• Transactions of the Korean Society of Mechanical Engineers
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• v.19 no.1
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• pp.202-211
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• 1995

Heat and hydrogen transfer characteristics have been experimentally investigated for a hydride reaction bed, in which hydride material LaN $i_{4,7}$A $l_{0.3}$ is contained for hydrogen storage. This problem is of particular interest in the design of metal hydride devices such as metal-hydride refrigerators, heat pumps, or metal-hydride storage units. Transient behavior of hydrogen transfer through the hydride materials as well as heat transfer is studied during absorption and desorption processes in detail. The experimental results obtained indicate that the mass flow of the hydrogen is strongly affected by the governing parameters, such as the initial pressure of the reaction bed, absorption or desorption period, and cooling or heating temperature. These mass transfer results are along with the heat transfer rate between hydride materials and heat transfer medium in the reaction bed.d.d.

• Nuclear Engineering and Technology
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• v.33 no.2
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• pp.192-200
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• 2001

Hydride blisters were formed on the outer surface of Zr-2.5Nb pressure tube by a non- uniform steady thermal diffusion process. A thermal gradient was applied to the pressure tube with a heat bath kept at a temperature of 415$^{\circ}C$ and an aluminum cold finger cooled with flowing water of 15$^{\circ}C$. Optical microscopy and tree-dimensional laser profilometry were used to characterize the hydride blisters with different hydrogen concentrations and thermal diffusion time. Hydride blisters were expected to start at a hydrogen concentration of 30 - 70 ppm and a thermal diffusion time of 4 - 6$\times$10$^{5}$ sec. The hydride blister size increases with higher hydrogen concentrations and longer thermal diffusion time . Some of the samples revealed cracks on the hydride blisters. The ratio of hydride blister depth to height was estimated as approximately 8: 1.

• Bulletin of the Korean Chemical Society
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• v.5 no.1
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• pp.37-41
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• 1984

The pseudolattice calculations in the CNDO/2 level of approximation are carried out for polymeric beryllium hydride, polyethylene and polymeric boron hydride. Since there is no evidence on the geometry for polymeric boron hydride, the two possible geometries are assumed. One is a polyethylene-type geometry and the other is a polymeric beryllium hydride-type geometry. In order to compare their relative stability, we calculate polyethylene and polymeric beryllium hydride and then compare with polymeric boron hydride having the assumed structures. The total energy calculation indicates that a polymeric beryllium bydride-type geometry is more stable than a polyethylene-type geometry. Our results obtained for polyethylene are in good agreement with those given by CNDO/2 crystal orbital. From the convergence problem with respect to the number of unit cells (M), the calculation with value of 4 for M can be considered to give the convergence limit results.

• Transactions of the Korean hydrogen and new energy society
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• v.31 no.6
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• pp.564-570
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• 2020

Metal hydride is suitable for safe storage of hydrogen. The hydrogen storage kinetics of the metal hydride are highly dependent on its heat transfer characteristics. This study presents a metal hydride-expended graphite composite with improved thermal conductivity and its hydrogen storage kinetics. To improve the heat transfer characteristics, a metal hydride was mixed and compacted with a high thermal conductivity additive. As the hydrogen storage material, AB5 type metal hydride La0.9Ce0.1Ni5 was used. As an additive, flakes-type expended graphite was used. With improved heat transfer characteristics, the metal hydride-expended graphite composite stores hydrogen four times faster than metal hydride powder.

• Nuclear Engineering and Technology
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• v.54 no.5
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• pp.1579-1587
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• 2022

The effects of hydride amount (20-850 wppm), orientation (circumferential and radial), and temperature (room temperature, 100 ℃, 200 ℃) on the axial mechanical properties of Zircaloy-4 cladding were comprehensively examined. The fraction of radial hydride fraction in the cladding was quantified using PROPHET, an in-house radial hydride fraction analysis code. Uniaxial tensile tests (UTTs) were conducted at various temperatures to obtain the axial mechanical properties. Hydride orientation has a limited effect on the axial mechanical behavior of hydrided Zircaloy-4 cladding. Ultimate tensile stress (UTS) and associated uniform elongation demonstrated limited sensitivity to hydride content under UTT. Statistical uncertainty of UTS was found small, supporting the deterministic approach for the load-failure analysis of hydrided Zircaloy-4 cladding. These properties notably decrease with increasing temperature in the tested range. The dependence of yield strength on hydrogen content differed from temperature to temperature. The ductility-related parameters, such as total elongation, strain energy density (SED), and offset strain decrease with increasing hydride contents. The abrupt loss of ductility in UTT was found at ~700 wppm. Demonstrating a strong correlation between total elongation and offset strain, SED can be used as a comprehensive measure of ductility of hydrided zirconium alloy.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.132-138
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• 1994

Bis(diethylamino)aluminum hydride was utilized in a systematic study of the approximate rates and stoichiometry of the reaction of excess reagent with 55 selected organic compounds containing representative functional groups under standardized conditions (THF, $0^{\circ}C$, reagent to compound=4 : 1) in order to define the characteristics of the reagent for selective reductions. The reducing action of BEAH was also compared with that of the parent aluminum hydride. The reducing action of the reagent is quite similar to that of aluminum hydride, but the reducing power is much weaker. Aldehydes and ketones were readily reduced in 1-3 h to the corresponding alcohols. However, unexpectedly, a ready involvement of the double bond in cinnamaldehyde was realized to afford hydrocinnamyl alcohol. The introduction of diethylamino group to the parent aluminum hydride appears not to be appreciably influential in stereoselectivity on the reduction of cyclic ketones. Both p-benzoquinone and anthraquinone utilized 2 equiv of hydride readily without evolution of hydrogen, proceeded cleanly to the 1,4-reduction products. Carboxylic acids and acid chlorides underwent reduction to alcohols slowly, whereas cyclic anhydrides utilized only 2 equiv of hydride slowly to the corresponding hydroxylacids. Especially, benzoic acid with a limiting amount of hydride was reduced to benzaldehyde in a yield of 80%. Esters and lactones were also readily reduced to alcohols. Epoxides examined all reacted slowly to give the ring-opened products. Primary and tertiary amides utilized 1 equiv of hydride fast and further hydride utilization was quite slow. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Among them, benzamide and N,N-dimethylbenzamide gave ca, 90% yields of benzaldehyde. Both the nitriles examined were also slowly reduced to the amines. Unexpectedly, both aliphatic and aromatic nitro compounds proved to be relatively reactive to the reagent. On the other hand, azo- and azoxybenzenes were quite inert to BEAH. Cyclohexanone oxime liberated 1 equiv of hydrogen and utilized 1 equiv of hydride for reduction, corresponding to N-hydroxycyclohexylamine. Pyridine ring compounds were also slowly attacked. Disulfides were readily reduced with hydrogen evolution to the thiols, and dimethyl sulfoxide and diphenyl sulfone were also rapidly reduced to the sulfides.

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.416-421
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• 1995

The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.

• Nuclear Engineering and Technology
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• v.50 no.7
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• pp.1138-1147
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• 2018

Delayed hydride cracking (DHC) is an important failure mechanism for Zircaloy tubes in the demanding environment of nuclear reactors. The threshold stress intensity factor, $K_{IH}$, and critical hydride length, $l_C$, are important parameters to evaluate DHC. Theoretical models of them are developed for Zircaloy tubes undergoing non-homogenous temperature loading, with new stress distributions ahead of the crack tip and thermal stresses involved. A new stress distribution in the plastic zone ahead of the crack tip is proposed according to the fracture mechanics theory of second-order estimate of plastic zone size. The developed models with fewer fitting parameters are validated with the experimental results for $K_{IH}$ and $l_C$. The research results for radial cracking cases indicate that a better agreement for $K_{IH}$ can be achieved; the negative axial thermal stresses can lessen $K_{IH}$ and enlarge the critical hydride length, so its effect should be considered in the safety evaluation and constraint design for fuel rods; the critical hydride length $l_C$ changes slightly in a certain range of stress intensity factors, which interprets the phenomenon that the DHC velocity varies slowly in the steady crack growth stage. Besides, the sensitivity analysis of model parameters demonstrates that an increase in yield strength of zircaloy will result in a decrease in the critical hydride length $l_C$, and $K_{IH}$ will firstly decrease and then have a trend to increase with the yield strength of Zircaloy; higher fracture strength of hydrided zircaloy will lead to very high values of threshold stress intensity factor and critical hydride length at higher temperatures, which might be the main mechanism of crack arrest for some Zircaloy materials.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1588-1592
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• 2009

Lithium cyanoaluminum hydride (LCAH) was prepared by the metal cation exchange reaction of sodium cyanoaluminum hydride with lithium chloride in tetrahydrofuran. The reducing characteristics of LCAH were explored systematically by the reaction with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0 ${^{\circ}C}$). The reducing ability of LCAH was also compared with of the sodium derivative, sodium cyanoaluminum hydride (SCAH). Generally, the reducing behavior of LCAH resembles that of SCAH closely, but the reactivity of LCAH toward representative organic functional groups appeared to be stronger than that of SCAH. Thus, the regent reduces carbonyl compounds, epoxides, amides, nitriles, disulfides, carboxylic acids and their acyl derivatives to the corresponding alcohols or amines, at a relatively faster rate than that of SCAH. The cyano substitution, a strong election-withdrawing group, diminishes the reducing power of the parent metal aluminum hydrides and hence effects the alteration of their reducing characteristics.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.873-881
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• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.