• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1161-1164
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• 1998

The catalytic transformation of sterically bulky tertiary stannane n-Bu3SnH by the Cp2MCl2/Red-Al (M=Ti, Zr, Hf) and M(CO)6 (M=Cr, Mo, W) catalysts yielded two kinds of catenated products: one is a cross-linked polystannane as minor product, and the other is hexabutyldistannane (n-Bu3Sn)2 as major product. The distannane was produced by simple dehydrocoupling of n-Bu3SnH, whereas the cross-linked polystannane could be obtained via redistribution/dehydrocoupling combination process of n-Bu3SnH. The redistribution/dehydrocoupling combination process may initially produce a low-molecular-weight oligostannane with partial backbone Sn-H bonds which could then undergo an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane.

• Bulletin of the Korean Chemical Society
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• 제18권12호
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• pp.1264-1268
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• 1997

The poly(methylsilene) (1) was modified with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalyst and with the group 6 metal carbonyl M(CO)6 (M = Cr, Mo, W) catalyst, producing the highly cross-linked isoluble polymer and the lowly cross-linked soluble polymer, respectively. An interrelationship between molecular weight and percent ceramic residue yield with metal within the respective group was not found. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weight and lower percent ceramic residue yield than the polymers modified with the group 6 metal carbonyl catalysts do. The catalytic activity of group 4 metallocene combinations appears to be higher at ∼100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls. The pyrolysis of the modified 1 yielded SiC ceramic.

• Bulletin of the Korean Chemical Society
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• 제18권12호
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• pp.1291-1295
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• 1997

The catalytic dehydrocoupling of di-n-butylstannane n-Bu2SnH2 by the Cp2MCl2/Red-Al (M = Ti, Zr, Hf) and M(CO)6/Red-Al in situ combination catalysts yielded a mixture of two kinds of catenated products: one is a cross-linked insoluble solid, and the other is a non-cross-linked soluble solid (≒Sn5) or viscous oil (≒Sn2). The soluble oligostannanes could be produced by simple dehydrocoupling of n-Bu2SnH2, whereas the insoluble polystannanes could be obtained via disproportionation/dehydrocoupling combination process of n-Bu2SnH2. The disproportionation/dehydrocoupling combination process may initially produce a low-molecular-weight oligostannane with partial backbone Sn-H bonds which could then undergo an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane.

• 폴리머
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• 제24권2호
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• pp.159-167
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• 2000

폴리메틸렌 다리를 가진 3가지 dinuclear half-titanocene [(CH$_2$)$_{n}$(C$_{5}$ H$_4$)$_2$[TiCl$_3$]$_2$(n=5(10), 7(11), 9(12))을 합성하고 이들의 중합특성을 조사하였다. 이들은 해당되는 리간드의 리튬염을 trimethyltin chloride와 미리 반응시켜 얻을 distannyl기가 치환된 리간드를 TiCl$_4$와 반응시키는 경로를 통해 합성될 수 있었다. 합성된 화합물들은 IR, $^1$H NMR, $^{13}$C NMR과 질량분석기를 통해 구조와 조성을 규명하였다. 합성된 dinuclear half-titanocene의 중합특성을 조사하기 위해 조촉매 MMAO 존재 하에서 스티렌의 중합실험을 진행하였으며, 그 결과 (i) 합성된 세 가지의 촉매는 모두 SPS를 제조하는데 성공적인 촉매였으며, ( ii ) 촉매 중에서는 CpTiCl$_3$ 사이가 가장 긴 다리리간드로 연결된 화합물 12가 활성면에서는 가장 높았으나 생성된 고분자의 분자량은 가장 낮게 나타났다. 이런 결과들은 다리리간드인 polymethylene이 미치는 전기적 및 입체적 영향으로 설명될 수 있다. 다리의 길이가 길어지면 polymethylene이 가지는 전자주게 특성이 활성점을 안정화시켜 활성을 향상시키며, 다리의 길이가 길어지면 두 활성점 사이의 거리가 멀어져 활성점 사이에 작용하는 입체적인 영향을 감소시켜 정지반응인 $\beta$-H 제거가 잘 일어나 생성되는 syndiotactic polystyrene의 분자량이 감소하게 된다.다.

• 구강회복응용과학지
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• 제25권3호
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• pp.293-306
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• 2009

본 연구에서는 알카리 열처리 티타늄 임플란트상에서 백서 태자 두개관 세포의 생물학적 반응을 알아보고자 하여 다음과 같은 결과를 얻었다. 알카리 열처리 티타니움 표면에서 Ti-6Al-4V 합금 표면에서보다 세포증식도가 유의하게 높았다 (p<0.01). 면역효소 분석에서 interleukin $(IL)-1{\beta}$와 IL-6의 합성은 배양 시간이 길수록 증가하였다. Herbimycin으로 전처치한 경우에는 세포 배양 7일 째에 IL-6의 합성이 유의하게 억제되었다(p<0.01). 알카리인산 분해 효소 활성은 알카리 열처리 임플란트에서 타이타늄, Ti-6Al-4V 합금 표면에서 보다 유의하게 더 높았다 (p<0.001). 유전자 분석에서 알카리 열처리 임플란트에서 배양된 세포들의 alkaline phosphatase, bone sialoprotein, receptor activated nuclear factor ligand 유전자의 발현이 증가하였다. Herbimycin과 SB203580으로 전처치시 $IL-1{\beta}-induced$ IL-6 유전자의 발현이 감소하였다. 이상의 결과는 알카리 열처리된 티타늄 임플란트가 조골세포의 분화를 자극하고 골개조를 촉진시킴을 시사한다.

• 통합자연과학논문집
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• 제3권1호
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• pp.1-6
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• 2010

Bis(silyl)alkylbenzenes such as bis(1-sila-sec-butyl)benzene (1) and 2-phenyl-1,3-disilapropane (2) were synthesized in high yields by the reduction of the corresponding chlorosilanes with $LiAlH_4$ in diethyl ether. The dehydrocoupling of 1 and 2 was performed using group IV metallocene complexes generated in situ from $Cp_2MCl_2$/Red-Al and $Cp_2MCl_2$/n-BuLi (M = Ti, Hf), producing two phases of polymers. The TGA residue yields of the insoluble polymers were in the range of 64-74%. The molecular weights of the soluble polymers produced ranged from 700 to 5000 ($M_w$ vs polystyrene using GPC) and from 500 to 900 ($M_w$ vs polystyrene using GPC). The dehydropolymerization of 1 and 2 seemed to initially produce a low-molecular-weight polymer, which then underwent an extensive cross-linking reaction of backbone Si-H bonds, leading to an insoluble network polymer.

• 대한치과보철학회지
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• 제45권2호
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• pp.169-181
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• 2007

Statement of problem: Titanium is well known as a proper metal for the dental restorations, because it has an excellent biocompatibility, resistance to corrosion, and mechanical property. However, adhesion between titanium and dental porcelains is related to the diffusion of oxygen to the reaction layers formed on cast-titanium surfaces during porcelain firing and those oxidized layers make the adhesion difficult to be formed. Many studies using mechanical, chemical and physical methods to enhance the titanium-ceramic adhesion have been actively performed. Purpose: This study meant to comparatively analyse the adhesion characteristics depending on different titanium surface coatings after coating the casts and wrought titanium surfaces with Au and TiN. Material and method: In this study, the titanium specimens (CP-Ti, Grade 2, Kobe still Co. Japan) were categorized into cast and wrought titanium. The wrought titanium was cast by using the MgO-based investment(Selevest CB, Selec). The cast and wrought titanium were treated with Au coating($ParaOne^{(R)}$., Gold Ion Sputter, Model PS-1200) and TiN coating(ATEC system, Korea) and the ultra low fusing dental porcelain was fused and fired onto the samples. Biaxial flection test was done on the fired samples and the porcelain was separated. The adhesion characteristics of porcelain and titanium after firing and the specimen surfaces before and after the porcelain fracture test were observed with SEM. The atomic percent of Si on all sample surfaces was comparatively analysed by EDS. In addition, the constituents of specimen surface layers after the porcelain fracture and the formed compound were evaluated by X-ray diffraction diagnosis. Result: The results of this study were obtained as follows : 1. The surface characteristics of cast and wrought titanium after surface treatment(Au, TiN, $Al_2O_3$ sandblasting) were similar and each cast and wrought titanium showed similar bonding characteristics. 2. Before and after the biaxial flection test, the highest atomic weight change of Si component was found in $Al_2O_3$ sandblasted wrought titanium(28.6at.% $\rightarrow$ 8.3at.%). On the other hand, the least change was seen in Au-Pd-In alloy(24.5at.% $\rightarrow$ 9.1at.%). 3. Much amount of Si components was uniformly distributed in Au and TiN coated titanium, but less amount of Si's was unevenly dispersed on Al2O3 sandblasting surfaces. 4. In X-ray diffraction diagnosis after porcelain debonding, we could see $Au_2Ti$ compound and TiN coating layers on Au and TiN coated surfaces and $TiO_2$, typical oxide of titanium, on all titanium surfaces. 5. Debonding of porcelain on cast and wrought titanium surface after the biaxial flection is considered as a result of adhesion deterioration between coating layers and titanium surfaces. We found that there are both adhesive failure and cohesive failure at the same time. Conclusion: These results showed that the titanium-ceramic adhesion could be improved by coating cast and wrought titanium surfaces with Au and TiN when making porcelain fused to metal crowns. In order to use porcelain fused to titanium clinically, it is considered that coating technique to enhance the bonding strength between coating kKlayers and titanium surfaces should be developed first.

• Journal of Welding and Joining
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• 제32권6호
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• pp.47-55
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• 2014

The purpose of the study is to produce a mechanically improved weld and minimum variation of color through comparing unpulsed and pulsed GTAW (Gas Tungsten Arc Welding) for pure titanium (CP grade7) tube. Pulsed GTAW using 60 A peak current and 20 A background current (1:9) achieved the wider window of welding conditions having part and full penetration without burn-through than the case of unpulsed GTAW. Moreover, the pulsed welding reduced a discoloration on the back bead of the weld and the size of microstructures (basket weave and serrated ${\alpha}$). That is because the pulsed welding has it's a low heat input and severe weld flow induced from electric current variation. Furthermore, the pulsed welding improved the bending property of the welded Ti tube. The enhanced bending property for the pulsed GTAW was due to the insignificant discoloration on the weld surface with maintaining the metal polish.

• 동력기계공학회지
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• 제14권5호
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• pp.41-47
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• 2010

티타늄과 티타늄 합금은 재료적 특이성 때문에 심장 혈관 임플란트에서 일반적으로 사용되어 왔다. 일찍이 적용된 예로는 인공심장판막, 심박조율기의 보호케이스, 혈액 순환 장치 등이 있다. 하지만 물질유도혈전증(Material-induced thrombosis)은 혈전폐색에 의해 기인한 기능 손실로 심장혈관 임플란트 장치의 주된 합병증으로 존재하고 있으며, 심장혈관 임플란트의 혈전유전자는 심장혈관장치의 발달에 주된 난관 중 하나로 남아있다. 그리고 텍스처 혈액 접합 물질(Textured blood-contacting material)은 1960년대 초반 이후부터 혈액순환 보조 장치의 임상실험에 사용되고 있다. 접합 물질에 내장된 텍스처 섬유조직 표면은 형성, 성장, 안정적 부착, 생물학적 내벽(neointimal layer) 등 유도 혈액(entrapping blood) 성분에 의해 형성된다. 공동(cavity) 형상의 용해 가능한 미립자를 사용하는 SCPL법(Solvent casting/particulate leaching method)은 티타늄 기질 이전에 형성된 폴리우레탄 위에 텍스처(texture)를 생성하기 위해 사용되었다. 또한 콜라겐의 부동화(不動化)에 의한 공동(cavity)은 혈액 접합면에 잔존하기 위한 내피세포를 고정할 수 있는 효과가 있다. cpTi로 층화된 PU 기소공성(microporous)은 구조적 특성과 혈전증 감소를 위한 생물학적 내벽 사용의 잠재성을 평가하기 위한 세포 공동체 실험을 통해서 평가되었다.

• 통합자연과학논문집
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• 제5권2호
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• pp.79-83
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• 2012

Trialkyltin n-$Bu_3SnH$, an endocrine disruptor, was slowly converted by the catalytic action of group 4 $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) to produce two phases of products: one is an insoluble cross-linked solid, polystannane in 7-23% yield as minor product via redistribution/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 69-90% yield as major product via simple dehydrocoupling process. Redistribution/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, leading to an insoluble polystannane. This is the first exciting example of redistribution/dehydrocoupling of a tertiary hydrostannane catalyzed by early transition metallocenes.