• 한국분말야금학회:학술대회논문집
• /
• 한국분말야금학회 2006년도 Extended Abstracts of 2006 POWDER METALLURGY World Congress Part 1
• /
• pp.240-241
• /
• 2006

Metal/diamond binary composite coatings on Al substrate without grit blasting were deposited by cold spray process with insitu powder preheating. Microstructural characterization of the as-sprayed coatings with different diamond size, strength and with/without Ti coating on diamond was carried out by OM and SEM. The assessment of basic properties such as tensile bond strength and hardness of the coatings, and the deposition efficiency was also carried out. Particular attention on the composite coatings was on the diamond fracture phenomenon during the cold spray deposition and the interface bonding between the diamond and the Fe-based metal matrix.

• Bulletin of the Korean Chemical Society
• /
• 제9권3호
• /
• pp.121-126
• /
• 1988

The molecular interaction of $Mo_2(OR)_4({\mu}-OR)_2$$ unit has been studied for carbonyl and acetylene ligands by means of extended Huckel calculations. We have extended the extended Hckel calculations to unknown apex bridged $Mo_2(OR)_6({\mu}-X)$ complexes (X = $SO_2$H, and Cl) in order to compare the stability of the complexes. In the $C_2H_2$and H apex bridged complexes, one finds a relatively small HOMO-LUMO gap. However, both complexes are stabilized due to Jahn-Teller distortion. The stability of both complexes is comparable to that of $Mo_2(OR)_6(CO)$ complex. The comparisons and predictions in the stability of known and unknown complexes are the subject of this study.

• Bulletin of the Korean Chemical Society
• /
• 제17권9호
• /
• pp.845-849
• /
• 1996

Bis(N,N-dimethyl-2-aminomethylthiophenium)tetrahalocuprate(Ⅱ) salt, (dmamtH)2CuCl4 and (dmamtH)2CuBr4 were prepared and characterized by spectroscopic (IR, UV-Vis, EPR, XPS), electrochemical method, and magnetic susceptibility measurement. The experimental results reveal that the compounds have pseudotetrahedral symmetry around copper(Ⅱ) site due to the steric hinderance of the bulky 2-(dimethylaminomethyl)thiophene in the complex. The N-H…Cl type hydrogen bonding is expected in (dmamtH)2CuCl4 from the XPS and IR data. Magnetic susceptibility data show that both of the compounds follow Curie-Weiss law in the range of 77-300 K with negative Weiss constant exhibiting antiferromagnetic interaction between copper(Ⅱ) ions in solid state.

• Bulletin of the Korean Chemical Society
• /
• 제19권2호
• /
• pp.231-235
• /
• 1998

Two holmium β-diketonate complexes, Ho(hfa)3(H2O)2 (1) and [Ho(hfa)3(H2O)2](triglyme) (2), have been prepared and characterized by IR, TGA, and single-crystal X-ray analyses. These complexes show polymeric chains by the intermolecular hydrogen bondings. The donor atoms of the intermolecular hydrogen bonding in both complexes are hydrogen atoms of the coordinated water molecules. The acceptor atoms in 1 are the carbonyl oxygen atoms of β-diketonate ligands whereas those in 2 are oxygen atoms of the triglyme ligand. While compound 1 decomposes cleanly to Ho2O3, compound 2 sublimes intact. Crystal data for 1 and 2 are as follows: Ho(hfa)3(H2O)2 triclinic P1, a=10.158(4), b=11.628(2), c=12.579(6) Å, α=67.02(3)°, β=73.95(4)°, γ=76.12(2)°, V=1299.8(8) Å3. [Ho(hfa)3(H2O)2](triglyme), monoclinic P21/c, a=12.559(3), b=19.111(2), c=16.789(6) Å, β=110.59(4)°, V=3772(2) Å3.

• 헤리티지:역사와 과학
• /
• 제55권2호
• /
• pp.200-211
• /
• 2022

청자 투각고리문 의자는 4점 일괄유물로 경기도 개성에서 출토된 것으로 전해진다. 청자 의자는 고려시대 당시 청자 제작기술의 우수성과 화려한 생활상을 보여주는 등 미술사적으로 가치가 높아 보물로 지정 관리되어 왔다. 그러나 일괄유물 중 1점의 경우 과거 수리 복원된 것으로, 처리 재료의 열화, 처리자의 미숙함 등으로 인해 미적가치가 하락되었고, 구조적으로 불안하여 재처리의 필요성이 제기되었다. 처리 전 보존상태를 조사한 결과, 물리적 손상은 전반적으로 제조상 결함부위를 중심으로 인위적 손상이 가중되어 구조적으로 취약한 상태를 보였다. 균열부위 및 탈락된 편은 접합면이 맞지 않고 접착제가 청자 표면에 흐른 자국과 접착제 표면에 분진 등 2차적 오염물이 생겨 변질된 상태였다. 수리복원 상태를 조사하기 위해 자외선과 확대현미경을 이용하여 균열부의 접합 부위의 위치와 범위, 상태를 파악하였다. 적외선분광 분석(FT-IR)과 휴대용 X-선 형광분석을 실시하여 보존처리에 사용한 재료를 분석한 결과, 접착제로 셀룰로오스계 수지와 에폭시계 수지가 사용된 것을 확인하였다. 또한 일부 힘을 받는 접합부위에서는 접합강도를 높이기 위해 접착제에 석고(CaSO₄·2H₂O) 또는 골분(Ca₁₀ (PO₄)₆(OH)₂)을 첨가한 것을 알 수 있었다. 상태조사 결과를 바탕으로, 유물의 보존처리는 기존 접합된 상태에서 전면 해체하고 물리적으로 취약한 부분을 중심으로 접합·복원을 통해 보강하는데 중점을 두었다. 기존에 사용된 접착제를 제거하고 해체한 결과, 청자 의자는 크게 상부와 하부, 굽다리, 일부 고리 문 등 총 6개 편으로 분리되었다. 해체 후 접합면에 남아 있는 잔류 접착제 및 오염물은 화학적 및 물리적으로 제거하고 스팀세척기로 파단면 세척을 통해 재접합의 효율을 높였다. 유물의 접합은 접합부위와 크기에 따라 접착제를 다르게 적용하였다. 편의 위치만 고정하는 접합부에는 시아노아크릴계 수지 Loctite^® 401을 사용하고 구조적으로 안정화시키는 부분에는 가역성을 위해 아크릴계 수지인 Paraloid^® B-72 20%(in xylene)로 단면처리한 후 에폭시계 수지 Epo-tek^® 301-2를 이용하여 접합하였다. 상·하부 접합 같이 힘을 받는 부위는 Epo-tek^® 301-2에 Kaolin을 첨가하여 접합강도를 보강하였다. 연속되는 문양으로 추정 가능한 고리문의 결실 부분은 SN-Sheet로 뼈대를 만들고 Wood epos^®로 파손단면을 연결하여 모델링하면서 고리문을 복원하였다. 그 외 접합하면서 생긴 복원 부위는 심미적 및 구조적 안정화를 위해 Wood epos^®로 메움처리하였다. 복원부위 및 메움처리한 부분은 추후 전시활용에 있어 이질감이 없도록 색맞춤하였다. 다양한 과학기술을 활용한 조사와 처리과정은 체계적으로 기록하여 보존 관리하는데 기초자료로 활용하도록 하였다.

• 한국응용과학기술학회지
• /
• 제7권1호
• /
• pp.93-105
• /
• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• 분석과학
• /
• 제20권4호
• /
• pp.355-360
• /
• 2007

The title complex, $(C_3H_{12}N_2)[\{Cd(H_2O)(C_6H_5O_7)\}_2]{\cdot}6H_2O$, I, has been prepared and its structure characterized by FT-IR, EDS, elemental analysis, ICP-AES, and X-ray single crystallography. It is triclinic system, $P{\bar{1}}$ space group with a = 10.236(2), b = 11.318(2), c = $13.198(2){\AA}$, ${\alpha}=77.95(1)^{\circ}$, ${\beta}=68.10(1)^{\circ}$, ${\gamma}=78.12(1)^{\circ}$, V = $1373.5(3){\AA}^3$, Z = 2. Complex I has constituted by protonated 1,3-diaminopropane cations, citrate coordinated cadmium(II) anions, and free water molecules. The central cadmium atoms have a capped trigonal prism geometry by seven coordination with six oxygen atoms of three different citrate ligands and one water molecule. Citrate ligands are bridged to three different cadmium atoms. Each cadmium atom is linked by carboxylate and hydroxyl groups of citrate ligand to construct an one-dimensional ladder-type assembly structure. The polymeric crystal structure is stabilized by three-dimensional networks of the intermolecular O-H${\cdots}$O and N-H${\cdots}$O hydrogen-bonding interaction.

• Bulletin of the Korean Chemical Society
• /
• 제33권9호
• /
• pp.2971-2975
• /
• 2012

Second-order rate constants $k_N$ have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 8 is linear with ${\beta}_{nuc}$ = 0.84. The ${\beta}_{nuc}$ value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., ${\beta}_{nuc}$ = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$, in which expulsion of the leaving-group from $T^{\pm}$ occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, $T^{\pm}$ and its deprotonated form $T^-$ on the basis of the fact that the plots of pseudo-first-order rate constant $k_{obsd}$ vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.

• 소성∙가공
• /
• 제16권7호
• /
• pp.530-537
• /
• 2007

This paper is concerned with the analysis of plastic deformation of bimetal co-extrusion process. Two sets of material combination have been adopted for analysis, i.e. combinations of Cu/Al and Fe/Al. In the first set of material combination, the selected materials are AA 1100 aluminum alloy as hard material and CDA 110 as soft one. This type of material selection is to examine the effect of hard core and soft sleeve and vice versa on the deformation pattern in terms of plastic zone and velocity discontinuity along the contact surface between construction materials. Four different cases of co-extrusion process in terms of material combination and interference bonding were simulated to investigate the effect of material arrangement between core and sleeve, and of bonding on the plastic zones and velocity discontinuity. In the other set of material combination, model materials used as core and sleeve were AA 1100 and AISI 1010, which are relatively soft and hard, respectively. Process parameters except diameter ratio of core to sleeve material such as semi-die angle, reduction in area in global sense and die comer radius have been set constant throughout the simulation to concentrate our effort on the analysis of influence of diameter ratio on deformation behavior such as deformation zone, surface expansion, exit velocity discontinuity between composite materials, and extrusion forces.

• Bulletin of the Korean Chemical Society
• /
• 제30권10호
• /
• pp.2393-2397
• /
• 2009

Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.