Chloride Bath로부터 전기도금된 나노결정립 니켈 박막의 잔류응력 변화에 대한 연구

박덕용,Park, Deok-Yong 한국전기화학회 2011 한국전기화학회지 Vol.14 No.3

첨가제 농도, 전류밀도, 도금용액 pH가 Ni 박막의 잔류응력, 표면형상, 미세조직에 미치는 영향을 관찰하기 위하여 chloride 도금용액으로부터 나노결정립 Ni 박막이 제조되었다. Ni 박막에서 잔류응력은 첨가제인 saccharin의 농도가 증가함에 따라 인장응력모드(약 150 MPa)로부터 압축응력모드(약 -100 MPa)로의 천이가 관찰되었다. Ni 박막의 미세구조는 도금용액 내에 saccharin의 유무에 따라 변화되었다. Saccharin이 첨가되지 않은 도금용액으로부터 전기도금된 Ni 박막은 주로 FCC(111) 과 FCC(200) 상들로 구성되어 있다. 그러나 Saccharin이 첨가된 도금용액으로부터 전기도금된 Ni 박막은 FCC(111), FCC(200), FCC (311) 상[때로는 FCC (220)]들로 구성되어 있다. 전류밀도는 Ni 박막의 잔류응력에 영향을 미치는 것으로 관찰되었다. $2.5\sim2.5{\mu}10mA{\cdot}cm^{-2}$의 전류밀도에서 가장 낮은 압축응력 값(약 -100 MPa)을 나타내었다. 도금용액의 pH 도 역시 Ni 박막의 잔류응력에 영향을 미쳤다. 한편, 도금용액에 saccharin의 첨가는 Ni 박막의 결정립 크기에 영향을 나타내었다. Saccharin이 첨가되지 않은 경우 Ni 박막의 결정립 크기가 약 60 nm로 측정되었으며, saccharin 함량이 0.0005 M 이상 첨가된 경우 Ni 박막의 결정립 크기가 24~38 nm로 측정되었다. Ni 박막의 표면 형상은 saccharin이 첨가됨에 따라 nodular 형상으로부터 매끄러운 (smooth) 형상으로 변화되었다. Nanocrystalline Ni thin films were electodeposited from chloride baths to investigate the influences of additive concentration, current density and solution pH on residual (or internal) stress, surface morphology, and microstructure of the films. It was observed that residual stress in Ni thin film was changed from tensile stress mode (about 150 MPa) to compressive stress mode (about -100 MPa) with increasing saccharin concentration as an additive. Microstructure of Ni thin films was changed with/without saccharin in baths. Ni thin films electrodeposited from saccharinfree bath mainly consisted of both FCC(111) and FCC(200) phases. However, Ni thin film electrodeposited from the baths containing saccharin exhibited FCC(111), FCC(200) and FCC (311) phases [sometimes, FCC (220)]. Current density influenced residual stress of Ni thin films. It was measured to be the lowest compressive stress value (about-100 MPa) in range of current density of $2.5\sim10mA{\cdot}cm^{-2}$. Solution pH also influenced residual stress of Ni thin film. Addition of saccharin in baths affected grain size of Ni thin films. Grain sizes of Ni thin films were measured to be about 60 nm without saccharin and 24~38 nm with more than 0.0005M saccharin concentration. Surface of Ni thin films was changed from nodular to smooth surface morphology with addition of saccharin.

Citrate Baths로부터 전기도금된 나노결정립 CoW 합금 박막/후막의 응력변화에 대한 연구

조익종,박덕용,인현만,Cho, Ik-Jong,Park, Deok-Yong,Ihn, Hyun-Man 한국전기화학회 2006 한국전기화학회지 Vol.9 No.4

Nanocrystalline CoW thin/thick film alloys were electodeposited from citrate baths to investigate the influences of metal ion concentration, current density and solution pH on chemical composition, current efficiency, residual stress, surface morphology, and microstructure of the film. Deposit W (tungsten) content in CoW thin/thick film increased with increasing W ion concentration, current density, and solution pH in the plating bath. It was observed that residual stress in CoW thin/thick film decreased with increasing W ion concentration and solution pH. CoW thin film exhibited mixed phases of hop Co [(100) and (002)] and hcp $Co_3W$ [(002) and (201)] at W ion concentration with 0.02 to 0.08 M. The microstructure of CoW thin film at W ion concentration of 0.1 to 0.2 M was close to amorphous phase. The dominant phases were found to be hop Co (002) and hop $Co_3W$ [(200), (002) and (201)] at the current densities of 5, 10, 25, and $100mA{\cdot}cm^{-2}$ CoW thin film at the current densities of 50 and $75mA{\cdot}cm^{-2}$ was close to amorphous phase. At solution pH 8.7, CoW thin film exhibited hcp Co (002) and hop $Co_3W$ [(200), (002) and (201)]. Below solution pH 8.7, CoW thin film exhibited amorphous microstructure. The optimum electrodeposition conditions for CoW thin/thick film were found to be W ion concentration of 0.08 M, current density of $10mA{\cdot}cm^{-2}$, and solution pH 8.7. 도금용액 내 텅스텐 이온 농도, 전류밀도, 도금용액 pH의 변화가 CoW 박막/후막의 화학조성, 전류효율, 잔류응력, 표면형상, 미세결정 구조, 결정립 크기에 미치는 영향을 조사하기 위하여, citrate 도금용액으로부터 전기도금공정에 의해 나노결정립 CoW 박막/후막 합금을 제조하였다. CoW 박막/후막에서 전기도금된 텅스텐 함량은 도금용액내의 텅스텐 이온 농도, 전류밀도, pH를 증가시킴에 따라 증가하였다. CoW 박막/후막에서 잔류응력은 도금용액내의 텅스텐 이온 농도와 pH를 증가시킴에 따라 감소함을 관찰하였다. CoW 박막/후막은 0.02M로부터 0.08M 범위의 텅스텐 이온 농도에서 hcp Co [(100), (002)]와 hop $Co_3W$ [(002), (201)] 혼합된 상들을 나타내었다. 그러나 0.1 M로부터 0.2M 범위의 텅스텐 이온 농도에서는 비정질에 가까운 상들을 나타내었다. 5, 10, 25, $100mA{\cdot}cm^{-2}$의 전류밀도에서 CoW 박막/후막은 hop Co (002)와 hcp $Co_3W$ [(200), (002), (201)] 상들로 구성되어 있다 그러나 50과 $75mA{\cdot}cm^{-2}$의 전류밀도에서는 비정질에 가까운 상들을 나타내었다. 8.7의 도금용액 pH에서 CoW 박막/후막은 hcp Co (002)와 hcp $Co_3W$ [(200), (002), (201)]상들을 나타내었다. 그러나 8.7 이하위 도금용액 pH 에서는 비정질에 가까운 상을 나타내었다. CoW 박막/후막의 최적 전기도금조건은 0.08M의 텅스텐 이온농도, $10mA{\cdot}cm^{-2}$ 전류밀도, 8.7의 도금용액 pH로 관찰되었다.

금속 Ni 분말을 용해하여 제조된 용액에서 Ni 농도 변화가 전기도금 된 Ni 필름 특성에 미치는 영향

윤필근,박덕용,Yoon, Pilgeun,Park, Deok-Yong 한국표면공학회 2019 한국표면공학회지 Vol.52 No.2

Chloride baths for electrodeposited Ni thin films were fabricated by dissolving metal Ni powders with the mixed solution consisting of HCl and de-ionized water. Current efficiency, residual stress, surface morphology and microstructure of Ni films with the change of metal ion ($Ni^{2+}$) concentrations in the plating solution were studied. Current efficiency was measured to be more than 90% with increasing $Ni^{2+}$ concentrations in the plating solution. Residual stress of Ni thin film was increased from about 400 to 780 MPa with increasing $Ni^{2+}$ concentration from 0.2 to 0.5 M. It is gradually decreased to 650 MPa at 0.9 M $Ni^{2+}$ concentration. Smooth surface morphologies were observed over 0.3 M $Ni^{2+}$ concentration, but nodule surface morphology at 0.2 M. Ni films consist of FCC(111), FCC(200), FCC(220) and FCC(311) peaks in XRD patterns. Preferred orientation of FCC(111) was observed and its intensity was slightly decreased with increasing $Ni^{2+}$ concentration. The average grain size was slightly increased at 0.3 M $Ni^{2+}$ concentration and then slightly decreased with increasing $Ni^{2+}$ concentration.

전기도금 된 Cu 필름 특성에 미치는 피로인산구리용액의 화학성분의 영향

신동율,구본급,박덕용,Shin, Dong-Yul,Koo, Bon-Keup,Park, Deok-Yong 한국전기화학회 2015 한국전기화학회지 Vol.18 No.1

전기도금공정을 이용하여 상온에서 제조된 Cu박막의 특성에 미치는 피로인산구리용액의 화학성분($Cu^{2+}$ 농도, $K_4P_2O_7$ 농도, 첨가제 농도)의 영향에 대한 연구를 수행하였다. 전류효율은 도금용액의 $Cu^{2+}$ 농도가 0.3 M까지 높아짐에 따라 거의 100%까지 증가하는 경향을 나타내었다. $K_4P_2O_7$ 농도는 1.5~1.8 M 농도에서 전류효율의 감소를 나타내었으나, 0.9~1.3 M과 2.1~2.4 M에서는 거의 100%의 전류효율을 나타내었다. 첨가제의 농도 변화는 전류효율에는 거의 영향을 미치지 않았다. 전기도금 된 Cu 박막의 잔류응력은 도금용액의 $Cu^{2+}$ 농도가 0.15 M 이하에서는 약 20 MPa로 측정되었으나, $Cu^{2+}$ 농도가 증가함에 따라 증가하다가 0.25 M 에서 약 120 MPa의 최대치를 나타내었다. 한편 도금용액의 $K_4P_2O_7$ 농도가 0.9 M로부터 2.4M로 증가할수록 잔류 응력은 80MPa로부터 0 MPa까지 감소하는 경향을 나타내었으며, 첨가제의 농도는 잔류응력에 영향을 미치지 않은 것으로 관찰되었다. 표면형상의 경우 $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도는 상당한 영향을 미쳤으나, 첨가제는 약간의 영향만을 나타내었다. XRD 분석 결과 $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도는 Cu 박막의 미세조직에 상당한 영향을 미쳤으나, 첨가제는 거의 영향을 미치지 않는 것으로 나타났다. $Cu^{2+}$ 농도와 $K_4P_2O_7$ 농도가 증가할수록 (111) 피크의 강한 우선방향성이 나타내었다. Effects of chemical composition ($Cu^{2+}$, $K_4P_2O_7$ and additive concentrations) of baths on properties of Cu thin films electrodeposited from pyrophosphate copper bath were investigated. Current efficiency was increased to be near 100% with increasing $Cu^{2+}$ concentrations from 0.02 to 0.3M. Decrease of current efficiency was observed in the range of 1.5~1.8M $K_4P_2O_7$ concentration, but current efficiency of about 100% was measured in the ranges of both 0.9~1.3M and 2.1~2.4M. The change of additive concentration did not influenced current efficiency. Residual stress of electrodeposited Cu thin films was measured to be about 20 MPa below 0.15 M $Cu^{2+}$ concentration and increased with the increase of it to 0.25 M. Maximum residual stress of 120MPa was observed at 0.25M $Cu^{2+}$ concentration. On the other hand, residual stress decreased from 80 to near 0 MPa as $K_4P_2O_7$ concentration varied from 0.9 to 2.4M and but The change of additive concentration did not affected on residual stress. $Cu^{2+}$ and $K_4P_2O_7$ concentrations significantly affect on surface morphology of electrodeposited Cu thin films, but additive concentration slightly affected. From XRD analysis, the microstructures of electrodeposited Cu thin film was affected from the changes of $Cu^{2+}$ and $K_4P_2O_7$ concentrations, but not from that of additive concentration. Strong preferred orientation of (111) peak was observed with increasing $Cu^{2+}$ and $K_4P_2O_7$ concentrations.

만성 족관절 외측 불안정성의 관절경적 소견 및 치료

이승용,김갑래,박덕용,Lee, Seung-Yong,Kim, Gab-Lae,Park, Deok-Yong 대한족부족관절학회 2007 대한족부족관절학회지 Vol.11 No.2

Purpose: To assess the arthroscopic findings in chronic lateral ankle instability and to evaluate the results of modified $Brostr{\ddot{o}}m$ operation and arthroscopic procedures. Materials and Methods: Twenty-nine cases with chronic lateral ankle instability were treated with modified $Brostr{\ddot{o}}m$ operation and ankle arthroscopy from May 2004 to January 2007. There were 19 male and 10 female with the mean age of 29.7 years. Mean follow up period was 15.8 months. All patients were checked preoperative stress anterior drawer and varus test with X-ray. Results: Associated injuries were 28 fat impingement projected into the joint between distal tibio-fibular space, 20 anterior impingement of soft tissue, 19 osteochondral defects and 13 loose body. Preoperative AOFAS score of pain, function and alignment were 28.9, 34.1 and 7.9 each other. They were improved into 38.7, 40.8 and 9.8 postoperatively. Conclusions: Modified $Brostr{\ddot{o}}m$ operation with ankle arthroscopy for chronic lateral ankle instability is believed to be a reliable option to obtain satisfactory results. Careful attention to the associated injuries such as distal fat impingement, anterior impingement, osteochondral defect and loose body is needed during the arthroscopy.

Ni Sulfamate-chloride 전기도금 용액에서 전류밀도와 첨가제의 농도 변화가 Ni 박막에 미치는 영향

윤필근(Pilgeun Yoon),박덕용(Deok-Yong Park) 한국표면공학회 2018 한국표면공학회지 Vol.51 No.1

Sulfamate plating solution containing a small amount of chloride bath was fabricated to study the properties of the electrodeposited Ni thin films. Effects of the changes of current density and additive concentration on current efficiency, residual stress, surface morphology and microstructure of Ni thin films electrodeposited from Ni sulfamate-chloride baths were investigated. The current efficiency was measured to be more than about 95%, independent of the changes of current density and saccharin concentration in the baths. Residual stress of Ni thin film was appeared to be the compressive stress modes in the range of 5~30 mA/㎠ current density. Maximum compressive stress was observed at the current density of 10 mA/㎠. Compressive stress values of Ni thin/thick films were increased to be about -85~-100 MPa with increasing saccharin concentration from 0 to 0.0195 M(4 g/L). Surface morphology was changed from smooth to nodule surface appearance with increasing the current density. Smooth surface morphology of Ni thin films electrodeposited from the baths containing saccharin was observed, independent of the saccharin concentration. Ni thin/thick films consist of FCC(111), FCC(200), FCC(220), FCC(311) and FCC(222) peaks. It was revealed that the FCC(200) peak of Ni thin films is the preferred orientation in the range of 5~30 mA/㎠ current density. The intensity of FCC(200) peak was gradually decreased and the intensity of FCC(111) peak was increased with increasing saccharin concentration in the baths.

피로인산구리용액으로부터 전기도금 된 Cu 필름의 특성에 미치는 도금조건의 영향

신동율,심철용,구본급,박덕용,Shin, Dong-Yul,Sim, Chulyong,Koo, Bon-Keup,Park, Deok-Yong 한국전기화학회 2013 한국전기화학회지 Vol.16 No.1

Effects of current density, electrodeposition temperature and solution pH on properties of Cu thin films electrodeposited from pyrophosphate bath were investigated. Current efficiency was decreased with increasing current density and increased with increasing temperature. But solution pH slightly influenced on current efficiency and current efficiency was measured to be above 90% at both room temperature and $55^{\circ}C$. Residual stress of Cu thin film electrodeposited at room temperature was decreased with increasing current density, while current density reaches to 60 $mA/cm^2$ or more, stress became close to zero. Cu thin films electrodeposited at $55^{\circ}C$ exhibited the residual stress range of 0~40 MPa. At room temperature, dendritic surface morphology was observed above the current density of 30 $mA/cm^2$ and at $55^{\circ}C$, above the current density of 100 $mA/cm^2$. Cu thin films electrodeposited from bath solution with room temperature and $55^{\circ}C$ mainly consisted of (111) peaks. Specially, Cu thin film electrodeposited at 30 $mA/cm^2$ and $55^{\circ}C$ exhibited strong preferred orientation of (111) peaks. 피로인산구리용액에서 전기도금공정을 이용하여 상온과 $55^{\circ}C$에서 각각 제조된 Cu박막의 특성에 미치는 전류밀도, 도금용액 온도, pH의 영향에 대한 연구를 수행하였다. 전류효율은 전류밀도가 증가함에 따라 감소하였으나, 도금용액의 온도가 증가함에 따라 증가하는 경향을 나타내었다. 그러나 pH 는 전류효율에 거의 영향을 미치지는 않았으며, 상온과 $55^{\circ}C$에서 모두 90% 이상으로 측정되었다. 상온에서 전기도금 된 Cu 박막의 잔류응력은 전류밀도의 증가에 따라 감소하며, 60 $mA/cm^2$ 이상에서는 거의 0에 근접하였다. $55^{\circ}C$에서 전기도금 된 Cu 박막은 0~40 MPa의 잔류응력을 나타내었다. 상온에서 도금하는 경우 수지상 표면 형상이 30 $mA/cm^2$ 이상의 전류밀도로부터 관찰되었고, $55^{\circ}C$에서는 100 $mA/cm^2$ 이상의 전류밀도부터 관찰되었다. 상온과 $55^{\circ}C$의 도금용액으로부터 전기도금 된 Cu 박막은 거의 (111) 피크들로 구성되어 있다. 특히 $55^{\circ}C$, 30 $mA/cm^2$에서 전기도금 된 Cu 박막의 경우 (111) 피크의 강한 우선방향을 나타내었다.

금속분말 Ni을 용해 한 Chloride Bath로 도금된 니켈후막의 입자크기에 대한 전류밀도 영향

박근용(Keun Yung Park),엄영랑(Young Rang Uhm),최선주(Sun Ju Choi),박덕용(Deok-Yong Park) 한국자기학회 2013 韓國磁氣學會誌 Vol.23 No.1

Nanocrystalline nickel (Ni) tick films were synthesized by direct current electrodeposition at current density from 1 to 30 mA/cm² and pH = 4. The basic composition of the bath, which was prepared by dissolving Ni metal particles in HCl, was 0.2M Ni ions. The effects of the current density on the average grain size of Ni deposits were investigated by XRD and SEM techniques. The results showed that the surface roughness was decreased as the saccharin addition was increased up to 2 g/l. The experimental results showed that the increase in the current density had a considerable effect on the average grain size of the Ni deposits. The perpendicular magnetization was raised as the thickness of coating layer was increased.

63Ni 밀봉선원용 Ni 전기도금 박막에서 Ni 농도가 잔류응력에 미치는 영향

윤필근(Pilgeun Yoon),박덕용(Deok-Yong Park) 한국표면공학회 2017 한국표면공학회지 Vol.50 No.1

Chloride plating solution was fabricated by dissolving metal Ni powders in a mixed solution with HCl and de-ionized water. Effects of Ni2+ and saccharin concentrations in the plating baths on current efficiency, residual stress, surface morphology and microstructure of Ni films were studied. In the case of 0.2 M Ni2+ concentration, current efficiency was decreased to about 65 % with increasing saccharin concentration, but, in the case of 0.7 M Ni2+ concentration, it was shown more than 90 % with the increase of saccharin concentration. Residual stress of Ni thin film was appeared to be about 400 MPa up to 0.0244 M saccharin concentration at the 0.2 M Ni2+ concentration and surface morphology with severe cracks was observed in the range of 0.0487~0.0975 M saccharin concentration. Residual stress of Ni thin films was measured to be about 750 MPa without saccharin addition and 114~148 MPa at the range of 0.0097~0.0975 M saccharin concentration for the 0.7 M Ni2+ concentration. Relatively low residual stress values (114~148 MPa) of the Ni films at the range of 0.0097~0.0975 M saccharin concentration may be resulted from codeposition of S from saccharin. Ni films at 0.7 M Ni2+ concentration showed smooth surface morphology and were independent of saccharin concentration. Ni films at 0.7 M Ni2+ concentration consist of FCC(111), FCC(200), FCC(220) and FCC(311) peaks and the intensities of FCC(111) and FCC(200) peaks increased with increasing saccharin concentration. Also, the average grain size decreased with increasing saccharin concentration from about 30 nm to about 15 nm.

Sulfamate-Chloride Bath에서 Co 농도의 변화에 따른 Ni-Co 필름의 특성 변화

윤필근(Pilgeun Yoon),박덕용(Deok-Yong Park) 한국표면공학회 2020 한국표면공학회지 Vol.53 No.1

Sulfamate-chloride baths were fabricated to study the properties of the electrodeposited Ni and NiCo thin films. The dependences of current efficiency, deposit composition of Ni and Co, residual stress, surface morphology and microstructure of electrodeposited Ni and NiCo thin films on CoCl₂ concentration in sulfamatechloride baths were investigated. The current efficiency was measured to be more than about 90%, independent of the changes of CoCl₂ concentration in the baths. Residual stress of Ni and NiCo thin films was increased from about 45 to about 250 ㎫ with varying CoCl₂ concentration from 0 to 0.210 M CoCl₂ in the baths and then reached to a plateau, about 250 ㎫ above 0.420 M CoCl₂ concentration. Nodular surface morphologies were observed at most CoCl₂ concentrations in the baths except 0.210 M. NiCo thin film electrodeposited from the bath with 0.210 M CoCl₂ concentration showed an acicular surface morphology. Pure Ni thin film consists of FCC(111), FCC(200), FCC(220), and FCC(311) peaks without any preferred orientation. On the other hand NiCo thin films make up of HCP(100), FCC(111), HCP(101), FCC(200), FCC(220) or HCP(110), FCC(311) or HCP(112) and FCC(222) peaks. It was revealed from the analysis of XRD result that FCC(111) peak at the NiCo thin film electrodeposited from the bath with 0.084 M CoCl₂ concentration can be regarded as the preferred orientation. However the peak of the preferred orientation was changed to FCC(220) or HCP(110) above 0.084 M CoCl₂ concentration in the baths. Then the intensity of FCC(220) or HCP(110) peak was gradually decreased with increasing CoCl₂ concentration further. The crystalline size of pure Ni thin film was observed to be about 53 ㎛ and those of NiCo thin films were in the range of 35~45 ㎛.