The concept of cryogenic fracturing is that a sharp thermal gradient developed by applying a cryogenic fluid on a rock surface causes a strong local tensile stress that initiates fractures. Prior field tests suggest that field application with special equipment rated for cryogenic temperatures may deliver potential benefits. The tests did not, however, identify the fracture mechanisms at work in downhole conditions. In this study, we present our laboratory designs and procedures developed for studying cryogenic fracturing mechanisms in a well environment, and examine typical data indicative of the performance of the system. The experimental apparatus and procedures were specifically designed to conduct cryogenic fracturing tests in specimens under confining stress, with integrated cryogen transport, measurements, and fracture characterization. A true-triaxial loading system was built to simulate reservoir stress levels and anisotropic stress application, and was designed to avoid thermal stresses in tests involving cryogen by arranging discrete components in an open chamber. To maximize thermal shock on the wellbore surface, tubing and wellhead are configured so that liquid nitrogen enters the borehole and flow out after contributing to thermal shock. The temperature at boreholes and along flow lines, borehole pressure, and liquid nitrogen consumption are monitored throughout treatments. Acoustic transmission and pressure-decay measurements are used to characterize fractures before and after the experiments. Breakdown tests performed on un-stimulated specimens and stimulated specimens compare breakdown pressures of the two groups and thus evaluate the performance of thermal fracturing. The laboratory design was able to effectively apply cryogenic stimulations to laboratory rock specimens. The characterization methods were able to capture fracture creation and rock property changes due to cryogenic fracturing.

Oriented microstructures are widely found in various biological systems for multiple functions. Such anisotropic structures provide low tortuosity and sufficient surface area, desirable for the design of high-performance energy storage devices. Despite significant efforts to develop supercapacitors with aligned morphology, challenges remain due to the predefined pore sizes, limited mechanical flexibility, and low mass loading. Herein, a wood-inspired flexible all-solid-state hydrogel supercapacitor is demonstrated by morphologically tuning the aligned hydrogel matrix toward high electrode-materials loading and high areal capacitance. The highly aligned matrix exhibits broad morphological tunability (47–12 µm), mechanical flexibility (0°–180° bending), and uniform polypyrrole loading up to 7 mm thick matrix. After being assembled into a solid-state supercapacitor, the areal capacitance reaches 831 mF cm−2 for the 12 µm matrix, which is 259% times of the 47 µm matrix and 403% times of nonaligned matrix. The supercapacitor also exhibits a high energy density of 73.8 µWh cm−2, power density of 4960 µW cm−2, capacitance retention of 86.5% after 1000 cycles, and bending stability of 95% after 5000 cycles. The principle to structurally design the oriented matrices for high electrode material loading opens up the possibility for advanced energy storage applications.

A laboratory study of cryogenic fracturing was performed to test its ability to improve oil/gas recovery from low-permeability reservoirs. Our objective is to develop well-stimulation technologies using cryogenic fluids [e.g., liquid nitrogen (LN)] to increase permeability in a large reservoir volume surrounding wells. The new technology has the potential to reduce formation damage caused by current stimulation methods and minimize or eliminate water usage. The concept of cryogenic fracturing is that a sharp thermal gradient (thermal shock) created at the surfaces of formation rocks by applying cryogenic fluid can cause strong local tensile stress and start fractures. We developed a laboratory system for cryogenic fracturing under true-triaxial loading, with LN-delivery/control and -measurement systems. The loading system simulates confining stresses by independently loading each axis up to approximately 5,000 psi on 888-in. cubes. Temperature in boreholes and at block surfaces and fluid pressure in boreholes were continuously monitored. Acoustic and pressure-decay measurements were obtained before and at various stages of stimulations. Cubic blocks (8 88-in.) of Niobrara shale, concrete, and sandstones were tested, and stress levels and anisotropies varied. Three schemes were considered: Gas fracturing without cryo-stimulation, gas fracturing after low-pressure cryogen flow-through, and gas fracturing after high-pressure cryogen flow-through. Results from pressure-decay tests show that LN stimulation clearly increases permeability, and repeated stimulations further increase the permeability. Acoustic velocities and amplitudes decreased significantly after cryo-stimulation, indicating fracture creation. In the gas fracturing without the stimulation, breakdown (complete fracturing) occurs suddenly without any initial leaking, and major fracture planes form along the plane containing principal-stress and intermediate-stress directions, as expected theoretically. However, in the gas fracturing after cryogenic stimulations, breakdown occurred gradually and with massive leaking because of thermal fractures created during stimulation. In addition, the major fracture direction does not necessarily follow the plane containing the principal-stress direction, especially at low confining-stress levels. In tests, we observed that cryogenic stimulation seems to disrupt the internal stress field. The increase in borehole temperature after stimulation affects the permeability of the specimen. When a stimulated specimen is still cold, it maintains high permeability because fractures remain open and local thermal tension is maintained near the borehole. When the rock warms back, fractures close and permeability decreases. In these tests, we have not used proppants. Overall, fractures are clearly generated by low- and high-pressure thermal shocks. The added pressure of the high-pressure thermal shocks helps to further propagate cryogenic fractures generated by thermal shock. Breakdown pressure is significantly lowered by LN stimulation, with observed breakdown-pressure reductions up to approximately 40%.

In cryogenic fracturing, a rock surface exposed to cryogenic fluids undergoes a large thermal gradient, and the resultant local tensile stress overcomes rock strength and initiates fractures. This study investigates the development of cracks generated from the cryogenic treatment of a borehole under no external confining stress on specimens. The experiments were performed on transparent PMMA specimens to observe fracture proliferation around boreholes. Liquid nitrogen was flowed through the boreholes to cool the borehole surface. The results show that initial fracture growth is characterized by abrupt starts and stops, and as the fracture propagates outward, the growth appears more continuous. In an early stage, horizontal/radial fractures and vertical fractures are the defining patterns. Horizontal fractures tend to be separated by a specific exclusion distance (i.e., spacing between cracks). While distinct horizontal/vertical fractures and exclusion distance manifest themselves at an early stage, fractures resulting from fracture interactions and curvatures can develop into complex shapes at later stages. Cryogenic thermal loading induces distinctively curved fractures. The tendency of curvature may prevent greater penetration. An increase in the borehole pressure during liquid nitrogen flow, however, can lessen fracture tortu-osity and facilitate radial propagation. A high flow pressure and rate are also advantageous in that they accelerate cooling and fracture propagation.

Leakage risk assessment is an inevitable procedure in permanent sequestration and storage of CO2 in deep saline aquifers and depleted oil and gas reservoirs, where the integrity of caprock is most critical. Low porosity and low permeability concrete cubes were employed as caprock analogs to investigate the supercritical CO2 injection-induced fracturing processes under true tri-axial stress conditions. A systematic experimental procedure, consisting of active acoustic emission measurement, pressure decay, injection pressure and temperature monitoring, fracture coloring, and gas fracturing, is formulated to qualitatively and quantitatively characterize the injection-induced fracturing processes and fracture morphology. Occurrence of injection-induced fracturing can be directly identified from peaks of borehole pressure profiles as well as sharp drops on temperature profiles due to CO2 expansion, but generally there was no fracture propagation plateau appearing for the 20 cm rock cubes with zero pore pressure. Acoustic wave signatures, including both waveform change and arrival time delay, can effectively capture the extension of induced fractures inside the opaque rock. Initiation and propagation of supercritical CO2 injection-induced fractures are highly dominated by the tri-axial stresses, following the general trend of continuum mechanics at high stress levels with large stress difference. As the stress difference decreases, induced fractures branch off in relatively arbitrary directions. For these supercritical CO2 injection-induced fracturing experiments, poroelastic mechanics model makes a decent fit with the measured breakdown pressure of the caprock analogs. Findings in this study are valuable for risk analysis and operation optimization of geological CO2 sequestration and storage as well as for CO2 fracturing design and implementation in shale and tight reservoirs.

Niobrara shale cubes of 20 cm from Colorado were employed to investigate gas and supercritical CO2 injection-induced fracturing in naturally fractured caprocks of deep aquifers/depleted reservoirs and fractured shale reservoirs. Under tri-axial stresses, gas or supercritical CO2 was injected into the center of the cubes to induce fracturing. Real-time pressure and temperature, acoustic wave, pressure decay, fracture coloring, and gas fracturing were used to characterize the fracturing process and fracture morphology. Without pore pressure, CO2 injection-induced fracturing occurred and completed instantly, accompanied by an evident temperature drop. Strongly bonded fractures barely affected transverse fracture propagation, whereas weakly bonded or open fractures arrested the injected fluid first and then allowed it to generate new fractures perpendicular to the minimum horizontal stress. Breakdown pressures for cubes with preexisting fractures using gas and supercritical CO2 are much lower than both poroelastic predictions and slick-water fracturing pressure, and some are even lower than the minimum horizontal stress. This is attributed to unconformable preexisting fractures and the low viscosity of CO2. Moreover, decreasing tri-axial stress levels and increasing stress differences tend to lower the breakdown pressure. This study is instructive for understanding and tackling geomechanical issues related to CO2 geological storage and fracturing of shale reservoirs.

Ice accumulation causes various problems in our daily life for human society. The daunting challenges in ice prevention and removal call for novel efficient antiicing strategies. Recently, photothermal materials have gained attention for creating icephobic surfaces owing to their merits of energy conservation and environmental friendliness. However, it is always challenging to get an ideal photothermal material which is cheap, easily fabricating, and highly photothermally efficient. Here, we demonstrate a low-cost, high-efficiency superhydrophobic photothermal surface, uniquely based on inexpensive commonly seen candle soot. It consists of three components: candle soot, silica shell, and polydimethylsiloxane (PDMS) brushes. The candle soot provides hierarchical nano/microstructures and photothermal ability, the silica shell strengthens the hierarchical candle soot, and the grafted low-surface-energy PDMS brushes endow the surface with superhydrophobicity. Upon illumination under 1 sun, the surface temperature can increase by 53 °C, so that no ice can form at an environmental temperature as low as -50 °C and it can also rapidly melt the accumulated frost and ice in 300 s. The superhydrophobicity enables the melted water to slide away immediately, leaving a clean and dry surface. The surface can also self-clean, which further enhances its effectiveness by removing dust and other contaminants which absorb and scatter sunlight. In addition, after oxygen plasma treatment, the surface can restore superhydrophobicity with sunlight illumination. The presented icephobic surface shows great potential and broad impacts owing to its inexpensive component materials, simplicity, ecofriendliness, and high energy efficiency.

Ice accumulation causes various problems in our daily life for human society. The daunting challenges in ice prevention and removal call for novel efficient antiicing strategies. Recently, photothermal materials have gained attention for creating icephobic surfaces owing to their merits of energy conservation and environmental friendliness. However, it is always challenging to get an ideal photothermal material which is cheap, easily fabricating, and highly photothermally efficient. Here, we demonstrate a low-cost, high-efficiency superhydrophobic photothermal surface, uniquely based on inexpensive commonly seen candle soot. It consists of three components: candle soot, silica shell, and polydimethylsiloxane (PDMS) brushes. The candle soot provides hierarchical nano/microstructures and photothermal ability, the silica shell strengthens the hierarchical candle soot, and the grafted low-surface-energy PDMS brushes endow the surface with superhydrophobicity. Upon illumination under 1 sun, the surface temperature can increase by 53 °C, so that no ice can form at an environmental temperature as low as -50 °C and it can also rapidly melt the accumulated frost and ice in 300 s. The superhydrophobicity enables the melted water to slide away immediately, leaving a clean and dry surface. The surface can also self-clean, which further enhances its effectiveness by removing dust and other contaminants which absorb and scatter sunlight. In addition, after oxygen plasma treatment, the surface can restore superhydrophobicity with sunlight illumination. The presented icephobic surface shows great potential and broad impacts owing to its inexpensive component materials, simplicity, ecofriendliness, and high energy efficiency.

During the past two decades, hydraulic fracturing has significantly improved oil and gas production from shale and tight sandstone reservoirs in the United States and elsewhere. Considering formation damage, water consumption, and environmental impacts associated with water-based fracturing fluids, efforts have been devoted to developing waterless fracturing technologies because of their potential to alleviate these issues. Herein, key theories and features of waterless fracturing technologies, including Oil-based and CO2 energized oil fracturing, explosive and propellant fracturing, gelled LPG and alcohol fracturing, gas fracturing, CO2 fracturing, and cryogenic fracturing, are reviewed. We then experimentally elaborate on the efficacy of liquid nitrogen in enhancing fracture initiation and propagation in concrete samples, and shale and sandstone reservoir rocks. In our laboratory study, cryogenic fractures generated were qualitatively and quantitatively characterized by pressure decay tests, acoustic measurements, gas fracturing, and CT scans. The capacity and applicability of cryogenic fracturing using liquid nitrogen are demonstrated and examined. By properly formulating the technical procedures for field implementation, cryogenic fracturing using liquid nitrogen could be an advantageous option for fracturing unconventional reservoirs.

Metal patterning via additive manufacturing has been phasing-in to broad applications in many medical, electronics, aerospace, and automotive industries. While previous efforts have produced various promising metal-patterning strategies, their complexity and high cost have limited their practical application in rapid production and prototyping. Herein, a one-step gold printing technique based on anion-assisted photochemical deposition (APD), which can directly print highly conductive gold patterns (1.08 × 10⁷ S m^-1 ) under ambient conditions without post-annealing treatment, is introduced. Uniquely, the APD uses specific ion effects with projection lithography to pattern Au nanoparticles and simultaneously sinter them into tunable porous gold structures. The significant influence of kosmotropic or chaotropic anions in the precursor ink on tuning the morphologies and conductivities of the printed patterns by employing a series of different ions, including Cl^- ions, in the printing process is presented. Additionally, the resistance stabilities and the electrochemical properties of the APD-printed gold patterns are carefully investigated. The high conductivity and excellent conformability of the printed Au electrodes are demonstrated with reliable performance in electrophysiological signal delivery and acquisition for biomedical applications. This work exploits the potential of photochemical-deposition-based metal patterning in flexible electronic manufacturing.