Effects of Freeze/Thaw Cycles and Gas Purging Method on Polymer Electrolyte Membrane Fuel Cells

At subzero temperature, the startup capability and performance of polymer electrolyte membrane fuel cell (PEMFC) deteriorates markedly. The object of this work is to study the degradation mechanism of key components of PEMFC-membrane-electrode assembly (MEA) and seek feasible measures to avoid degradation. The effect of freeze/thaw cycles on the structure of MEA is investigated based on porosity and SEM measurement. The performance of a single cell was also tested before and after repetitious freeze/thaw cycles. The experimental results indicated that the performance of a PEMFC decreased along with the total operating time as well as the pore size distribution shifting and micro configuration changing. However, when the redundant water had been removed by gas purging, the performance of the PEMFC stack was almost resumed when it experienced again the same subzero temperature test. These results show that it is necessary to remove the water in PEMFCs to maintain stable performance under subzero temperature and gas purging is proved to be the effective operation.

Typical Soft–Sediment Deformation Structures Induced by Freeze/Thaw Cycles: A Case Study of Quaternary Alluvial Deposits in the Northern Qiangtang Basin, Tibetan Plateau

With the objective of establishing a distinction between deformation structures caused by freeze/thaw cycles and those resulting from seismic activity, we studied three well–exposed alluvial deposits in a section at Dogai Coring, northern Qiangtang Basin, Tibetan Plateau. Deformation is present in the form of plastic structures(diapirs, folds and clastic dykes), brittle structures(micro–faults) and cryogenic wedges. These soft–sediment deformation features(except the micro–faults) are mainly characterized by meter–scale, non–interlayered, low–speed and low–pressure displacements within soft sediments, most commonly in the form of plastic deformation. Taking into account the geographic setting, lithology and deformation features, we interpret these soft–sediment deformation features as the products of freeze/thaw cycles, rather than of earthquake–induced shock waves, thus reflecting regional temperature changes and fluctuations of hydrothermal conditions in the uppermost sediments. The micro–faults(close to linear hot springs) are ascribed to regional fault activity;however, we were unable to identify the nature of the micro–faults, perhaps due to disturbance by subsequent freeze/thaw cycles. This study may serve as a guide to recognizing the differences between deformation structures attributed to freeze/thaw cycles and seismic processes.

Significant Improvement of Mechanical Properties for Polyvinyl Alcohol Film Prepared from Freeze/Thaw Cycled Gel

The mechanical properties of polyvinyl alcohol (PVA) films prepared by evaporating water from freeze/thaw cycled gel were investigated as a function of the number of freeze/thaw cycles. The maximum stress of the PVA film prepared by freeze/thaw cycling was larger than that prepared without the freeze/thaw cycle process. The largest maximum stress was 46.2 MPa for a film prepared with 10 freeze/thaw cycles, which was twice as large as that for a cast PVA film without freeze/thaw cycling (22.3 MPa). This is due to the formation of small crystallites during the freeze/thaw cycle process. Furthermore, when the film was annealed at 130°C, the maximum stress was as high as 181 MPa which was comparable to that for PVA films prepared using additives. The crystallinity is not the main factor that determines the maximum stress for either the non-annealed or annealed freeze/thaw cycled films, but the glass transition temperature is well correlated with the maximum stress, irrespective of the annealing process. This is due to the different molecular morphology;the non-annealed freeze/thaw cycled film consists of many small crystallites, but the annealed film consists of larger crystallites formed during the annealing process.

Effects of freeze-thaw cycles on sandstone in sunny and shady slopes

A growing rock engineering activity in cold regions is facing the threat of freeze-thaw(FT)weathering,especially in high mountains where the sunny-shady slope effects strongly control the difference in weathering behavior of rocks.In this paper,an investigation of the degradation of petrophysical characteristics of sandstone specimens subjected to FT cycle tests to simulate the sunny-shady slope effects is presented.To this aim,non-destructive and repeatable testing techniques including weight,ultrasonic waves,and nuclear magnetic resonance methods on standard specimens were performed.For the sunny slope specimens,accompanied by the enlargement of small pores,100 FT cycles caused a significant decrease in P-wave velocity with an average of 23%,but a consistent rise of 0.18%in mass loss,34%in porosity,67%in pore geometrical mean radius,and a remarkable 14.5-fold increase in permeability.However,slight changes with some abnormal trends in physical parameters of the shady slope specimens were observed during FT cycling,which can be attributed to superficial granular disaggregation and pore throat obstruction.Thermal shocks enhance rock weathering on sunny slopes during FT cycles,while FT weathering on shady slopes is restricted to the small pores and the superficial cover.These two factors are primarily responsible for the differences in FT weathering intensity between sunny and shady slopes.The conclusions derived from the interpretation of the experimental results may provide theoretical guidance for the design of slope-failure prevention measures and the selection of transportation routes in cold mountainous regions.

Quantification of the concrete freeze–thaw environment across the Qinghai–Tibet Plateau based on machine learning algorithms

The reasonable quantification of the concrete freezing environment on the Qinghai–Tibet Plateau(QTP) is the primary issue in frost resistant concrete design, which is one of the challenges that the QTP engineering managers should take into account. In this paper, we propose a more realistic method to calculate the number of concrete freeze–thaw cycles(NFTCs) on the QTP. The calculated results show that the NFTCs increase as the altitude of the meteorological station increases with the average NFTCs being 208.7. Four machine learning methods, i.e., the random forest(RF) model, generalized boosting method(GBM), generalized linear model(GLM), and generalized additive model(GAM), are used to fit the NFTCs. The root mean square error(RMSE) values of the RF, GBM, GLM, and GAM are 32.3, 4.3, 247.9, and 161.3, respectively. The R^(2) values of the RF, GBM, GLM, and GAM are 0.93, 0.99, 0.48, and 0.66, respectively. The GBM method performs the best compared to the other three methods, which was shown by the results of RMSE and R^(2) values. The quantitative results from the GBM method indicate that the lowest, medium, and highest NFTC values are distributed in the northern, central, and southern parts of the QTP, respectively. The annual NFTCs in the QTP region are mainly concentrated at 160 and above, and the average NFTCs is 200 across the QTP. Our results can provide scientific guidance and a theoretical basis for the freezing resistance design of concrete in various projects on the QTP.

Surface crack evolution patterns in freeze-thaw damage of fissured rock bodies

To explore the effects of freeze‒thaw cycles on the mechanical properties and crack evolution of fissured sandstone,biaxial compression experiments were carried out on sandstone subjected to freeze‒thaw cycles to characterize the changes in the physical and mechanical properties of fissured sandstone caused by freeze‒thaw cycles.The crack evolution and crack change process on the surface of the fissured sandstone were recorded and analysed in detail via digital image technology(DIC).Numerical simulation was used to reveal the expansion process and damage mode of fine-scale cracks under the action of freeze‒thaw cycles,and the simulation results were compared and analysed with the experimental data to verify the reliability of the numerical model.The results show that the mass loss,porosity,peak stress and elastic modulus all increase with increasing number of freeze‒thaw cycles.With an increase in the number of freeze‒thaw cycles,a substantial change in displacement occurs around the prefabricated cracks,and a stress concentration appears at the crack tip.As new cracks continue to sprout at the tips of the prefabricated cracks until the microcracks gradually penetrate into the main cracks,the displacement cloud becomes obviously discontinuous,and the contours of the displacement field in the crack fracture damage area simply intersect with the prefabricated cracks to form an obvious fracture.The damage patterns of the fractured sandstone after freeze‒thaw cycles clearly differ,forming a symmetrical"L"-shaped damage pattern at zero freeze‒thaw cycles,a symmetrical"V"-shaped damage pattern at 10 freeze‒thaw cycles,and a"V"-shaped damage pattern at 20 freeze‒thaw cycles.After 20 freeze‒thaw cycles,a"V"-shaped destruction pattern and"L"-shaped destruction pattern are formed;after 30 freeze‒thaw cycles,an"N"-shaped destruction pattern is formed.This shows that the failure mode of fractured sandstone gradually becomes more complicated with an increasing number of freeze‒thaw cycles.The effects of freeze‒thaw cycles on the direction and rate of crack propagation are revealed through a temperature‒load coupled model,which provides an important reference for an in-depth understanding of the freeze‒thaw failure mechanisms of fractured rock masses.

Change in Grain-Size Composition of Lignite under Cyclic Freezing-Thawing and Wetting-Drying

The paper presents the change in grain-size composition of lignite under cyclic freezing-thawing (FTC) and wetting-drying (WDC). The article shows that in the spring and autumn periods the lignites can be subjected to repeated freezing-thawing and wetting-drying, which determines the possibility of changing their grain-size composition and structure. Experimental studies in laboratory conditions on the influence of cyclic freezing-thawing (FTC) and wetting-drying (WDC) on the quality indicators of lignites have been carried out, their granulometric (fractional) composition has been studied. Freezing-thawing cycle conditions are as follows (FTC): minimum exposure temperature: -20°C;maximum: +5°C;relative humidity: 30%;number of processing cycles: 3. Wetting-drying cycles are as follows (WDC): drying temperatures are +20, +40, +60, +80°C, drying time 90 minutes, the coals are further subjected to rain (soaking) for a period of water saturation to humidity of 30% - 40% and dry again. The number of wetting-drying cycles is 3 times. The tests have revealed the destructive effects of FTC and WDC on the samples of lower metamorphic grade coal, and the cycles of wet-dry lead to the much higher yield of fine sizes (-6+0;-13+0 mm) than the cycles of freeze-thaw. Furthermore, it is found that the increase in the yield of fines depends on the heating temperature: coal disintegration proceeds more intensively at a higher temperature of drying.

Diurnal freeze/thaw cycles of the ground surface on the Tibetan Plateau

The exchange of energy and water between the lithosphere and atmosphere mainly takes place at the ground surface. Therefore, freeze/thaw condition at the ground surface is an important factor in ex- amining the interactions between the land surface and atmosphere. Based on the observation data obtained by CEOP/CAMP-Tibet, the diurnal freeze/thaw cycles of the ground surface near Naqu, central Tibetan Plateau was preliminarily analyzed. The results show that the surface layer was completely frozen for approximately one month. However, the time that the ground surface experienced diurnal freeze/thaw cycles was about 6 months. The high frequency of freeze/thaw cycles at the ground surface significantly influences water and energy exchanges between ground and atmosphere over half a year. The interaction processes between the ground and atmosphere under different soil conditions (such as complete thaw, complete freeze and diurnal freeze/thaw cycles) are issues worthy of further examina- tion.

Experimental study of dynamic resilient modulus of subgrade soils under coupling of freeze–thaw cycles and dynamic load

Although the dynamic properties of subgrade soils in seasonally frozen areas have already been studied, few researchers have considered the influence of shallow groundwater during the freeze–thaw(F–T) cycles. So a multifunctional F–T cycle system was developed to imitate the groundwater recharge in the subgrade during the freezing process and a large number of dynamic triaxial experiments were conducted after the F–T cycles. Some significant factors including the F–T cycle number, compaction degree, confining pressure, cyclic deviator stress, loading frequency, and water content were investigated for the resilient modulus of soils. The experimental results indicated that the dynamic resilient modulus of the subgrade was negatively correlated with the cyclic deviator stress, F–T cycle number, and initial water content, whereas the degree of compaction, confining pressure, and loading frequency could enhance the resilient modulus. Furthermore, a modified model considering the F–T cycle number and stress state was established to predict the dynamic resilient modulus. The calculated results of this modified model were very close to the experimental results. Consequently, calculation of the resilient modulus for F–T cycles considering the dynamic load was appropriate. This study provides reference for research focusing on F–T cycles with groundwater supply and the dynamic resilient moduli of subgrade soils in seasonally frozen areas.

Effect of freeze-thaw cycles on uniaxial mechanical properties of cohesive coarse-grained soils

Freeze-thaw cycles are closely related to the slope instability in high-altitude mountain regions. In this study, cohesive coarse-grained soils were collected from a high-altitude slope in the Qinghai–Tibet Plateau to study the effect of cyclic freeze-thaw on their uniaxial mechanical properties. The soil specimens were remolded with three dry densities and three moisture contents. Then, after performing a series of freeze-thaw tests in a closed system without water supply, the soil specimens were subjected to a uniaxial compression test. The results showed that the stress-strain curves of the tested soils mainly performed as strain-softening. The softening feature intensified with the increasing dry density but weakened with an increase in freeze-thaw cycles and moisture content. The uniaxial compressive strength, resilient modulus, residual strength and softening modulus decreased considerably with the increase of freeze-thaw cycles. After more than nine freeze-thaw cycles, these four parameters tended to be stable. These parameters increased with the increase of dry density and decreased with the increasing moisture content, except for the residual strength which did not exhibit any clear variation with an increase in moisture content. The residual strength, however, generally increased with an increase in dry density. The soil structural damage caused by frozen water expansion during the freeze-thaw is the major cause for the changes in mechanical behaviors of cohesive coarse-grained soils. With results in this study, the deterioration effect of freeze-thaw cycles on the mechanical properties of soils should be considered during the slope stability analysis in high-altitude mountain regions.

Effects of Freeze–thaw Cycles on Soil Mechanical and Physical Properties in the Qinghai–Tibet Plateau

Extreme freeze-thaw action occurs on the Qinghai-Tibet Plateau due to its unique climate resulting from high elevation and cold temperature.This action causes damage to the surface soil structure, as soil erosion in the Qinghai-Tibet Plateau is dominated by freeze-thaw erosion.In this research,freezing–thawing process of the soil samples collected from the Qinghai–Tibet Plateau was carried out by laboratory experiments to determinate the volume variation of soil as well as physical and mechanical properties, such as porosity, granularity and uniaxial compressive strength, after the soil experiences various freeze–thaw cycles.Results show that cohesion and uniaxial compressive strength decreased as the volume and porosity of the soil increased after experiencing various freeze–thaw cycles, especially in the first six freeze–thaw cycles.Consequently, the physical and mechanical properties of the soil were altered.However, granularity and internal friction angle did not vary significantly with an increase in the freeze–thaw cycle.The structural damage among soil particles due to frozen water expansion was the major cause of changes in soil mechanical behavior in the Qinghai–Tibet Plateau.

Effects of freeze-thaw cycle on engineering properties of loess used as road fills in seasonally frozen ground regions,North China

Compacted loess is widely used as fills of road embankments in loess regions of northern China.Generally, densely-compacted loess can satisfy the requirements of embankment strength and postconstruction deformation. However, uneven subsidence, pavement cracks and other related damages can affect the integrity of loess subgrade after several years of operation,and even cause some hazards, especially in North China, where the strong freeze-thaw erosion occurs. In this study, cyclic freeze-thaw tests for both densely and loosely compacted loess samples were performed to determine the variation in engineering properties such as volume, void ratio, collapsible settlement,microstructure, and the related mechanisms were addressed. The experimental results showed that an obvious water migration and redistribution occurred within the samples during freeze-thaw cycles. Ice lenses and fissures could be identified in the upper frozen layers of the samples. After freeze-thaw cycles,the dry densities of the upper layers of samples changed significantly due to strong freeze-thaw erosion. The dry densities decreased for the dense sample and increased for the loose sample. It can be found that dense samples become loose, while loose samples became dense with the increasing number of freeze-thaw cycles. Their related void ratios changed reversely. Both void ratios tended to fall into a certain range, which verified the concept of a residual void ratio proposed by Viklander. The loosening process of densely compacted samples involves the formation of large pores, volume increase and density reduction as well as the related changes in mechanical properties because freeze-thaw cycles may be important contribution to problems of loess road embankments.Adverse effects of freeze-thaw cycles, therefore,should be taken into account in selecting loess parameters for the stability evaluation of road embankment in seasonally frozen ground regions.

Simulated change in the near-surface soil freeze/thaw cycle on the Tibetan Plateau from 1981 to 2010

The near-surface freeze/thaw cycle in cold regions plays a major role in the surface energy budget,hydrological activity,and terrestrial ecosystems.In this study,the Community Land Model,Version 4 and a suite of high-resolution atmospheric data were used to investigate the changes in the near-surface soil freeze/thaw cycle in response to the warming on the Tibetan Plateau from1981 to 2010.The in situ observations-based validation showed that,considering the cause of scale mismatch in the comparison,the simulated soil temperature,freeze start and end dates,and freeze duration at the near-surface were reasonable.In response to the warming of the Tibetan Plateau at a rate of approximately 0.44°C decade-1,the freeze start-date became delayed at an area-mean rate of1.7 days decade-1,while the freeze end-date became advanced at an area-mean rate of 4.7 days decade-1.The delaying of the freeze start-date,which was combined with the advancing of the freeze end-date,resulted in a statistically significant shortening trend with respect to the freeze duration,at an area-mean rate of 6.4 days decade-1.Such changes would strongly affect the surface energy flux,hydrological processes,and vegetation dynamics.We also found that the rate of freeze-duration shortening at the near-surface soil layer was approximately 3.0 days decade-1lower than that at a depth of 1 m.This implied that the changes in soil freeze/thaw cycles at the near surface cannot be assumed to reflect the situation in deeper soil layers.The significant correlations between freeze duration and air temperature indicated that the shortening of the near-surface freeze duration was caused by the rise in air temperature,which occurred especially in spring,followed by autumn.These results can be used to reveal the laws governing the response of the near-surface freeze/thaw cycle to climate change and indicate related changes in permafrost.

Cracking in an expansive soil under freeze–thaw cycles

Expansive soils located in cold regions can easily endure the action of frost heaving and cyclic freezing–thawing. Cracking can also occur in expansive clayey soils under freeze–thaw cycles, of which little attention has been paid on this issue.In this study, laboratory experiment and cracking analysis were performed on an expansive soil. Crack patterns were quantitatively analyzed using the fractal concept. The relationships among crack pattern, water loss, number of freeze–thaw cycles, and fractal dimension were discussed. It was found that crack patterns on the surface exhibit a hierarchical network structure that is fractal at a statistical level. Cracks induced by freeze–thaw cycles are shorter, more irregularly oriented,and slowly evolves from an irregularly rectilinear pattern towards a polygonal or quasi–hexagonal one; water loss, closely related to specimen thickness, plays a significant role in the process of soil cracking; crack development under freeze-thaw cycles are not only attributed to capillary effect, but also to expansion and absorption effects.

Deformation monitoring and analysis at two frost mounds during freeze–thaw cycles along the Qinghai–Tibet Engineering Corridor

This paper presents various deformation-monitoring technologies employed to monitor the frost heave and thaw settlement of two mounds along the Qinghai–Tibet Engineering Corridor(QTEC), China. The QTEC is known as a critical infrastructure and passage connecting inland China and the Qinghai–Tibet Plateau(QTP). Three technologies—global navigation satellite system(GNSS), terrestrial laser scanning(TLS), and unmanned aerial vehicle(UAV)—were used to estimate the freeze/thaw–induced 3D surface deformation of two frost mounds. Our results showed that (1) the two frost mounds exhibited mainly thaw settlement in thawing periods and frost heave in the freezing period, but frost heave dominated after repeated freeze–thaw cycles;(2) different zones of the mounds showed different deformation characteristics;(3) active-layer thickness(ALT) and elevation changes were highly correlated during thaw periods;(4) integrated 3D-measurement technologies can achieve a better understanding and assessment of hazards in the permafrost area.

Deterioration Mechanism of Sulfate Attack on Concrete under Freeze-thaw Cycles

The experiments of concrete attacked by sulfate solution under freeze-thaw cycles were investigated. The sulfate solution includes two types of 5% Na2SO4 and 5% MgSO4. Through the experiment, microstructural analyses such as SEM, XRD and TGA measurements were performed on the selected samples after freeze-thaw cycles. The corrosion products of the concrete were distinguished and quantitatively compared by the thermal analysis. Besides, the damage mechanism considering the dynamic modulus of elastically of concrete under the coupling effect was also investigated. The experimental results show that, under the action of freeze-thaw cycles and sulfate attack, the main attack products in concrete are ettringite and gypsum. The corrosion products exposed to MgSO4 solution are more than those to Na2SO4 solution. Furthermore, the content of gypsum in concrete is less than that of ettringite in test, and some of gypsum can be observed only after a certain corrosion extent. It is also shown that MgSO4 solution has a promoting effect to the damage of concrete under freeze-thaw cycles. Whereas for Na：SO4 solution, the damage of concrete has restrained before 300 freeze-thaw cycles, but the sulfate attack accelerates the deterioration process in its further test period.

Effect of Freeze-thaw Cycles on Bond Strength between Steel Bars and Concrete

The effect of freezing and thawing cycles on mechanical properties of concrete （compressive, splitting tensile strength） was experimentally investigated. According to the pullout test data of three kinds of deformed steel bars, the bond stress-slip curves after freezing and thawing were obtained. The empirical equations of peak bond strength were proposed that the damage accounted for effects of freezing and thawing cycle. Meanwhile, the mechanism of bond deterioration between steel bars and concrete after freezing and thawing cycles was discussed. All these conclusions will be useful to the durability design and reliability calculation of RC structures in cold region.

Shear behavior of ultrafine magnetite tailings subjected to freeze-thaw cycles

To study the shear behavior of the ultrafine magnetite tailings subjected to freeze-thaw cycles,unconsolidated-undrained shear tests were conducted on ultrafine-grained tailings that were subjected to 1-11 cycles of freeze-thaw and defined as a type of clayey silt under confining pressures of 100,200,and 300 kPa.Taking the number of freeze-thaw cycles,cooling temperature,initial dry density,and moisture content as the four main influencing factors of shear behavior of the tailings samples,the shear stress-strain curve,compression modulus,failure strength,cohesion,and internal friction angle were measured.The results show that the freeze-thaw cycle has an obvious weakening effect on the shear behavior of the tailings material,and the shear mechanical parameters are affected by a combination of confining pressure,freeze-thaw cycle condition,and initial physical-mechanical properties of the tailings samples.Through the microstructural analysis of the tailings samples subjected to freeze-thaw cycles,it shows that the freeze-thaw cycle mainly affects the porosity,bound water,and arrangement of the tailings particles.Subsequently,the macroscopic changes in shear strength indexes emerge,and then the stability of the tailings dam will decrease.

The influence of freeze-thaw cycles on the granulometric composition of Moscow morainic clay

The freeze-thaw cycling process considerably changes the composition, structure, and properties of soils. Since the grain size is the most important factor in determining soil characteristics, our current research primarily aims to investigate dynamic changes of the soil fraction when exposed to freeze-thaw conditions. We observed two series of Moscow morainic clayey specimens （gQⅡm）： （Ⅰ） the original series, and （Ⅱ） the remolded series. We subjected each series of soil specimens to different frequencies of freeze-thaw cycles （3, 6, 20, and 40 cycles）, and we used granulometric tests to analyze both series before and after exposure to freeze-thaw conditions. As a result of our experiments, the granulometric compositions tended to be distributed evenly after 40 freeze-thaw processes （i.e., content of fraction for 0.1-0.05 mm was increased after 40 freeze-thaw cycles） because the division of coarse grains and the aggregation of fine grains were synchronized during the freeze-thaw process. The soil grains in both series changed bi-directionally. In the original series, changes of the sand grains were conjugated with the clay grains, and in the remolded series, changes of the sand grains were conjugated with the silt grains, because potential energy difference caused the division and aggregation processes to relate to the counteraction process. The even distribution of soil grain size indicated the state of equilibrium or balance. The granulometric compositions were altered the most during the sixth freeze-thaw cycle, because the coefficient of the intensity variation of the grain fineness （Kvar） had its maximum value at that time.

Review of the influence of freeze-thaw cycles on the physical and mechanical properties of soil

Seasonally frozen soil is a four-phase material and its physical-mechanical properties are more complex compared to the unfrozen soil. Its physical properties changes during the freeze-thaw process; repeated fieeze-thaw cycles change the characteristics of soil, which can render the soil from an unstable state to a new dynamic equilibrium state. The freezing process changes the structttre coupled between the soil particle arrangements, which will change the mechanical properties of the soil. The method of significance and interaction between different fac tors should be considered to measure the influence on the propties of soil under freeze-thaw cycles.