treatment for healing, a paired effect of crack closure from the SMA reinforcement and partial liquefaction of the matrix occurs. These effects result in a compressive force across the crack surface, and, coupled with increased diffusion rates from the liquefied matrix, produces consolidation and healing in the composite structure. This work provides experimental and computational evidence for the healing mechanism under both tensile and fatigue conditions.

36 MATERIALS SCIENCE↗

Diffusion-Model-Assisted Supervised Learning of Generative Models for Density Estimation

Here, we present a supervised learning framework of training generative models for density estimation. Generative models, including generative adversarial networks (GANs), normalizing flows, and variational auto-encoders (VAEs), are usually considered as unsupervised learning models, because labeled data are usually unavailable for training. Despite the success of the generative models, there are several issues with the unsupervised training, e.g., requirement of reversible architectures, vanishing gradients, and training instability. To enable supervised learning in generative models, we utilize the score-based diffusion model to generate labeled data. Unlike existing diffusion models that train neural networks to learn the score function, we develop a training-free score estimation method. This approach uses mini-batch-based Monte Carlo estimators to directly approximate the score function at any spatial-temporal location in solving an ordinary differential equation (ODE), corresponding to the reverse-time stochastic differential equation (SDE). This approach can offer both high accuracy and substantial time savings in neural network training. Once the labeled data are generated, we can train a simple, fully connected neural network to learn the generative model in the supervised manner. Compared with existing normalizing flow models, our method does not require the use of reversible neural networks and avoids the computation of the Jacobian matrix. Compared with existing diffusion models, our method does not need to solve the reverse-time SDE to generate new samples. As a result, the sampling efficiency is significantly improved. We demonstrate the performance of our method by applying it to a set of 2D datasets as well as real data from the University of California Irvine (UCI) repository.

97 MATHEMATICS AND COMPUTING↗

Interfacial reaction in SiC{sub f}/Ti-6Al-4V composite by using transmission electron microscopy

The interfacial reactions of continuous SiC fiber reinforced Ti-6Al-4V matrix composite (SiC{sub f}/Ti-6Al-4V composite) and continuous SiC fiber coated by C reinforced Ti-6Al-4V matrix composite (SiC{sub f}/C/Ti-6Al-4V composite) were investigated by using micro-beam electron diffraction (MBED) and energy disperse spectroscopy (EDS) on transmission electron microscopy (TEM). The sequence of the interfacial reactions in the as-processed and exposed at 900°C for 50h SiC{sub f}/Ti-6Al-4V composites can be described as SiC||TiC||Ti{sub 5}Si{sub 3} + TiC||Ti-6Al-4V and SiC||TiC||Ti{sub 5}Si{sub 3}||TiC||Ti{sub 5}Si{sub 3}||TiC||Ti{sub 5}Si{sub 3}||Ti-6Al-4V, respectively. Additionally, both in as-processed and exposed composites, Ti{sub 3}SiC{sub 2} and Ti{sub 3}Si are absent at the interfaces. For the SiC{sub f}/C/Ti-6Al-4V composite exposed at 900 °C for 50 h, the sequence of the interfacial reaction can be described as SiC||C||TiC{sub F}||TiC{sub C}||Ti-6Al-4V before C coating is completely consumed by interfacial reaction. When interfacial reaction consumes C coating completely, the sequence of the interfacial reaction can be described as SiC||TiC||Ti{sub 5}Si{sub 3}||TiC||Ti-6Al-4V. Furthermore, in SiC{sub f}/C/Ti-6Al-4V composite, C coating can absolutely prevent Si diffusion from SiC fiber to matrix. Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed. - Highlights: • We obtained the sequence of the interfacial reactions in the as-processed and exposed at 900 °C for 50 h SiC{sub f}/Ti-6Al-4 V composites as well as in the SiC{sub f}/C/Ti-6Al-4 V composite exposed at 900 °C for 50 h. • We verified that both in as-processed and exposed SiC{sub f}/Ti-6Al-4 V composites, Ti{sub 3}SiC{sub 2} and Ti{sub 3}Si are absent at the interfaces. • Carbon coating can absolutely prevent silicon diffusion from SiC fiber to matrix. • Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed.

36 MATERIALS SCIENCE↗

Distributed strain sensing using Bi-metallic coated fiber optic sensors embedded in stainless steel

Silica fiber optic sensors are resistant to corrosive environments and high temperatures, making them attractive candidates for harsh conditions found in nuclear and aerospace industries. Moreover, fibers can be deployed remotely for continuous measuring of spatially distributed temperatures and strains. Here, this study investigated embedding a Ni/Cu bi-metallic coated fiber in a stainless-steel 316 (SS316) matrix using laser powder bed fusion towards functionalizing metal components for site-specific health monitoring. The embedded fiber was continuously interrogated during controlled heating to 1000°C. The measured fiber strains were similar to the expected differential thermal strains between the fiber and the SS316 matrix, until divergent behavior was observed at temperatures >500°C. No debonding at the matrix–coating–fiber interfaces was observed during microscopy, but significant interactions between the coatings and matrix resulted in diffusion-driven chemistry variations and Kirkendall void formation. Applying the strain-lag theory revealed plastic behavior in the Ni coating at temperatures >500°C, limiting the strain transfer to the fiber at higher temperatures. It was estimated that the elastic modulus in the Ni coating had decreased from ~200 GPa at room temperature to below 40 GPa, starting at 600°C. The low elastic modulus above 600°C is within the margin of what the tangent modulus would be in the case of bilinear isotropic hardening. Regardless of the divergent strain transfer at higher temperatures, the fiber was exposed to the equivalent of 1.9 % engineering strain at 1000°C, but measured only a 0.7 % engineering strain due to the poor strain transfer. Although compensating for the plastic behavior of Ni proved challenging, the bonding of a brittle silica fiber to a metal matrix surviving to 1000°C invites potential iterations on coating material for future application. For example, the embedded fiber is sufficient for acoustic energy transfer, realizing high temperature distributed acoustic sensing.

36 MATERIALS SCIENCE↗

High-temperature chromium diffusion in austenitic stainless steel: Ab initio molecular dynamics simulations

Chromium self-diffusion through stainless steel (SS) matrix and along grain boundaries is an important mechanism controlling SS structural materials corrosion. For this work, Cr diffusion in austenitic SS was simulated using canonical ab initio molecular dynamics with realistic models of type-316 SS bulk, with and without Cr vacancies, and a low-energy Σ3 twin boundary typically observed at active corrosion sites. Cr self-diffusion coefficients at 750 and 850 °C calculated using Einstein’s diffusion equation are 4.2 × 10 –6 and 8.1 × 10 –6 Å 2 ps –1 in pristine bulk, 3.8 × 10 –3 and 5.5 × 10 –3 Å 2 ps –1 in bulk including Cr vacancies, and 9.5 × 10 –2 and 1.0 × 10 –1 Å 2 ps –1 at a Σ3[1 1 1]60° twin boundary.

36 MATERIALS SCIENCE↗

Microstructure and oxidation behavior of high strength steel AISI 410 implanted with nitrogen ion

Surface treatment by implantation with nitrogen-ion was performed on the commercial feritic high strength steel AISI 410 which is termed for high temperature applications. The aim of this research was focused on the surface modification to improve its high temperature oxidation property in the early stages. Ion implantation was carried out at acceleration energy of 100 KeV and ion current 10 mA for 30, 60 and 90 minutes. The samples were subjected to the high temperature oxidation test by means of thermogravimetry in a magnetic suspension balance (MSB) at 500 °C for 5 hours. The scanning electron microscopy (SEM), X-ray diffraction spectrometry (XRD) and Vickers Hardness measurement were used for sample characterization. The formation of ferro-nitride phase after implantation did not occur, however a thin layer considered to contain nitrogen interstitials was detected. The oxidation of both samples before and after implantation followed parabolic kinetics indicating inward growth of oxide scale characteristically due to diffusion of oxygen anions towards matrix surface. After oxidation test relativelly stable oxide scales were observed. Oxidation rates decreased proportionally with the increasing of implantation time due to the formation of oxide layer which is considered to be effectiv inhibitor for the oxygen diffusion.

36 MATERIALS SCIENCE↗

Immobile Pore-Water Storage Enhancement and Retardation of Gas Transport in Fractured Rock

The effect of immobile pore-water on gas transport in fractured rock has implications for numerical modeling of soil vapor extraction, methane leakage, gaseous CO 2 leakage from sequestration operations, radionuclide transport from underground nuclear explosions, and nuclear waste disposal. While the ability for immobile pore-water storage to effect gas transport has been recognized in the past, the details and specific scenarios leading to enhanced, retarded, or unaffected gas transport have not been explored. In this paper, we performed numerical investigations into the enhancement and retardation of gas transport due to immobile pore-water storage in order to identify implications for gas transport applications. To do this, we developed a numerical approach to model gas transport with a single-phase flow solution coupled to the advection–dispersion equation modified to account for immobile pore-water storage. Other than the immobility of pore water, the formulation contains all other physics included in two-phase formulations (advective and diffusive gas transport in fractures and rock matrix and dissolution in immobile pore water). The assumption of immobile pore water is valid here since for many applications involving transport of soluble gases in fractured rock, the rate of aqueous transport is insignificant compared to gas transport. We verify our modeling approach with analytical solutions of: (1) 1D gas diffusion, (2) 1D gas advection, (3) barometric pumping of a fracture, and (4) gas transport with uniform fracture flow and diffusion into the matrix. We account for pore-water storage in our model by implementing a kinetic formulation of gas dissolution wherein the dissolved (aqueous) phase is considered an immobile constituent. Using this formulation, we model the effect of dissolution rate and saturation on the retardation of gas transport during pure diffusion and pure advection. We also demonstrate that although it is commonly believed that pore-water storage will always enhance gas transport in fractures during oscillatory flow (e.g., during reversing pressure gradients such as barometric pumping cycles), our simulations indicate that this may not always be the case. Our numerical investigations indicate that scenarios with lower effective diffusion coefficients ( &#x2A85;<!-- <≈ --> 10 &#x2212;<!-- - --> 5 &#xA0;m 2 / s ) and lower dissolution coefficients (i.e., the dissolution diffusion coefficient) ( &#x2A85;<!-- <≈ --> 10 &#x2212;<!-- - --> 11 &#xA0;m 2 / s ) will result in enhanced gas transport. Other combinations of gaseous diffusion and dissolution coefficients result in delayed gas transport or insignificant effect on gas transport. Based on these results, and given the fact that the free-air diffusion coefficients for many gases are slightly above 10 &#x2212;<!-- - --> 5 &#xA0;m 2 / s (near the boundary of enhanced/non-enhanced gas transport), tortuosity would have to be significant for gas transport enhancement to occur. Similarly, if we consider the free-water diffusion coefficient of gases (around 10 &#x2212;<!-- - --> 9 &#xA0;m 2 / s for many gases of interest) to be a maximum bound for the effective dissolution coefficients (i.e., the rate of diffusion into the water away from the air/water interface will limit the dissolution rate), the effective dissolution coefficient would have to be at least 2 orders of magnitude less for enhanced gas transport to occur. Otherwise, pore-water storage will delay or have negligible effect on the gas transport. The results also indicate that the assumption of instantaneous equilibrium, often invoked in numerical codes for dissolution processes (i.e., dissolution coefficient is effectively infinite), will fail to accurately capture important details of soluble gas transport. Finally, the implication of our results is that gas breakthrough times in fractured rock during oscillatory flow may be highly dependent on the effective gaseous diffusion and dissolution coefficients.

58 GEOSCIENCES↗

Implications of Grain-Scale Mineralogical Heterogeneity for Radionuclide Transport in Fractured Media

The geological disposal of nuclear waste is based on the multi-barrier concept, comprising various engineered and natural barriers, to confine the radioactive waste and isolate it from the biosphere. Some of the planned repositories for high-level nuclear waste will be hosted in fractured crystalline rock formations. The potential of these formations to act as natural transport barriers is related to two coupled processes: diffusion into the rock matrix and sorption onto the mineral surfaces available in the rock matrix. Different in situ and laboratory experiments have pointed out the ubiquitous heterogeneous nature of the rock matrix: mineral surfaces and pore space are distributed in complex microstructures and their distribution is far from being homogeneous (as typically assumed by Darcy-scale coarse reactive transport models). We use a synthetically generated fracture–matrix system to assess the implications of grain-scale physical and mineralogical heterogeneity on cesium transport and retention. The resulting grain-scale reactive transport model is solved using high-performance computing technologies, and the results are compared with those derived from two alternative models, denoted as upscaled models, where mineral abundance is averaged over the matrix volume. In the grain-scale model, the penetration of cesium into the matrix is faster and the penetration front is uneven and finger-shaped. The analysis of the cesium breakthrough curves computed at two different points in the fracture shows that the upscaled models provide later first-arrival time estimates compared to the grain-scale model. The breakthrough curves computed with the three models converge at late times. These results suggest that spatially averaged upscaled parameters of sorption site distribution can be used to predict the late-time behavior of breakthrough curves but could be inadequate to simulate the early behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Unravelling the origins of shale nanoporosity using small-angle neutron scattering (SANS)

Hydrocarbon production from tight rocks is constrained by slow diffusion within the shale matrix, limited by small pore sizes and low permeability. The nanopore proportion and size distribution significantly influence matrix permeability, a key property for optimizing hydrocarbon recovery and supporting hydrogen production while minimizing environmental impacts. Small-angle neutron scattering (SANS) has been an important tool for exploring the characteristics and structure of shale nanopores. This study used SANS to analyze nanoporosity and pore size distribution (<100 nm) in tight rocks with varying compositions to determine the influence of rock heterogeneity on SANS measurements. Results showed that nanoporosity correlates with clay content, with the highest clay-rich shale (52.48 wt% clay) exhibiting 8.8 % nanoporosity. SANS also revealed more nanopores than traditional nitrogen adsorption measurements, affirming its ability to reflect bulk mineralogy and upholding the relevance of experimental findings using this technique to optimize field operational approaches.

03 NATURAL GAS↗

Aerosol detection efficiency in inductively coupled plasma mass spectrometry

We used an electrostatic size classification technique to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Moreover, we counted size-segregated particles with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10 -5 to 10 -11 . Free molecular heat and mass transfer theory was applied, but evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Finally, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulation of Nonequilibrium Dynamics on a Quantum Computer

We present a hybrid quantum-classical algorithm for the time evolution of out-of-equilibrium thermal states. Here, the method depends on classically computing a sparse approximation to the density matrix and, then, time-evolving each matrix element via the quantum computer. For this exploratory study, we investigate a time-dependent Ising model with five spins on the Rigetti Forest quantum virtual machine and a one spin system on the Rigetti 8Q-Agave quantum processor.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗