中 原 大 學 醫 學 工 程 學 系
生 醫 材 料 力 學 暨 表 面 改 質 實 驗 室
國 立 成 功 大 學 材 料 科 學 及 工 程 學 系
生 物 醫 學 應 用 實 驗 室
主 持 人 : 廖 峻 德 博 士
歷 年 博、碩 士 論 文 中 英 摘 要
中原大學醫學工程學系/生醫材料力學暨表面改質實驗室/博士(P)、碩士(M)論文摘要集
(指導教授:廖峻德博士)1996/08-2002/07
曾雅君 87M01:連續式二氧化碳雷射對牙釉質、牙本質及生醫玻璃之交互作用研究(June 1998,1998材料科學學會論文獎第一名)
王明誠 87M02:三維人工髖關節模擬磨耗測試機之設計與製造(June 1998)
吳建宏 87M03:低溫高密度微電漿處理技術對高分子材料表面改質(June 1998)
游永祥 88M01:微波電漿與高週波電漿的特性研究(June 1999)
許迪竣 88M02:可攜式微生物毒性感測器之製作與評估(June 1999)(專利申請)
孫銘偉 88M03:利用微波電漿活化聚丙烯不織布纖維表面以固定蛋白質(June 1999)
尤昶清 88M04:髖關節模擬磨耗機對人工髖臼-球之磨耗殘屑研究(June
1999)
賴育誠 89M01:全人工髖關節之鬆脫問題的實驗模擬與評估(May 2000)(中文期刊一篇)
許高源 89M02:陣列式微波電漿對聚酯纖維聚醯胺纖維之表面功能性改質(June 2000)
翁志強 90M01:順流式遠端電漿對單層有機金屬表面反應機制之研究(July 2001)
邱耀慶 90M02:全人工髖關節損壞機制之研究:臨床與實驗取得殘屑之比較(June 2001)(中文期刊一篇)
劉光弘 90M03:利用紅外光光譜建立即時微量煙霧監測系統及經濟型二氧化碳感測器
吳奕德 91M01:利用真空濕式管以連續步驟完成生醫單體固定(June 2002)(Oct. 2002,2002國家同步輻射研究中心用戶會議論文比賽第二名)
謝登讚 91M02:具功能性尾端之單層有機金屬固定機制之研究(June 2002)(Dec. 2002,2002醫學工程年會論文比賽第一名)
陳冠宏 91M03:可攜式微生物毒性感測器之製作與評估:不同菌種對毒性反應的比較
林志達 91M04:經濟型血糖感測器之製作及市售電極片之評估(July 2002)
田育彰 91P01:固定生醫單體之生物活性與結構穩定性之探討(Sept. 2002)
王明誠 91P02:具官能基尾端之單層規則排列有機分子表面與生醫分子之界面反應機
林淑萍 92M01:固定幾丁聚醣於聚丙烯不織布應用在醫療抗菌敷布之研究(Jan. 2003)(國科會碩士論文獎)
高啟原 92M02:可攜式微生物感測器:工作電壓對於不同固定菌屬電極之最佳化探討
陳煌仁 92M03:可程式之人工全膝關節模擬磨耗機的研製(Jan. 2003)(Dec. 2002,2002生物力學學會壁報論文獎)
徐俊傑 92M04:應用版式電極製作可攜式快速尿酸感測裝置(Jan. 2003)
林明哲
92M05:電漿誘導聚酯纖維鍵結幾丁聚醣形成具抗菌功能性之表面(March 2003)
國立成功大學材料科學及工程學系/微機電系統研究所(E)/生物醫學應用實驗室/博士(P)、碩士(M)論文摘要集
(指導教授:廖峻德博士)2002/08-
游惟翔 93M01:電漿離子佈植在鈦合金及碳合金鋼表面產生型態及微結構變化之探討
劉駿逸 93M02:膠原蛋白製品的生物活性衰減與抗菌程度變化之研究(July 2004)
蔡濱丞 93M03:自我排列單分子層於順流式電漿系統中反應速率及機制之研究(Jan. 2005)
翁志強 95P01:氧含量在低溫電漿系統中對反應速率及反應機制影響之研究
楊允達 95P02:具誘導生長功能之神經修復導管的製作與效能的研究
吳奕德 95P03:高敏度表面分析與高解析技術對診斷具疾病表現之單一核苷酸多型性效
高啟原94EM01:以金屬蒸氣真空弧離子佈植技術進行氧化鋅透明導電薄膜之製作(Jan. 2006)
林哲瑩94M01:高敏度表面與高解析技術診斷具疾病表現之單一核苷酸多型性:運用SAMs技術固定寡核苷酸(June 2005)
黃芷翎94M02:以不同比例聚乳酸-聚甘醇酸共聚物製作多層孔隙型神經再生導管(June 2005)(2005 科林論文獎)
陳信宏94M03:利用氣態丙烯酸為中間劑以固定幾丁聚醣於電漿活化之L型聚乳酸薄膜表面(May 2006)
張正宏(成大醫工共同指導):植入式多極神經銬電極表面處理(July 2005)
張家維95EM01:以金屬蒸氣真空弧離子佈植技術進行氮化鈦微結構之研究(July 2006)
侯孟新95M01:多孔幾丁聚醣改質膠體對於不同重金屬離子之吸附研究(July 2006)
簡儀楨95M02:超薄蝕刻阻劑在金的圖形製作表面之抗蝕刻機制研究(July 2006)
潘冠廷95M03:多功能微波電漿處理系統之電漿診斷及光阻去除的研究(July 2006)
曾雅君87M01:連續式二氧化碳雷射對牙釉質、牙本質及生醫玻璃之交互作用研究(June 1998,1998材料科學學會論文獎)
中文摘要
突發性的外傷所造成之咬合面不平整,並有磨損碎裂現象產生
我們試著以一種生醫玻璃(DP-bioglass)粉末與磷酸混合,形成類似玻璃離子體的材料做為牙齒裂縫的填補劑
由TGA/DTA分析結果瞭解二氧化碳雷射會使牙釉質、牙本質中的水分蒸發並移除其
將補綴材料填入牙齒表面的裂縫,此材料會與牙釉質
目前在斷裂的牙齒之臨床治療上,多是將斷裂的牙齒拔除或是以複合樹
關鍵字詞:牙釉質、牙本質、二氧化碳雷射、綴補材料、微裂縫。
Y.-C. Tseng, The Interaction of CW-CO2-Laser Irradiation on Enamel, Dentin and DP-Bioglass
Sudden trauma or trauma associated with occlusal disharmonies or extreme clenching and gritting produce vertical fractures. The defect need not be a complete fracture, but may extend through part of the root or crown. If trauma is extreme, it could shatter the crown and root. The crack line usually appears near the developing groove and can extend toward the root or horizontally across the tooth. The crack itself can be an etiological factor in pulpal disease if it extends to the pulp cavity and irritates the pulp physically, or through leakage of liquids and bacterial toxins. It is very important for the clinical treatment to prevent crack line propagation in such a fracture. However, there are still pending to effectively prevent the crack line from propagation, which causes disaster happened.
We are to prepare a glass ionomer composed by self-developed DP-bioglass and phosphoric acid as the crack line repairing paste. CO2 laser will be followed to seal the crack line. In the study, we would like to know whether the chemical bonding could be formed between the interface of paste and fracture teeth after treatment. The microstructure, phase transformation, and thermal reaction among the developed glass ionomer, dental enamel, and dentin will be examined by XRD, FTIR, TGA/DTA and SEM, respectively, before and after exposed to CO2 laser.
The TGA/DTA analysis shows that CO2 laser causes evaporation of water and removal of organic substances from enamel and dentin. Grain growth, recrystallization of crystals and surface melting could be observed from the SEM photography after CO2 laser irradiate onto the enamel and dentin α-TCP which could be traced by XRD analysis appeared both in the dentin and enamel due to high temperature from CO2 laser radiation.
The restorative material was prepared by mixing 2g DP-bioglass with 4ml, 65% H3PO4. After mixed completely, the restorative materials was turned into calcium phosphate monobasic (Ca(H2PO4)2.H20)and silicate pyrophosphate(SiP2O7)in crystalline structure. The crystalline structure of the restorative material was no significant difference after CO2, laser irradiation.
Once pasted onto the surface of the fracture line, the restorative material will react with enamel and dentin to form calcium phosphate dibasic(CaHPO4.2H2O)along the interface of the restorative material and fracture teeth. The new phase appeared along interface was one of the evidence that restorative material and teeth would form chemical bonding after pasted, even in the room temperature. Though CaHPO4.2H2O is an unstable phase in oral environment, it will transform into calcium pyrophosphate(CaP2O7)and then become a stable phase after exposed to CO2 laser.
In nowadays, the fracture teeth should be extracted out and repaired with composite resin in the clinical treatment, but the teeth could not have the function of stress-bearing anymore. In the study, a fracture line on the teeth was pasted with a self-developed glass ionomer and then successfully sealed by CO2 laser. We suggest that the method can prevent crack line from propagation in a fracture teeth and would have a great potential in dental clinical application in the near future.
Keywords: Enamel, Dentin, CO2 laser, Restorative materials, Crack.
王明誠87M02:三維人工髖關節模擬磨耗測試機之設計與製造(June 1998)
中文摘要
人工髖關節在置換後的鬆脫問題,可能源自於應力遮蔽效應所造成的骨
本髖臼-球磨耗測試機之設計,即為加速取得人工髖臼-球組件,在人體骨骼-肌肉周邊之模擬生理環境下,受磨耗而漸進釋出殘屑的種類與數量
關鍵字詞:髖關節模擬磨耗機、設計、製作、磨耗殘屑。
M.-C. Wang,
Three-Dimensional Cup-on-Ball Hip Wear Simulator: Design and
Making
ABSTRACT
Loosening problem occurred gradually on the post-operative hip prosthesis, may be due to the effect of stress shielding that results bone losses, or load-bearing wear that causes wear debris released into its surrounding tissues, etc. These factors will eventually lead to a fixation failure. Rubbing phenomena usually appear at the articulating surfaces of acetabular cup and ball head. Surgeons and related researchers pay much attention to deal with the problem related to contour deformation, which arises as the polyethylene part bears and rubs with much hardened joint-component. They have tried to measure this internal and dynamic effect by separating them at a distance and taking radiographs to obtain macroscopic information about the degree of semi- spherical mismatch and dimensional alternation at the interface. However, this gradually rubbing behavior taking place at the articulating surfaces, displays a three-dimensional motion and a form of microscopic degradation. It still has difficulties to explain well the enlargement of mismatch gap between the implant and the surrounding tissues. Besides, it is also obscure to get the trace of in-situ released species.
Current design and making of cup-on-ball hip joint simulator is to obtain
the types and amount of wear debris generated under a physiological condition of
human skeletal muscle. This study has completed two types of design: one is
based upon hip joint biomechanics; the other is based upon an acceleration
process aiming for material testing. About the design, the loading is controlled
by oil-compressing system. It is variable by adjusting its position, as a fixed
loading form (type 1) or as a loading with cosine function (type 2). The desired
angles set at transverse and sagittal planes are possibly led by linking two
serve motors. The loading and angular setting are monitored by a feedback
control, which will be zeroed at the beginning of each cycle. Little accumulated
error is found. In addition, To collect and analyze the generated wear debris,
with varied testing time or different testing cycles under a simulated
environment, a device with close assemblage is made. It is, consequently,
provides an option to pick up wear debris for further in vitro
studies.
Keywords: Hip Wear
Simulator, Design, Making, Wear
debris.
吳建宏87M03:低溫高密度微電漿處理技術對高分子材料表面改質(June
1998)
中文摘要
本研究利用3-A可調整、陣列天線式微波激發與傳輸之電漿系統設計:最高輸出功率2 KW,12×12子陣列數、介電室能量傳輸類別,其具有高離子化密度、大面積處理
實驗結果顯示:對於PP不織布與PE膜,以600 W激發Ar、O2、N2三種氣體電漿處理,皆可於極短時間約數秒至數十秒
關鍵字詞: 微波電漿、PP不織布、PE膜、表面活化、表面改質。
C.-H. Wu, Effect of Temperature to High Density Microwave Plasma Technique Applied to Polymer Surface Modification
This study utilizes 3-A adjustable antenna-coupling microwave plasma system, with max. output power 2KW, 12 X 12 elements array (ca. 20 X 20 cm2) and fused-glass for wave or energy transformation. Such system enables a plasma generation of high density and uniform ion distribution that projected onto an extensible and effective domain at low temperature. Current work deals with two different materials: PP fabric or PE film, varied gas plasma: Ar, O2 and N2 and in sequence, desired monomers grafting: HEMA, AAc. To investigate the plasma-initiated functional groups at the modified surfaces, some analytical methods, such as ESCA, ATR/FTIR, SEM, peroxides concentration determination and wettability tests, are employed.
Our
result has shown that within several seconds of 600 W, Ar, O2 or
N2 plasma pretreatment, PP fabric and PE film are activated at
surface, so as surface tension of film and capillary attraction of fabric are
both augmented. In detail, water-holding capacity of the plasma-pretreated PP
fabric extends from 0% to 665%; surface tension of treated PE film increases
from 30 dyne.cm-1 to 38 dyne.cm-1 or receding
angels decreases from averaged 64°to 11°. The ESCA and ATR/ FTIR measurements
elucidate the formation of oxidative groups that contribute to surface
polarization. Furthermore, the characteristic properties of grafted p-HEMA or
p-Aac surfaces can be preserved. This research provides that with the advantages
of this microwave plasma system and subsequent addition of specific properties
for PP fabric and PE film, variety of surface properties can thus be
proposed.
Keywords: Microwave plasma, Polypropylene non-woven fabric, Polyethylene film, Surface activation, Surface modification.
游永祥88M01:微波電漿與高週波電漿的特性研究(June 1999)
中文摘要
電漿是由不平衡態的物質所組成。當電漿離子化程度增加
在指定參數條件下之研究結果顯示: 由量測系統所取到的數據有良好的重覆性(電漿反應室內的電漿均勻度
關鍵字詞:電漿離子化、電漿診斷、靜電式探針、計算模式。
J.-S. Yu,
Characterization of Microwave Plasma and Radio-frequency Plasma
System
ABSTRACT
Plasma is composed of non-equilibrium species. When plasma ionization is increased, the trend to stabilize it is also accelerated. Consequently, plasma diagnosis differs with the applied methods or computing models. Current design utilized a Platinum or Tungsten electro-static probe penetrated through the plasma reactive chamber, provided with positive and negative voltages, and statically measured the state of electron flow (or electron temperature) to monitor the electron (or ionization) density, uniformity and stability of generated plasma, varying with time.
The measurements have provided valuable information to adjust changing
condition in practical plasma applications. Compared microwave with radio
frequency (RF) plasma systems in assigned conditions, current design
demonstrated reproducible approaches to theoretical value on measuring the
electron temperature (or derivable to plasma density). Using the computation
models from Chen and Bohm, a 3-A antenna-coupling microwave plasma
generated an electron density of ca.
109~1010.cm-3 (for N2 and
O2 plasma), compared with RF plasma discharge (with bias electrodes)
of ca. 108~109.cm-3 (using t-test and ANOVA
tests, α=0.05). The result from Optical Emission Spectroscopy also indicated the
presence of various excited species. This study has contributed an economic
installation to monitor plasma processing and a reference for integrated
estimation on plasma generation.
Keywords: Plasma
ionization, Plasma diagnosis, Electro-static probe, Computing
model.
許迪俊88M02:可攜式微生物毒性感測器之製作與評估(June 1999)
中文摘要
本研究是關於生產事業單位廢水處理過程水質毒性的可攜性監測系統
本實驗利用三種毒性物質進行毒性試驗,並將本裝置應用於
關鍵字詞:生物感測系統、廢水的毒性、電化學反應、微生物。
D.-J. Shu, A
Biosensor Device with Portable Design and In-situ Toxicity Detection in Waste
Water
ABSTRACT
This study deals with a portable bio-sensing system combined with specific signal processing to detect water's toxicity or nutritivity, before processing treating water into biological treatment tank. Based upon the toxic water capable to inhibit micro-organic (or thus to consume less oxygen), the tiny current output is varied with biochemical or electro-chemical reactions on the electrode. This device is programmed to distinguish the degree of waster's toxicity and to measure the quantity of inhibited micro-organic according to biological activities induced current output effect.
Current device includes an amplifier, a signal filter, an
analogue-digital transformer, a DC supplier and a data processor. The printed
test plate with millions of attached micro-organic also integrates to the device
as a measuring system, which is miniaturized with a function of signal
processing and in-situ display. Evaluation of three different degrees of toxic
species and two case studies on an electronic and a textile factory have
demonstrated that the degree of toxicity on sampling specimen can be roughly
distinguished within 8 min. The result is mainly correlated with electro-induced
biological activities, however, it shows a non-linear relationship with
traditional chemical oxygen demand (COD) tests.
Keywords: bio-sensing
system, water's toxicity, electro-chemical reactions,
micro-organic.
孫銘偉88M03:利用微波電漿活化聚丙烯不織布纖維表面以固定蛋白質(June
1999)
中文摘要
為擴充聚丙烯不織布在醫療上的用途,本研究利用低溫微波電漿表面改
本研究利用3-A可調整、陣列天線式微波激發與傳輸之電漿系統,以氧氣電漿來進行聚
關鍵字詞:聚丙烯不織布、微波電漿、連結反應、蛋白質固定。
M.-W. Sun, To
Immobilize Proteins on Polypropylene Non-woven Fabric Surface Initiated by
Microwave Plasma
ABSTRACT
尤昶清88M04:髖關節模擬磨耗機對人工髖臼-球之磨耗殘屑研究(June 1999)
中文摘要
為了評估可能導致人工髖關節鬆脫原因中有關磨耗殘屑的問題
實驗結果顯示:有金屬離子與其氧化物、聚乙烯屑(可能為較低分子量
關鍵字詞:超高分子量聚乙烯、磨耗殘屑、形態、應變硬化。
C.-C. Yu,
Microscopic Studies of Wear Debris Generated by a Cup-on-Ball Hip Wear
Simulator
ABSTRACT
To evaluate the loosening problem caused by wear-associate debris after a hip-joint operation, a cup-on-ball simulator monitors the articulation. The design of this developed cup-on-ball hip wear simulator tends to approach hip biomechanics, to utilize maximum gait loading and therefore to accelerate an estimation of wear on the upper part of total hip prosthesis. A device with close assemblage is made, which may accumulate the wear species. By this design, it approaches to qualify and to quantify the wear substances. The release rate and sequence of wear debris can also be detected. The wear species analyzed by SEM, ICP-MS and ESCA with varied testing cycles (0.3, 0.6, 1.0 and 1,3 millions) include metallic ions, metal oxides, scissioned polyethylene (usually low Mw) or compounds from their mixtures. Two types of acetabular cup, classified as A (8 mm in thickness) and B (6 mm in thickness), were tested and the accumulation of mass increased with testing cycles, however, they were not shown as a linear relationship.
Experimental results have also shown that: B-type sample released the
greater gross amount than A-type one (likely influenced by the design of cup).
The accumulated wear debris both formed in spherical foam-like and were composed
of several microns in dimension primitively. As strain-hardening effect
greatened on the load-bearing polyethylene, the release of plate-like wear
debris augmented and caused upward increase in an added sequence. Measurements
on the circulating liquid have supported that Co, Cr and Mo elements would
partially penetrate the filter and obviously contain in the circulated liquid;
the release rate, though irregularly distributed (due to metal oxidation),
varied with the types of sample and different testing
cycles.
Keywords: UHMW
polyethylene, Wear debris, Morphology, and Strain
hardening.
賴育誠89M01:全人工髖關節之鬆脫問題的實驗模擬與評估(May 2000)
中文摘要
對於經過全人工髖關節手術後的患者,常會在其手術後的幾年內發生不
由實驗結果發現:以模擬磨耗機測試離子植入式髖臼杯,B-1016 ions/cm2在模擬磨耗130萬次後共釋出殘屑8 mg,比B-1013
ions/cm2的殘屑總重17 mg少,又比A產品的51.4 mg及B產品的74.7 mg來得更少。證實了離子植入式超高分子聚乙烯之抗磨耗效果佳
關鍵字詞:超高分子聚乙烯、磨耗、離子植入、微振磨耗。
Y.-C. Lai,
Laboratory Simulation and Assessment of Total Hip Prosthesis on Loosening
Problem
For patients inserted total hip joint prostheses, clinical findings on implant detachment, malfunction, and loosening-associate problems are frequently observed after a period of time. To evaluate various potential factors caused fixation failure, laboratory-assisted assessments are required. Present study using cup-on-ball hip wear simulator approaches to comply with gait analysis of hip, accelerates in-vitro tests by entering maximum angular setting and obtains relative abrasive condition at the interface. Morphologies and concentrations of wear debris may affect the attachment of peri-prosthetic tissues; consequently, this work deals with three main topics: (1) To improve wear resistance of UHMW polyethylene acetabular cup as the bearing part, the load-bearing properties of polyethylene are enhanced by nitrogen ion implantation; the doses with low current density differ from 1013 ions.cm-2 to 1016 ions.cm-2. (2) Wear debris generated from simulator is compared with in vivo particles taken from tissues surrounded the failure implant. (3) Initiation of fixation failure with musculo-skeletal system rises with fluctuations of stress-strain relation at the implant/tissue interface. Because of varied materials’ characteristic at the contact surfaces, relative friction causes mobility between adhesive components and gradual increase of plastic strain, and eventually brings about macro-scale dislocation between implant and surrounding tissues. This study is to propose a possible mechanism, using micro-motion tester to simulate the occurrence of implant displacement at the inserted interface before loosening.
Experimental result on the ion-implanted polyethylene has demonstrated
that an important surface-hardening transformation at polyethylene surface is
found. Using cup-on-ball hip joint simulator, the release rate and the sequence
of wear debris are detectable from the accumulated filters varied with testing
cycles up to 1.3 M, e.g. weight loss of non-treated polyethylene is ca.
74.7 mg; similarly, for the 1013 ions.cm-2 implanted polyethylene is 17 mg, while
for the 1016 ions.cm-2 implanted polyethylene is ca. 8
mg. Wear rate of ion-implanted polyethylene significantly decreases owing to the
formation of a hardened (or cross-linked) layer at surface. Analytical result
supports that morphologies and concentrations of wear debris vary with testing
cycles, which include delaminated species and carbonates from the scission of
polyethylene in foam- or plate-like dimension. On the other hand, because of
varied materials’ characteristic at the contact surfaces, their bearing
capabilities to keep in the elastic region are different. Micro-motion at the
fixed interface eventually provokes macro-scale dislocation between implant and
surrounding tissues. Present methodology proposes a possible mechanism occurred
at the inserted interface before loosening. The parameters used are correlated
with Ti-based femoral stem with respect to bone cement; the range of
micro-motion is assigned as ±40μm per cycle with constant speed of 0.0014 mm/s,
moving forward for 10,000 cycles each, and under a bearing load of 100 N.
Experimental result on micro-motion has indicated that boundary friction causes
plowing effect and thus reduced contact area; a localized edge effect occurs.
Further SEM observations and roughness tests provide that the edge-effected
width on bone cement is ca. 80
μm (due to ±40μm movement each
cycle); some 20μm are caused by the accumulation of wear debris. Along partial
edge of Ti-base pin, small amount of PMMA particles are adhered. The roughness
at both surfaces after micro-motion tests is corresponded to friction-to-wear
mechanics. When the inserted stem loses mechanical interlocks with bone cement,
a gradual slip at the interface decreases their adherence. The released species
may facilitate and accelerate their detachment and diminish the initial elastic
range of bone cement. This may create loosening or shrinking effect on the
inserted stem. A conclusion for both behaviors suggest that a variation of
relative and dynamic interface in use.
Keyword:
Total hip joint, Wear resistance, Ion implantation, Wear debris,
Micro-motion.
許高源89M02:陣列式微波電漿對聚酯纖維聚醯胺纖維之表面功能性改質(June 2000)
中文摘要
本研究針對一般合成纖維產物的聚酯纖維和聚醯胺纖維為基材
實驗結果顯示:檢測各紡織製程中,各流程處理步驟以後加工之後再進
關鍵字詞:聚酯、聚醯胺、微波電漿、親水性、生物活性。
K.-Y. Shu,
Functional Surface Modification of Polyester and Nylon-6 Fabrics Initiated by
Antenna-Coupling Microwave Plasma
ABSTRACT
This research utilizes polyethylene terephthalate (PET) and nylon-6, commonly fabricated fabric products, as the substrates for proceeding surface modification. Antenna-coupling microwave O2 plasma is applied to induce surface activation and subsequently to graft copolymerization with functional groups, like acrylic acid (AAc) and 2-hydroxyethyl-methacrylate (HEMA) in this study. Two main applications are performed: The first application evaluates the capability of water absorbency, moisture regains and wicking rate on the modified textiles; The second application immobilizes proteins on the pAAc- or pHEMA-grafted textile surfaces. Surface analyses are done using Fourier-transformed Infra-red equipped with Attenuated Total Reflection (FTIR-ATR) and X-ray Photoelectron Spectroscopy (XPS).
Experimental result included surveying procedures for the textiles has
provided that surface activation and hydrophilic treatment are much suitable for
the finished textiles. For the controlled amount of 148.4±6.2 μg.cm-2 AAc and 313.3±42.0
μg.cm-2 HEMA, water absorbency
increases up to ca. 57% for PET and ca. 170% for nylon-6, while moisture regain
increases up to ca. 50% for PET and ca. 55% for nylon-6. These improvements
result from the inclusion of O=C-OH or –OH group on the fabric surfaces, which
are interpreted by FTIR-ATR and XPS measurements. Subsequently, the pAAc- or
pHEMA-grafted surfaces are covalently bonded to collagen (-NH2) or
heparin (O=C-NH) by the addition of 1-ethyl-3-(3-dimethylaminopropy
Keywords: Polyethylene
Terephthalate, Nylon-6, Microwave Plasma, Hydrophilic,
Bioactivity.
翁志強90M01:順流式遠端電漿對單層有機金屬表面反應機制之研究。
中文摘要
本實驗使用以SAMs方式在金(111)晶面上固定上長鏈的碳(C18)結構,來模擬常用高分子表面結構,以整齊排列、無雜質
(1)微波產生器產生2.45GHz的微波由同軸電纜線傳至共振腔,配合自行設計的真空處理腔室
(2)單針式Langmuir
probe對電漿的電子溫度、電漿密度進行診斷,瞭解作用於基材表面的離子
藉由上述的研究探討順流式電漿機台在處理高分子時其電子、離子
(3)電漿中除上述離子、電子、自由基外尚有紫外光可能對基材作用
關鍵字詞:自行組合單層膜、Langmuir 探針、後輝光電漿、X光光電子能譜儀、接觸角。
C.-C. Weng, Chemical Reactions of Downstream Microwave Plasma to the Alkanethiolate Self-Assembled Monolayers on Gold Surface
Low-temperature plasma processing has been greatly considered as a vital technique for polymer surface modification. According to the characteristic of plasma generation, the applied processing parameters and the type of gas plasma, the organic substrate may arise some effects such as polymerization, superficial chemical reactions and cross-linking and create specific, applicable and functionalized surfaces. This study utilizes self-assembled monolayers of the octadecanethiol (C18H37SH, or ODT) on Au (111) surface to simulate an organic structure with well-packed and long carbon chains. In this experiment, downstream N2 microwave plasma is generated by 80 W under 1 torr; plasma-induced chemistries on the ODT/Au surface are studied. Using Langmuir probe, the state of electron temperature and the electron (or ionization) density are statically measured; they provide valuable information to adjust changing condition in practical plasma applications. The effect of UV generated in plasma, for the wavelengths higher than 200 nm, to ODT/Au is also evaluated. Water contact angle and X-ray Photoemission Spectroscopy (XPS) measurements are applied for verifying structural modification at surface.
Experimental result has indicated that current downstream plasma provides
plasma density of ca. or electron temperature of ca. 0.46 eV; it is regarded as
low-density plasma. Surface analyses by XPS have revealed that after
N2 plasma treatment, new chemical bonds such as C-N, C-O, C=O and
O=C-OH are formed on the modified ODT/Au surface. These polarizable groups arise
a hydrophilic characteristic at surface and decrease water contact angle from
120o to 18o. Analytical result also implies that
N2 plasma takes O2 and reacts with ODT/Au within 10sec.
After 30sec of plasma treatment, the C/Au ratio decreases, which is correlated
with etching effect on the ODT/Au surface. After 60sec of plasma projection onto
the ODT/Au surface, all N, O and C elements are decreased, however, relatively
small decrease ratio of C is found, which may be directed to the formation of
cross-linked structure at surface. Moreover, for introducing UV generated in
plasma, wavelengths longer than 200nm and up to 120 sec, the ODT/Au structure is
insignificantly affected. This consequence has confirmed that UV produced in
low-density plasma does not have the capability to provoke chemical reactions
with the ODT/Au surface.
Keywords: Downstream
Plasma, Langmuir Probe, Self-Assembled Monolayers, Hydrophilic Group, X-ray
Photoemission
Spectroscopy.
邱耀慶90M02:全人工髖關節損壞機制之研究:臨床與實驗取得殘屑之比較。
中文摘要
人工髖關節的鬆脫問題,一直是影響植入物執行效率的重要因素
實驗結果發現,以去離子水模擬關節滑液,孔徑100
μm聚丙烯濾紙收集磨耗殘屑,於體外模擬磨耗所得殘屑大小約為10~50 μm。若以小孔徑玻璃纖維濾紙(0.7 μm)進行收集,則可收集到較為小型殘屑(~10
μm)。殘屑重量累積速率隨測試次數的增加,並無顯著差異
關鍵字詞:免疫反應、人工髖關節磨耗機台、磨耗殘屑
Y.-C. Chiu, Failure
Mechanism of Hip Joint Prosthesis: Wear Debris Obtained from Tissue-Detached
Particles in Comparison with Laboratory Assessment
ABSTRACT
Loosening of total hip joint prosthesis provokes related orthopedic problems, which greatly influence the failure events from implant fixation. Aimed to study the wearing mechanics of joint components and the wear debris induced peri-prosthetic tissue responses, this work looks into the impact of wear debris generation in human physiological system and of bone resorption leading to eventual failure of hip joint prosthesis. A cross-mode cup-on-ball hip joint simulator is utilized for testing under assigned conditions. Study of laboratory-made wear debris compared with tissues-detached particles tries to interpret the occurrence of fixation failure for hip prosthesis.
Experimental result has demonstrated that using de-ionized water as
circulation liquid for lubricating, a filter with reduced pore dimensions (~0.7
μm)
is capable to obtain small particles such as ~10 mm in size. Similarly, this
filter is suitable to sieve tissue-detached particles and to prevent them from
agglomeration (~10 μm in size). Morphologies of laboratory-made wear
debris are correlated with the wearing modes at the bearing interface.
Mechanical properties of UHMW polyethylene acetabular cup against metallic ball
head diversify with the degree of applied loads and abrasion-induced effects
such as molecular rigidity or strain hardening at the outmost surface. In the
early stage, the scission of polymeric chains creates polarizable ends and
initiates foam-like agglomerates; then, crossing-mode abrasion provokes shear
stress on the gradually hardened layer and leads to the generation of plate-like
debris. Morphologies and compositions of laboratory-made wear debris differ with
testing cycles (TCs). An average mass release of ~16.5 mg per million TCs is
calculated, which corresponds to clinical findings as well as previous
simulations (~18 mg per million TCs). Laboratory-made debris and tissue-detached
particles do not obviously contain metallic elements. It is thus estimated that
wear debris is mainly composed of polyethylene species. In clinical case of
wearing concentration on polyethylene cup that causes metal ball head rubbing
through it and bearing with metal cup or mesh, the content of metal elements in
tissue-detached particles becomes evident.
Keywords: Total hip joint
prosthesis, Ultra-high molecular polyethylene, Laboratory-made wear debris,
Tissue-detached particles.
劉光弘90M03:利用紅外光光譜建立即時微量煙霧監測系統及經濟型二氧化碳感測器
中文摘要
本研究利用可調式長光徑管及傅立葉轉換紅外光譜儀建立即時監測煙霧
基本實驗利用模擬燃燒室對Nylon
6,在N2環境下經熱烈解後所產生的氣體分析其組成。Nylon
6為燃燒物種,其中含有醯胺的結構,受熱後可能會產生有害氣體,如:CO、CO2、HCN、NH3。利用熱重分析儀對Nylon
6分析,得到其在N2與Air環境中,反應溫度範圍分別為377~500
oC與375.7~500 oC,He環境之反應溫度範圍則與N2環境中相近,故以此結果為模擬燃燒室之加溫參數,並設定ASTM相容之模擬燃燒室,使加熱功率為600瓦連接至1-16 m可調式光徑管加以分析。燃燒室內氣體環境比例使用多孔道質量流量控
關鍵字詞:紅外光、煙霧感測系統、nylon 6、熱裂解、CO2感測器。
K.-H. Liu, On-line
Trace Smoke Analysis Using Infra-red Active Monitoring System and Making of
Economical Type CO2 Gas Sensor
ABSTRACT
This work utilizes a variable path cell and Fourier-Transformed Infrared Spectroscopy (FTIR) to establish on-line IR-active smokes detection system; based upon the investigation, we apply its principal to make an economic type of CO2 sensor. In the fundamental study, nylon-6 forms pyrolysis under oxygen-free N2 environment. Nylon-6 is naturally flammable and is composed of CO-NH group; thermally decomposed by-products such as CO, CO2, and HCN are toxic to human being. Analytical result using Thermal Gravity Analyzer (TGA) demonstrates that under N2 or air environment, the reactive temperatures of nylon 6 occur in the range of 377-500oC or 375.7-500 oC; the reactive temperatures under He are similar to N2 environment.
Taking TGA results as the references, practical experiments proceed in an
ASTM-comparable reactive chamber using a power of 600 W in diverse heating rates
and multi-channel mass flow controller to mix with different ratios of
N2, O2 and CO2; subsequently, the smokes flow
through a 1-16m variable path cell and are analyzed without delay. Analytical
result using Mass Analyzer indicates that the ratio of N:C:H of nylon-6 is equal to
11.66:61.30:9.80, which corresponds to a heat value of 26.6 KJ.g-1. Survey
for gaseous components designates the presences of IR-active absorbance in the
range of 2341-2360 cm-1 and 666-670 cm-1 for
CO2, 1670 cm-1 for CO, 1557 cm-1 for –CO- and
–CNH-, and 930 cm-1 for NH3, respectively. Such released
substances detected by Mass Spectroscopy present the molecular weight of 27
(HCN), 28 (CO), 43 (amide) and 44 (CO2), respectively. Using FTIR to
detect the trace amount of smoke is thus feasible and potentially applicable for
IR-active sensing devices to determine specific gaseous by-products. Applying
this study to identify low CO2 concentration, we minimize the
dimension of variable path cell and detect the intensity of IR wavelength around
4.3 μm. A correlation between CO2 concentrations (Y) and electrical
signals (X) is calculated as: Y = 26,239 – 103X with a correlation coefficient
of –0.99079. Data processing is recorded using CPU of 89C52 and is displayed on
LCD; the detectable range is 0-6,000 ppm. This minimized device is applicable
for air quality control in a public sector, or for early monitoring of irregular
CO2 increase in a close environment.
Keywords: Infrared,
Smokes detection system, Nylon 6, Pyrolysis, CO2
sensor.
吳奕德91M01:利用真空濕式反應室進行即時就地膠原蛋白固定之研究。(2002同步輻射研究中心學生論文獎第二名)
中文摘要
本研究使用順流式微波氮氣電漿對排列完整的自我組裝形成ODT在Au(111)、Ag(111)的單層膜結構反應,使其表面產生極性基團,並隨即以稀釋的氣態丙
關鍵字詞:自我組裝單層膜、順流式微波電漿、真空濕室化學反應室系
Y.-T. Wu: Wet Cell System for on-line characterization of collagen immobilization (Student Dissertation, Second price Winner, SRRC Eighth Users’ Meeting and Workshop on Application of Synchrotron Radiation in Biology, Oct. 31-Nov. 2, 2002.)
This study utilized nitrogen downstream microwave plasma to react with the well packed self-assembly monolayers (SAMs) of 1-Octadecanethiol (ODT) adsorbed on Au (111) or Ag (111) substrate. Plasma processing was to create polarizable groups for subsequent grafting with diluted acrylic acid (AAc) monomer. The functional group of AAc, O=C-OH, was purposely bonded on the plasma-treated surface without obvious damage to sulfur/metal bonds. We took SAMs of 11-mercaptoundecanoic acid (MUA) on Au or Ag surface as the reference. Collagen was subsequently immobilized on these two types of surfaces under a custom-made well cell system. Synchrotron soft X-rays combined with high-resolution X-ray Photoelectron Spectroscopy (XPS) were applied to characterize the variations of chemical structures. The S 2p, C 1s, N 1s and O 1s spectra were typically analyzed. Experimental result has demonstrated that using MUA/Au, Ag as the substrates, collagen immobilization process in wet cell system or in atmospheric environment did not have qualitative or quantitative difference. Firstly, our well cell system is feasible to carry out on-line collagen immobilization process. We also compared the plasma-treated ODT surface with that after AAc-grafting. Using similar method to immobilize collagen in wet cell system, both surfaces were capable to have collagen immobilized. Nevertheless, their immobilized quantities were significantly different. The most pronounced processes are the participation of oxygen to the plasma-treated ODT surface, the generated oxidative groups, particularly the limited amount of O=C-OH group, are likely to bind with protein molecules. Overall, this work has completed a combined collagen immobilized process in wet cell system, followed by on-line XPS characterization. Fundamental studies on reactive mechanisms for biomolecules are expectative.
Keywords: Self-Assembly Monolayers, Downstream Microwave Plasma, Wet Cell System, X-ray Photoelectron Spectroscopy.
謝登讚91M02:利用同步輻射源研究具功能性尾端之單層有機分子膜
中文摘要
本研究使用整齊排列的1-Octadecanethiol
(HS-(CH2)17-CH3,ODT)及11-mercaptoundecanoic acid
(HS-(CH2)10-COOH,MUA)自我排列單分子膜使其吸附在Au(111)或Ag(111)晶面上做為試片。以高光通量、準直性佳的同步輻射光為光源
關鍵字:自我排列單分子膜、同步輻射X光破壞、X光光電子能譜儀、硫-金屬鍵結。
This study utilizes well-packed self-assembled monolayers (SAMs) of
1-Octadecanethiol (HS-(CH2)17-CH3, ODT) and
11-mercaptoundecanoic acid (HS-(CH2)10-COOH, MUA) adsorbed
on Au(111) or Ag(111) surface as the substrates. Synchrotron radiation source
provides X-rays with high photon flux (PF) and excellent collimation, the
intensity of synchrotron soft X-rays increases high-resolution capacity for
X-ray Photoelectron Spectroscopy to analyze the irradiated ODT/Au and ODT/Ag
films. We discuss the relations of different scan numbers (SNs, or irradiation
time) or PF (or photon intensity) with respect to X-ray induced damages on
S-metal bonds (S 2p spectrum) and alkyl chains (C 1s spectrum). The critical
irradiation effect, which provokes S 2p doublet change, was estimated as PF of
0.6 nA and SNs over 5. On the other hand, the alkyl chains were supposedly
disordered or crosslinked when PF of 0.6 nA and SNs over 10, or PF of 1.2 nA and
SNs over 5 was reached. From S 2p and C 1s spectra, we found that ODT on Ag was
much resistant to X-ray induced damage than ODT on Au. Similar result was
obtained on the irradiated MUA/Au and MUA/Ag samples. Therefore, the intensity
of S-metal bonds is favorably employed as an index for the degree of synchrotron
X-ray induced damages. Our result has demonstrated that synchrotron X-rays have
similar damage effects to SAMs with –CH3 or O=C-OH tail group, and
S-Ag bond is much resistant to X-ray induced damage than S-Au bond.
Keywords: Self-Assembled
Monolayers, Synchrotron X-rays damage, X-ray Photoelectron Spectroscopy, S-metal
bond.
林志達91M03:經濟型血糖感測器之製作及市售電極片之評估
中文摘要
本研究是利用酵素能夠識別特定分子的特性,並且催化這些分子進行氧
關鍵詞:酵素,電極,電位,葡萄糖。
Abstract
This work is based upon the characteristic of an enzyme capable to
recognize specific molecules, to promote their oxidative reactions, and to
provoke quantitative changes of a particular reactant or product. The extent of
substance can be furthermore transformed into electrical signals when
electrochemical reactions occur. Variation of signals can be expressed as the
relation between the consummation of enzyme and the quantity of the specific
molecule. For a spontaneous process, a required energy is provided to the
reactants, the applied voltage for the energy is studied and fixed at 0.8V. This
voltage supply system includes a working electrode and a reference electrode.
The reference electrode controls the potential at the working electrode, which
records electrical currents from varied enzymatic reactions occurred at the
electrode. By evaluating three dependent parameters: working voltage of enzyme
electrode, pH value of enzymatic reactions and detecting range of glucose
concentration, the voltage or current derivative from the reaction can be
measured. This study is also extended to commercially available electrodes and
applied to assess their output voltage and quality of measurement. The
appropriate detecting range of glucose concentration is optimized in the range
of 100-290mg/dl. The most sensible working voltage is fixed at 0.8V. With these
detecting levels, the pH value in the range of 6.6-7.6 for enzymatic reactions
does not significantly affect ΔV/Δt (the change of measured voltage with respect to
the measuring time). Similarly, we examine the influential factor of glucose
concentration to ΔV/Δt, a significant difference is obtained and the
result is highly reproducible. It is therefore applicable to design or to make
glucose sensors. The suitable measuring duration is set in the range of
35-70sec, when ΔV/Δt is approximately linear. To avoid electrical
disturbance and to keep a quick response, a measuring time of 40sec is
optimized. Based upon these factorial studies, the commercially available
electrodes, R、B及A, are assessed. Within the measuring time, the ΔV/Δt for R is highest and its
correlation coefficient is around 0.90-0.99. The result of this study is
therefore valuable to provide a quick quality assessment for making as well as
selecting glucose sensors.
Keywords: Enzyme,
electrode, potential,
glucose.
陳冠宏91M04:枯草桿菌與嗜熱桿菌固定於板式電極對不同濃度的毒性水樣之微生物
中文摘要
本研究之微生物感測系統內建特殊算數程式以檢測廢水毒性
關鍵字:微生物感測系統,抑制率,計算模式,相關係數。
Abstract
In
this study, a microbial sensing system (MSS) with a built-in special processing
algorithm has been developed for detecting wastewater’s toxicity. Bacillus
subtilis, Bacillus Stearothermophilus and Bacillus Sphaericus
were utilized as sensing components of the system to initiate biological and
subsequent electrochemical reactions. The infinitesimal currents are correlated
with the variation of defined dosages of toxicity on the bacteria-attached
electrodes. The addition of toxic substances tends to inhibit oxygen uptake rate
of the bacteria, which leads to induce electrochemical or charge transfer
effects and therefore their relationship can be correlated with the toxicity of
sampling water. The characteristic voltage-time curves are fairly interpreted
using four types of calculation methods, with which specific inhibition rates
(I%) are thereafter expressed. Using the calculated I% close to the value
measured by Oxygen Dissolved Analyzer (ODA) and the shortest response time of
such method, an optimized MSS with such built-in processing algorithm is
provided. With the optimized reactivation time and bioactivity for the bacteria
attached on the electrode, the analytical result has demonstrated that these
bacteria-attached electrodes are capable to detect phenyl concentration in the
range of 800-4800mgl-1, Cu2+ concentration in the range of
80-160mgl-1; however, Bacillus Sphaericus-attached electrode
exhibits the most sensitive interpretation to Cu2+. The Bacillus
subtilis-attached electrode has difficulty to distinguish octanol at low
concentrations; nevertheless, the other two electrodes are capable to detect
octanol’s concentration in the range of 80-400mgl-1. The correlation
coefficients between measurements using MSS and ODA are 0.962 for Bacillus
subtilis-, 0.945 for Bacillus Stearothermophilus-, 0.781 for
Bacillus Sphaericus-attached electrode, respectively.
Keywords: Microbial sensing system, Inhibition rate, Calculation method,
Correlation coefficient.
田育彰91P01:固定生醫單體之生物活性與結構穩定性之探討
中文摘要
利用低溫高密度氧氣微波電漿活化聚丙烯不織布,經電漿處理數秒可使
關鍵詞:聚丙烯不織布、微波電漿、生物單體、生物活性、滅菌測試。
Yu-Chang Tyan 91P01:Study of Bioactivity and
Structural Stabilization of Immobilized Biomolecules
Abstract
Low-temperature high-density O2 microwave plasma was utilized for the activation of non-woven polypropylene (PP) fabric. With several seconds of plasma treatment, highly oxidative groups were created at surface. The diluted acrylic acid (AAc) was subsequently graft-copolymerized to obtain a surface with functional and hydrophilic structure. The grafting amount was 187±0.54 μg/cm2. To originate biocompatible function for biomedical uses, bio-molecules: collagen type III, gelatin, heparin and chitosan, were then immobilized on the fabric using EDC as coupling agents. The biomolecule-immobilized substrates were carried out blood compatible and sterilization tests to characterize their surface properties. The collagen-bonded PP non-woven fabric was employed for sterilization test and for the index to find out an appropriate dose. The structural denaturation of immobilized collagen induced by irradiation or energy accumulation was also discussed. Using Fourier-Transformed Infrared with Attenuated Total Reflection and Electron Spectroscopy for Chemical Analysis, we examined the chemical structures of samples with different treatments. To quantify the immobilized amount of biomolecules, coloring or weighting method was applied. Experimental result demonstrated that The O=C-OH group of the grafted pAAc was covalently bonded with biomolecule and formed the amide bond (O=C-NH). The functional groups of the immobilized biomolecules were well identified. Using blood clot tests, these four kinds of the immobilized biomolecules still retained their original bioactivities. Nevertheless, the immobilized quantity and the bioactivity of the immobilized heparin were influenced by the processing pH environment and ionic strength. The bioactive collagen-immobilized samples were then sterilized using UV-254nm or gamma ray irradiation, which provoked α-helix, amide I and II damages. Subsequently, the sterilized samples in different degrees were assessed by activated partial thromboplastin time, thrombin time, and fibrinogen concentration tests. By means of cell counter and Scanning Electron Microscopy, we counted red blood cells and platelets adhesion in the modified porous matrix, as well as the morphologies of platelets. The above-mentioned observations were significantly changed with the increase of UV exposure time or gamma ray irradiation dose. From “upholding bioactivity” point of view, the optimized UV exposure time should be less than 20 hrs or gamma ray irradiation dose less than 10 KGy. Still, from our sterilization test, the gamma ray irradiation dose could be reduced to 7.5 KGy, whereas the UV exposure time should be higher than 20 hrs. In the latter case, UV exposure would significantly diminish the bioactivity of the immobilized collagen.
Keywords: PP non-woven
Fabric, Microwave plasma, Biomolecules, Bioactivity,
Sterilization.
王明誠91P02:利用同步輻射源進行電漿誘導生成官能基對生物單體固定之模式研究
中文摘要
本研究利用順流式微波氮氣電漿,對排列在Au(111)、Ag(111)表面的直鏈碳及芳香環自我組裝單分子膜進行表面反應,並以同步輻射光作為高強度X光光源,配合高能量解析度之X光光電子能譜儀進行表面分析,探討電漿內的物種對於單分子膜表面的物理化學作用。再者,以電漿作用後的自我組裝單分子膜隨即與氮氣稀釋之5 %丙烯酸氣體進行氣態接枝反應,在不破壞金屬與單分子膜鍵結的情形下,使單分子膜的碳鏈末端活化位置接上羧基,以利於後續對特定生物單體接著及做為分子診斷之應用。
由於高強度同步輻射光源對自我組裝單分子膜表面可能造成結構之破壞,實驗設計中加以評估與討論。實驗結果顯示:於390 eV的光能量下,隨著掃描次數或光子密度增加,S 2p光譜表示束縛能會由S與金屬鍵結的162.0 eV逐漸位移到163.2 eV左右,說明了S與金屬的鍵結可能受到高強度同步輻射光源破壞而斷鍵。然而,只要在光通量為Ni mesh = 0.6 nA下,掃描次數低於10次以下,則直鏈碳自我組裝單分子膜不受到光源照射的影響。此結果有利於本論文所利用同步輻射光作為X光光源而進行的研究。
於電漿物理特性方面,本論文設計是要產生低離子化密度、但高自由基含量之電漿物種。利用靜電式單探針量測電漿電性參數並計算結果顯示:試片處理端的電漿密度控制在 ,換算電子溫度為0.46 ± 0.04 eV之順流式電漿。以此低離子化密度對直鏈碳及芳香環自我組裝單分子膜作用,其分析結果顯示:電漿物種可使直鏈碳自我組裝單分子膜的表面產生以C、O為主的極性基團,並使處理後的表面由疏水性轉變為親水性,推測為電漿中自由基所引起的化學作用。於相同直鏈碳鏈長下,Ag為基材的自我組裝單分子層表面抵抗此電漿破壞能力比Au為基材的表面要強;而對同質基材而言,直鏈碳鏈長愈長,其抵抗電漿破壞能力就愈強,而芳香環自我組裝單分子膜表面抵抗電漿破壞的能力又比直鏈碳要弱。另一項發現就是於單分子膜受到電漿作用後,可於被處理表面觀察到強的O 1s峰值的存在,表示低壓無氧環境中,行進的反應性電漿物種帶走管壁吸附,極低含量之氧的物種參與電漿的反應,進而成為單分子層表面新的化學組成的一部分。
使用電漿活化處理後的單分子膜與稀釋之丙烯酸氣體進行氣態接枝反應,經表面分析之結果顯示:具有含氧基團之直鏈碳與芳香環自我組裝單分子膜表面可接著丙烯酸,並測得羧基之官能基團。再於真空系統中,利用特製真空濕式反應室,在未曝於空氣環境下,將膠原蛋白與羧基作用而進行醯胺鍵結反應,固定於接著丙烯酸的表面。此結果與原本就具備功能性羧基之單分子膜固定膠原蛋白後比對,兩者在化學結構的定性上無顯著差異,表示利用電漿表面處理與之後丙烯酸氣態接枝之直鏈碳與芳香環自我組裝單分子膜可以創造出羧基官能基團,並可利用此基團成功地固定膠原蛋白。這樣的電漿形成的化學反應模式,可以進一步應用到特定生物單體或其片段的接著,將之固定於直鏈碳與芳香環自我組裝單分子膜的表面,做為具有生物功能性的外露表面並應用於分子診斷等相關的應用。
關鍵字:微波氮氣電漿,自我組裝單分子膜,X光光電子能譜術,表面改質,生物分子接著。
High-resolution photoelectron spectroscopy was applied to study the modification of alkanethiolate self-assembled monolayers (SAMs) on gold (111) and silver (111) substrates by nitrogen downstream microwave plasma. In addition to the plasma treatment, we exposed the samples to 5 vol % diluted AAc monomers (using 95 vol % high purity N2 as the carrier gas) to create the terminal O=C-OH group for the subsequent attachment of biologically relevant molecules for diagnostic to specific diseases.
Because of the SAMs structure is easily destroyed by synchrotron radiation, investigation on damage effect by synchrotron radiation is necessary. Experimental result has indicated that the evolution of the S 2p spectra implies that the synchrotron radiation damage causes the transformation of the pristine binding energy 162.0 eV into 163.2 eV. To avoid X-ray-induced damage, photon flux and scan numbers should be controlled e.g. Ni mesh = 0.6 nA, scan number less then 10. The sample resulted in a low density and energy of the ionizing particles in the afterglow zone.
As shown by the plasma characterization using a Langmuir probe, experimental result has indicated that current downstream plasma provides plasma density of ca. or electron temperature of ca. 0.46 eV; it is regarded as low-density plasma. Surface analyses by XPS have revealed that after low density plasma treatment, new chemical bonds such as C-N, C-O, C=O and O=C-OH are formed on the modified surface. These polarizable groups arise a hydrophilic characteristic at surface. The general character of the plasma-induced changes was found to be the same for all investigated films, independent of the substrate and alkyl chain length. The experimental data imply a higher activation barrier for the thiolate-sulfonate transformation in the case of Ag substrate as compared to Au, which suggests a stronger bonding of the thiolate species to the former substrate. At a given substrate, the length of the aliphatic chain noticeably affects the rates and desorption processes. A disordering, extensive oxidation, and partial or total desorption of alkylsulfonate moieties takes place, being mostly mediated by the oxygen radicals and reactive oxygen-derived species in plasma. The oxidation affects both alkyl matrix and the thiolate-substrate interface, where the pristine thiolate species are transformed to sulfonates (predominantly). The AAc(Acrylic Acid) monomer is then introduced through diluted and vaporized phase. We dilute vapor-phase AAc with N2, and the consistency is 5%. Such plasma-induced process is performed in a reduced pressure and the modified alkylthiols SAMs surface is characterized in ultra-high vacuum using sample transferring system. The structures of pAAc-grafted chains are reactive with activated alkyl chains, the presence of C1s at 289.5 eV (O=C-O) are regarded as the evident of coupled grafting. Subsequently, the coupling O=C-O . may react with NH2-tail proteins or enzymes and form O=C-NH bonding, eventually for specific applications such as the sensing surface as biomedical receptors.
Keywords:Biomolecular Immobilization, self-assembled monolayers, nitrogen downstream microwave plasma, X-ray photoelectron spectroscopy, surface modification林淑萍92M01:固定幾丁聚醣聚丙烯不織布在抗菌與醫療上的應用
中文摘要
本研究乃是將聚丙烯不織布經表面改質後,進一步固定上幾丁聚醣
利用陣列天線式氧氣低溫微波電漿進行聚丙烯不織布表面活化
關鍵詞:聚丙烯不織布、微波電漿、幾丁聚醣、抗菌測試法
Su-Ping Lin: Immobilized Chitosan onto Polypropylene Non-Woven Fabric Surface for Anti-bacterial and Biomedical Applications
Abstract
Polypropylene (PP) non-woven fabric was surface-modified and subsequent to immobilize chitosan. Feasibility of applying such samples to wound dressing related uses was evaluated. The work was separated into three parts: qualitative and quantitative studies, anti-bacterial tests, and blood compatibility tests.
Low-temperature antenna-array O2 microwave plasma was utilized
for the activation of non-woven PP fabric. With several seconds of plasma
treatment, oxidative groups were massively created at surface. Using thermal and
reduction-oxidation reactions, the diluted acrylic acid (AAc) was subsequently
graft-copolymerized. Chitosan was then immobilized on the fabric using EDC-NHS
as coupling agents to originate O=C-OH (from the functional group of AAc) and
–NH2 (from the side group of chitosan) and to form covalently the
amide bonds (O=C-NH). The chitosan-immobilized substrates were reacted with CBR
3B-A, using UV/VIS absorbance measured at 575 nm for quantitative analysis.
Applying Fourier-Transformed Infrared with Attenuated Total Reflection and
Electron Spectroscopy for Chemical Analysis, we examined the chemical structures
and the element functionabilities of the modified surfaces. The JIS L 1902
testing method for fabric products was applied for the chitoson-immobilized
samples on the anti-bacterial capability tests. Such modified samples were then
contacted with blood plasma for the assessment of activated partial
thromboplastin time, thrombin time, and fibrinogen concentration tests.
Simultaneously, the absorption rates of red blood cells, platelets and white
blood cells on the chitosan-immobilized surfaces were calculated to assess their
bioactivities. Scanning Electron Microscopy was used to take the morphologies of
the blood-contacted sample. Experimental result has demonstrated that the
chitosan-immobilized quantity was ca. 47.91±2.51 μg·cm-2,
while the linkage between AAc and chitosan was confirmed as expected as the
amide bond. The anti-bacterial index of the sample was over the standard value,
2.2, whereas the index related to the capability of bacteria inhibition was
higher than the standard value, 0. It revealed that the immobilized chitosan
maintained its capability to inhibit bacterial proliferation. From the blood
clotting tests, the chitosan-immobilized surface did not affect the intrinsic
clotting pathway. Nevertheless, the surface was capable to adsorb red blood
cells, platelets and white blood cells in the blood tests. Furthermore, red
blood cells accumulated on the chitosan-immobilized surface was observed using
SEM. These phenomena could be referred to the characteristic of chitosan
itself.
Keywords: PP non-woven Fabric, Microwave plasma, Chitosan, Anti-bacterial test, Bioactivities.
高啟原 92M02:可攜式微生物感測器:工作電壓對於不同固定菌屬電極之最佳化探討
中文摘要
本研究針對實驗室先前開發之微生物感測系統,其具有內建特殊算數程
關鍵字:微生物感測系統,工作電壓,抑制率,微生物,生物活性。
Chi-Yuan Kao: Portable Microbial Biosensor, Optimization of Working Voltage for Varied Bacteria-Attached Electrode
Abstract
In
this study, our previous microbial sensing system with a built-in special
processing algorithm has been upgraded and further developed for detecting
wastewater’s toxicity. Bacillus subtilis, Escherichia coli and
Pseudomonas putida were utilized as sensing components of the system to
initiate biological and subsequent electrochemical reactions. The bacteria were
incubated in batch and tested under different temperatures, pH values and
working voltages. We tried to find out the optimized working environment of such
bacteria. Bacterial numbers and their bioactivities were estimated using the
oxygen uptake rate of bacteria, the plate count method, the turbidimetric method
and the microscopic count method, respectively. The bacterial solutions
incubated under such optimized combination were then attached onto the
electrodes of the system. The infinitesimal currents were correlated with the
variation of the defined dosages of toxicity tested on the bacteria-attached
electrodes. The addition of toxic substances can inhibit oxygen uptake rate of
the bacteria, which leads to induce electrochemical or charge transfer effects.
Thereafter, based upon this relationship, the toxicity of sampling water could
be distinguished. In this work, different working voltages were applied to
improve the identification of wastewater’s toxicity in accordance with the
output voltage. The characteristic voltage-time curves were fairly interpreted
using three types of calculation methods, with which specific inhibition rates
(I%) were thereafter expressed. Using the calculated I% close to the value
measured by Oxygen Dissolved Analyzer (ODA) and the shortest response time of
such method, an optimized microbial sensor with such built-in processing
algorithm was provided. With the optimized reactivation time and bioactivity for
the bacteria attached on the electrode, the analytical result demonstrated that
the optimized working voltages, which provoked the maximum oxidation-reduction
reaction rate or oxygen uptake rate of bacteria, for different bacteria-attached
electrodes were 0.85 V for Bacillus subtilis, 0.65 V and 0.70 V for
Escherichia coli, 0.70 V and 0.75 V for Pseudomonas putida,
respectively. Taking phenyl solutions as the reference, these three bacteria
were capable to detect the solutions in the ranges of 400-320 mgl-1
for Bacillus subtilis, 200-1600 mgl-1 Escherichia coli,
400-2400 mgl-1 Pseudomonas putida, respectively. In addition,
the calculation models exhibited significant variations in determining phenyl’s
toxicity with respect to the result of ODA. Using the best-fitted calculation
model, the correlation coefficients were 0.951 for Bacillus subtilis,
0.903 for Escherichia coli, 0.921 for Pseudomonas putida,
respectively.
Keywords: Microbial sensing
system, Inhibition rate, Calculation method, Correlation
coefficient.
陳煌仁92M03:可程式之人工全膝關節模擬磨耗機的研製
中文摘要
本研究在於設計並製作一可程式之人工膝關節模擬磨耗機
關鍵字詞:可程式的、膝關節模擬磨耗機、高密合度、旋轉中心。
Huang-Jen Chen:
Design and Making of A Programmable Knee Wear Simulator
This work deals with a design and making of a programmable knee wear
simulator (KWS). The main concept of the design is based upon the gait cycle of
human knee movement. The input gait profile to KWS is provided by known data,
which include normal people, patients with knee reconstruction. In the
experiment, the initial profile and simulated curves thereafter perform the
calculation of fitting process, according to linear regression and fundamental
statistics. Analytical result has demonstrated that the output gait movement
simulation is affected by the completion of testing time and the mechanical
tolerance of the KWS to finish an input cyclic curve. Also, patients with knee
reconstruction are relatively feasible to perform a simulation with high fitting
rate. The delay of testing time to complete a simulation is similar for the
input curves from normal people and patients. It implies that the movement of
KWS may achieve an assigned program on time. Current KWS provides a
flexion-extension movement with one fixed rotation center, which is partially
incomparable to biomechanical contours. An uprising force is therefore generated
as the femur condyles slide forwards. This irregular loading force is obviously
reduced by extending a required time to complete a testing cycle,
simultaneously, by adjusting PID control, which enhances the consistence among
applied loading, flexion-extension and rotation of meniscus. This KWS is
therefore a valuable tool for the evaluation of materials’ quality and
biomechanical design of products. Furthermore, it can be applied for the
post-operation studies, particularly on material responses, host responses, as
well as the lifetime of knee prosthesis.
Keywords: Programmable,
Knee wear simulator, High fitting rate, Rotation
center.
徐俊傑 92M04:應用版式電極製作可攜式快速尿酸感測裝置
中文摘要
本研究是利用酵素能夠藉由氧化還原作用以識別特定分子的基本特性
關鍵字:尿酸感測器、固定尿酸酶電極試片、電壓-時間曲線、計算模式、相關係數。
Jin-Chai Hsu:
Applied screen-printed carbon electrode to make a portable and rapid-response
uric acid sensing device
Abstract
This work is based upon the characteristic of an enzyme capable to
recognize a particular molecule through an oxidation-reduction effect. In this
study, the uricase is utilized as the sensing components of our sensor system to
initiate biological and subsequent electrochemical reactions. After the
reactions, the output infinitesimal currents are transformed into voltages shown
as electrical signals. Firstly, the variation of the defined uric acid
concentrations is correlated with the dissimilar expression of electrical
signals. Secondly, the characteristic voltage-time curves are fairly interpreted
using three types of calculation models, End-point measurement, Quasi-kinetic
measurement I, and Quasi-kinetic measurement II. Specific uric acid
concentrations are thereafter expressed in such sensor system with a built-in
special processing algorithm. For the part of the enzyme-attached electrode,
polyvinylpyrrodine is utilized to embed the uricase, and under an optimized
working voltage of 0.70 V, pH value of 7.4 at 25oC, the uric acid
concentration in the range of 2~16 mg/dl can be well distinguished. Using the
optimized calculation method of End-point measurement, the correlation
coefficient of uric acid concentration with respect to standard solution and
colorimetric method can reach to 0.995 and 0.998, respectively. Simultaneously,
the sensitivity of measurement of the uric acid sensor is insignificantly
affected by the pH values of 7.0, 7.4 and 7.8 at 25oC. The reaction
rate of the uricase-attached electrode to uric acid becomes stabilized, or
unaffected by the increase of the uric acid concentrations, as the sampling
concentrations are higher than 6 mg/dl. Nevertheless, the measurement is likely
disturbed by added Vitamin C, as low concentration of uric acid is tested. In
the preservation study, the functionability of the uricase-attached electrode,
under appropriate temperature and relative humidity, can be hold up to 43
days.
Keywords: Uric acid sensor,
Uricase-attached electrode, Voltage-time curve, Calculation model, Correlation
coefficient.
林明哲
92M05:電漿誘導聚酯纖維鍵結幾丁聚醣形成具抗菌功能性之表面
中文摘要
本研究以聚酯纖維(PET)為基材,利用陣列天線式氧氣微波電漿對纖維的表面進行活化前處理
關鍵字詞:聚酯纖維、微波電漿、幾丁聚醣、抗菌。
游惟翔 93M01:電漿離子佈植在鈦合金及碳合金鋼表面產生型態及微結構變化之探討(July 2004)
中文摘要
離子佈植方法是物理的技術能夠在金屬表面產生一擴散漸進層,其不同於鍍層技術經常會改變原基材的尺寸或大小。其中,電漿離子佈植技術利用低溫氣體電漿做為離子源。基材經施加一固定的脈衝負偏壓,之後,電漿中的離子對目標基材轟擊,在表面可能形成數百奈米的擴散深度的處理層。其中,電漿離子佈植方法可以將氮、碳、氧等間隙元素植入金屬基材中。然而,此方法之電漿離子的種類及所植入離子的深度均受到限制。本研究中以三種碳合金鋼,即304不鏽鋼、M2高速鋼、420J2麻田散鋼、以及Ti-6Al-4V為基材。利用表面分析儀器,如:X光光電子能譜儀、歐傑電子能譜儀、及低掠角X光繞射儀,來探討離子佈植表面結構的變化。對碳合金鋼,使用50% C2H2 and 50% N2而言,由於離子的動能與大小的差異,僅有氮元素可進入基材內,而碳衍生物質則是在表面產生堆疊。舉例而言,在高的偏壓下,如:20 KV時,同時造成表面粗糙度大幅上升,但離子佈植表面的奈米硬度呈下降趨勢。氮元素能進入基材表面形成微裂縫與疊差,可能對原本緻密的結構造成破壞。對Ti-6Al-4V,使用100% N2而言,處理後的試片表面會有TiN鍵結能的發現,但由於在低掠角X光繞射分析結果並未有結晶相之TiN產生,因此推測其形成之TiN為非晶型。其效應使得處理後試片表面變平整,奈米硬度上升,但在耐磨損磨之耗微振磨耗測試方面,因處理試片深度為極表面,故觀測不出顯著之變化。
關鍵字詞:間隙元素、脈衝負偏壓、電漿離子佈植、鈦六鋁四釩、碳合金鋼。
W.-X. Yu, Plasma ion implantation on Ti-based alloy and carbon steel: study of modification on surface morphologies and microstructures
ABSTRACT
Ion implantation methods are physical techniques capable to create a diffused layer into a metal surface and are dissimilar to coating techniques, which usually alter the size or the dimension of the substrate. Among them, plasma ion implantation technique utilizes low-pressure gaseous plasma as the source of ionized elements. The substrate is exerted a constant and negative impulse bias; plasma ions thereafter bombard into the target substrate, which may result in a layer of several hundreds nm depth. Plasma ion implantation method is competent to insert interstitial elements such as nitrogen, carbon or oxygen, into a metal. Nevertheless, both the type of plasma ions and the ion-implanted depth are limited by applying this method. In this work, three kinds of carbon alloy, i.e. 304 stainless steel, M2 high speed steel and 420J2 martensite steel, and Ti-6Al-4V were employed. Surface analyses using X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES) and Glancing Incidence X-ray Diffraction were utilized to explore the modified structures of the ion-implanted surface. In the case of carbon alloys using 50% C2H2 and 50% N2, only nitrogen elements could enter the substrate, detected by AES, whereas carbon-derivative species were accumulated on the surface, owing to the difference of the kinetic energy and the dimension of the ionized mass. For example, at high bias voltage such as 20 KV, surface roughness significantly increased, simultaneously nanohardness of the ion-implanted surface obviously decreased. The nitrogen elements were capable of entering the substrate surface and forming creaks and stacking faults on it, which might damage the densely packed structure. In the case of Ti-6Al-4V using 100% N2, TiN binding energy, detected by XPS, was found on the ion-implanted surface, whereas no TiN crystalline structure was sought using GIXRD. It is therefore presumable that the formation of TiN was non-crystalline. In addition, this effect was superficial that made the ion-implanted surface smooth and increased its nanohardness, whereas the abrasion resistance of the treated surface to micromotion test was unobvious.
Keywords: negative impulse bias, interstitial elements, Plasma ion implantation, Ti-6Al-4V, carbon alloy.
劉駿逸 93M02:膠原蛋白製品的生物活性衰減與抗菌程度變化之研究(July 2004)
中文摘要
膠原蛋白為天然的生醫用材料,具有優異的生醫功能特性,可促進軟組織修復或使傷口癒合而無痂疤的形成;其多種應用因此已見於保健與美容相關方面。為降低使用含膠原蛋白衍生品的成本,其它途徑,例如:以水解膠原蛋白片段取代成為類似膠原蛋白物質或將之固定在高分子基材上的方式,已經廣被考慮。水解膠原蛋白較缺乏生物可反應性,但在護膚保濕的能力則廣被認可。固定膠原蛋白或水解膠原蛋白經常藉由共價鍵結的方法,然而,固定膠原蛋白的生物活性會隨著存放時間而退化。除此之外,含膠原蛋白製品仍需經過滅菌處理,此可能使得膠原蛋白結構受到破壞,造成其生物活性再降低至某種程度。本研究利用氧氣電漿活化聚丙烯不織布,隨之,將之接枝丙烯酸單體使修飾的表面具官能基與親水性的結構,再以媒合劑固定Type III膠原蛋白或水解膠原蛋白片段於其上。使用減弱全反射-傅立葉轉換紅外光譜儀及X光光電子能譜儀對改質後之表面進行化學分析,實驗結果顯示:接枝丙烯酸的羧基(O=C-OH)與兩種膠原蛋白分子均可形成共價鍵結的醯胺鍵結(O=C-NH)。由於生物分子大小的不同,水解膠原蛋白之固定量較Type III膠原蛋白多約4.2 μg/cm2;然而,Type III膠原蛋白仍保有促凝血之生物活性,水解膠原蛋白則無。兩種固定膠原蛋白之試片可在照射254 nm的紫外線20小時後達到滅菌的效果;同時,固定的膠原蛋白之大部分的生物活性仍然保有。在含膠原蛋白物質中可以抑制細菌生長的添加物可以有效地降低紫外線照射所需時間,因而更可保有固定膠原蛋白的生物活性。
關鍵字詞:膠原蛋白固定、水解膠原蛋白片段、生物活性、紫外線滅菌。
J.-Y. Liu, Effects of UV Sterilization and Additives on Bioactivity of Collagen
ABSTRACT
Collagen is a natural biomaterial that retains excellent bio-functional properties in repairing soft tissues or healing wound without scar formation. Many applications have therefore been relevant to health care as well as cosmetics. To reduce the cost of utilizing collagen-containing derivatives, alternative solutions such as replacing dehydrated collagen segments as a collagen-like substance or immobilizing collagen upon a polymeric substrate have been widely considered. The dehydrated collagen segments are relatively short of bio-reactivity, however, its capability of upholding moisture for skin care is generally recognized. To immobilize collagen or dehydrated collagen segments, the covalently bonded method is usually utilized, whereas the bioactivities of collagen are likely degraded along storing time. In addition, collagen-containing substances should be validated to a sterilization process that may provoke structural damages of collagen and thus reduce its bioactivity to a certain degree. In this study, O2 plasma was utilized to activate non-woven polypropylene (PP) fabric and then the fabric was grafted co-polymerized with acrylic acid (AAc) to obtain a modified surface with functional and hydrophilic structure. Collagen type III or dehydrated collagen segments was then immobilized on the pAAc-grafted fabric using coupling agents. Fourier-Transformed Infrared with Attenuated Total Reflection and X-ray Photoelectron Spectroscopy were employed for surface analyses on the modified samples, experimental results demonstrated that the O=C-OH group from pAAc was covalently bonded with both collagens and formed the amide bond (O=C-NH). Owing to the variation of bio-molecular sizes, the immobilized quantity of the dehydrated collagen segments was �l4.2 μg/cm2 more than that of Type III collagen. Using blood-clotting tests, the immobilized Type III collagen still retained their original bioactivities; however, little bioactivity was found for the immobilized dehydrated collagen segments. Both collagen-immobilized fabrics could be sterilized after 20 hrs of UV-254 nm irradiation, while the bioactivity of the immobilized collagen was mostly preserved. A chemical additive that was effective to inhibit bacterial proliferation in the collagen-containing substances could also reduce the required UV exposure time and therefore significantly uphold its bioactivity.
Keywords: dehydrated collagen segment, bioactivity, UV sterilization, collagen immobilization.
蔡濱丞 93M03:自我排列單分子層於順流式電漿系統中反應速率及機制之研究(Jan. 2005)
中文摘要
自我排列單分子層(Self-Assembled Monolayers;SAMs)之技術已廣泛運用於基礎物理及化學現象的探討及研究。而利用低溫電漿進行有機高分子的表面處理,則可在表面上產生聚合、交錯連結及表面的化學反應,創造出具功能性的表面結構。本研究以N2和Ar作為順流式電漿的激發氣體,對於吸附於Au(111)及Ag(111)上的ODT、DDT SAMs進行不同時間的處理,以探討電漿與SAMs的界面反應中,電漿氣體的選擇、AT分子鏈長及吸附基材的影響效應。
在實驗中,原基材及經處理後的試片使用位於同步幅射中心的高解析X光光電子能譜儀(HRXPS)進行表面分析,以決定表面結構的變化情形。結果顯示,隨著電漿處理時間的增加,表面鍵結變化的情形也隨之發生,且無論在Ar或N2的電漿環境下,表面鍵結的變化皆以氧化物為主。後續的分析上,由C-C(~285.0eV)、S-metal(~162.0eV)兩鍵結曲峰配湊的結果求得的衰退速率作為各組試驗中反應速率比較的依據。主要的討論結果可整理如下:當使用相同的電漿氣體,對吸附於同樣基材上不同鏈長的AT分子進行處理時,短鏈的DDT分子的反應速率較ODT快;以相同的電漿氣體,對同樣的AT分子吸附於Au或Ag的試片進行處理時,吸附於Au的AT分子反應速率較吸附於Ag快;而分別以N2與Ar電漿對同一組試片進行處理時,N2電漿的反應速率較快。文中則以上述實驗結果為基礎,對於此系統中電漿與SAMs的界面反應機制作進一步的討論。
關鍵字詞:順流式電漿、自我排列單分子層、高解析X光光電子能譜儀。
B.-C. Tsai, The study of the reaction rate and mechanism of self-assembled monolayers treated in the downstream plasma system
ABSTRACT
Self-assembled monolayers (SAMs) have been widely applied in field such as fundamental research of physics and chemical phenomenon. Surface modification of organic polymer utilized low-temperature plasma could create functionalized surface by polymerization, crosslink and other chemical reaction. In the study, modification of self-assembled Octadecanethiol (ODT) / Dodecanethiol (DDT) on Au (111) / Ag (111) substrate using low-density nitrogen and argon downstream microwave plasmas with different interval. Chain length of alkanethiolate molecules adsorbed upon a substrate and the applied gaseous plasma are three major factorial bodies that may influence the reaction rate and mechanism at the plasma/SAMs/S-metal interfaces.
Surface characterization of the pristine and the plasma-treated films was performed using high-resolution x-ray photoelectron spectroscopy at the U5 undulator beamline of the National Synchrotron Radiation Research Center. Obviously, with increasing plasma treatment time, noticeable changes on SAMs are observed by HRXPS, whereas the oxygen species play the dominant role in the boundary reactions that produce oxygen-based functional groups whatever in nitrogen or argon plasma process. Further, the intensity of specific bondings, C-C (285.0eV) and S-metal (162.0eV), of each sample were calculated using curve-fitting data. Comparing with the decay trends of C-C and S-metal bonding, one might display the relation of all factors in this system. The main feature of the experimental results can be summarized as follows. Firstly, on the given substrate, the length of alkyl chain noticeably affects the rate and extent of oxidation and desorption processes, while the DDT film either on Au or on Ag can be vastly removed. Secondly, the thin-film SAMs on Ag are much more resistant to plasma-induced degradation than those on Au. Overall, the minor oxygen species in nitrogen plasma is much reactive than those in argon plasma owing to the difference of energy transferring system for the reactive species.
Keywords: high-resolution x-ray photoelectron spectroscopy, downsteam plasma, self-assembled monolayers.
高啟原94EM01:以金屬蒸氣真空弧離子佈植技術進行氧化鋅透明導電薄膜之製作(Jan. 2006)
中文摘要
透明導電薄膜是一種吸收紫外光、穿透可見光與反射紅外線的材料,傳統上多使用氧化銦錫(ITO),但因為其成本較高,所以一直有新材料的發現和成膜技術想取代它,ZnO:Al(AZO)即是一例,在適當條件下可製作出與ITO相媲美之特性且價格低廉,極具競爭優勢。本研究有別於一般製作ZnO:Al之成膜技術與方法,乃利用金屬蒸氣真空弧(MeVVA)佈植技術植入鋁離子,改質氧化鋅(ZnO)透明導電薄膜,藉由不同鋁離子植入劑量與控制機台參數,進而改變ZnO薄膜的導電特性與透光度,並探討離子植入後 之結構、光學與電性質的改變。實驗中使用一般鈉玻璃作為基板,並利用射頻磁控濺鍍(RF reactive magnetron sputtering)系統沉積ZnO薄膜與對照組ZnO:Al(2%)薄膜,然後以MeVVA來改質ZnO薄膜。
金屬蒸氣真空弧技術是將純金屬離子化至氣態,進而轟擊基材,此種技術可在表面形成數百奈米深的處理層,因此可對所選定的基材進行表面改質。本研究分為二階段作討論,第一階段探討RF磁控濺鍍與MeVVA植入系統參數對ZnO薄膜性質的影響,包括:薄膜厚度、沉積速率、透光率、電性與植入形貌;第二部分藉由前述的實驗結果,選擇最佳之離子植入參數來改質ZnO薄膜,並以ZnO:Al薄膜作為基礎對照,探討鋁離子植入改質後之ZnO薄膜的特性。研究結果顯示:在基板不加熱以及厚度為261 nm的條件下,沉積出的純ZnO薄膜電阻值高,但經由MeVVA離子佈植之改質技術(劑量:1.4×1016 ions/cm2)可以改善ZnO薄膜之高電阻值(3.02×107 Ω下降至3.03×104 Ω)並保有高透光率(91.5%),極具發展之潛力。
關鍵字:金屬蒸氣真空弧,離子植入,射頻磁控濺鍍,透明導電薄膜。
C.-Y. Kao, Fabrication of ion-implanted ZnO thin film with transparent conductive properties using metal vapor vacuum arc technique.
ABSTRACT
Transparent conductive thin film which is a material could absorb ultraviolet, transmit visible light and reflect infrared ray. Because of the price is too high to prepare the traditional thin film-ITO, new material finding and coating technique would replace it all the time. As the suitable parameters, we can prepare as better properties as Tin-doped indium oxide (ITO), for example Al-doped ZnO (AZO). In this study, we utilize metal vapor vacuum arc (MeVVA) technique, which can implant aluminum ions into zinc oxide (ZnO) thin film. By using different ion doses, it can improve the conductivity and the changes of optical properties. In our experiment, we use glass as the substrate, then coating a thin film of ZnO and ZnO:Al(2%) by using RF reactive magnetron sputtering deposition (RF-MSD) system. At last, we utilize MEVVA technique to modify the surface of ZnO.
MeVVA technique can vaporize the metal by arc, then accelerate it to bombard the target substrate. It can create several hundred nano-meter depth of diffused layer. In our study, we separate it into two parts to discuss. In first part, we discuss about the parameters of RF-MSD and MeVVA system which influence the properties of ZnO thin film a lot, including thickness of thin film, deposition rate, transparency, conductivity and surface morphology. The second part, we find out the satisfying implant parameters to modify ZnO thin film, then we compare with ZnO:Al thin film to gain the difference between each other. As the results, under the situation of non-thermal and thickness of 261 nm, the conductivity of ZnO thin film was poor (3.02×107 ohm). After MeVVA treatment, it can develop the conductivity and still reserve for higher transparency (91.5%) in 550 nm.
Keywords: Metal Vapor Vacuum Arc, Ion Implantation, RF reactive magnetron sputtering, Transparent Conductive Oxide Thin Film.
林哲瑩94M01:高敏度表面與高解析技術診斷具疾病表現之單一核苷酸多型性:運用SAMs技術固定寡核苷酸(June 2005)
中文摘要
自組裝單分子層(Self-Assembled Monolayers,SAMs)具有穩定性高、製程簡單、以及末端官能基的可變異性,目前廣被運用在基礎科學研究所需的理想的表面、具功能性的生物感測表面等。SAMs可以化學鍵結方式固定生物單體物種,以用來進行生物分子辨識的應用,如:單一核苷酸多型性(Single Nucleotide Polymorphism,SNP)。本研究中,運用SAMs技術在Au(111)面上化學吸附硫端,並外露末端官能基O=C-OH,緊接著以EDC、NHS作為表面活化劑與媒合劑,結合在寡核苷酸分子5’端修飾的胺基(-NH2),利用O=C-OH與-NH2在SAMs表面形成醯胺鍵,達到DNA序列片段固定在Au表面的目的。
實驗中針對不同溫度、pH值以及媒合劑濃度的變化,建立固定寡核苷酸引子的成效較佳化條件。分析方面則採用同步輻射中心之高解析式X光光電子能譜儀以及75°低掠角反射傅立葉轉換式紅外線光譜儀,針對不同過程的表面做原子鍵結及元素分佈的分析,並由螢光顯微鏡的觀察,建立在Au面上進行核酸雜合反應的效能評估。在表面型態分析部分則以原子力顯微鏡針對表面掃描分析,觀察試片表面經過固定寡核苷酸分子與核酸雜合反應後的表面型態變化。
研究結果顯示,在本研究所採用的不同條件(溫度、pH值)中,以37℃且在酸鹼度為pH值4.5的緩衝溶液的條件下進行寡核苷酸引子固定在晶片上,其固定結果較好;在進行核酸雜合反應時,效能也較佳。當媒合劑濃度為100 mM條件下,固定寡核苷酸引子比媒合劑濃度為1 mM或10 mM的效果要好。對於寡核苷酸引子固定在SAMs上,各階段新的化學結構變化也給予驗證。
關鍵字詞:自我組裝單分子層、高解析式X光光電子能譜儀、單一核苷酸多形性、 核酸雜合反應、75°低掠角反射傅立葉轉換式紅外線光譜儀。
C.-Y. Lin, High-sensetive Surfaces and High-resolution Techniques to Diagnose the Single Nucleotide Polymorphism: Use SAMs technique to immobilize oligonucleotides.
ABSTRACT
Self-Assembled Monolayers (SAMs) provide a highly stable structure, easily prepared process and flexible functional group. Nowadays SAMs is widely used as an ideal surface on basic science research and for functional surface of Biosensors. Bio-monomer can be immobilized onto SAMs by chemical bonding and applied for molecular recognition, e.g. Single Nucleotide Polymorphism, SNP. The objective of this study is to immobilize DNA primers onto gold surface by introducting SAMs. In the experiment, SAMs was chemically adsorbed on Au(111) and created a tailor functional group of O-C=OH, which was then activated by coupling EDC and NHS, and subsequent to link with 5’ modified Amino group Oligonucleotides by amide bond forming with O-C=OH functional group of SAMs. The factors of different temperatures, pH values, and the concentration of coupling reagents for oligonucleotides immobilization were investigated. The optimized recombination was build using HRXPS (High Resolution X-ray Photoelectron Spectroscopy) of NSRRC (National Synchortron Radiation Research Center) and 75 degrees grazing angle FTIR (Fourier Transform Infrared Spectrometer). The instruments were used to analyze atomic binding energies, elements distribution, and absorbance of functional groups. DNA hybridization was observed using Fluorescence Microscope, and their surface morphologies were mapped by AFM (Atomic Force Microscope). Experimental results demonstrated that the optimized condition for DNA hybridization was determined at 37℃, pH value of 4.5 and the concentration of coupling agent around 100 mM. In accordance with oligonucleotides immobilization, the presences of new chemical structures at different stages were also identified in this study.
Keywords: 75 degrees grazing angle FTIR, HRXPS, Self-assembled monolayers, Single nucleotide polymorphism, DNA hybridization.
黃芷翎94M02:以不同比例聚乳酸-聚甘醇酸共聚物製作多層孔隙型神經再生導管(June 2005) (2005 科林論文獎)
中文摘要
神經導管接合術是利用顯微手術將神經兩斷端縫入生醫材料所製備之神經導管以橋接神經斷裂的兩端,神經可藉由軸突的再生而重新連接缺口兩端的神經使功能恢復,導管可減少神經拉扯時造成的張力並引導軸突的再生,亦可承載神經生長因子促進神經再生,此外,也可以將阻礙神經再生的細胞及其分泌物阻擋在管外。本研究將以聚乳酸、聚乳酸-聚甘醇酸共聚合物(75:25)、聚乳酸-聚甘醇酸共聚合物(50:50)做為研究材料,以檸檬酸誘發碳酸氫銨發泡之氣泡成型法製作具有相連通孔隙之高分子薄膜,再將高分子薄膜捲製成特殊多層的導管,製作具有多層孔隙之新型神經再生導管,以電子能譜化學分析及減弱式全反射-傅立葉轉換紅外線光譜分析進行成份分析及化學元素測定;以電荷耦合元件攝影機、掃瞄式電子顯微鏡進行多層孔隙型神經導管巨觀及微觀形態結構觀察;以示差掃瞄熱量量測分析玻璃轉換溫度、奈米三維量測彈性模數及硬度;以及進行降解性質測定,並以掃瞄式電子顯微鏡進行降解後之導管微觀結構形態觀察。實驗結果顯示:聚乳酸、聚乳酸-聚甘醇酸共聚物(75:25)、聚乳酸-聚甘醇酸共聚物(50:50)三種材料經檸檬酸誘發碳酸氫銨發泡之氣泡成型法製程並不造成碳酸氫銨之殘留。聚乳酸-聚甘醇酸共聚物(50:50)的玻璃轉換溫度低於人體正常體溫,故降解28天後,導管的孔隙已融合成為緻密的表面,且於降解56天後完全降解;聚乳酸-聚甘醇酸共聚物(75:25)降解速率較慢,且降解56天後,孔隙略有融合的現象;而聚乳酸經檸檬酸誘發碳酸氫銨發泡再以捲製成型,可製造出具有較高的孔隙率及相連通的開孔結構之多層孔隙型神經導管,且降解56天後,仍可維持良好的孔隙率以維持導管的通透性質。
關鍵字:聚乳酸、聚乳酸-聚甘醇酸共聚物、神經導管、多層孔隙、碳酸氫銨
C.- L. Huang, Novel nerve regeneration conduits made by different ratios of poly (L-lactide-co-glycolide) forming with porous and multi-layered structure
ABSTRACT
Nerve bridging is suture a biomaterial-made conduit and to overpass the damaged nerve end to end with microsurgery. Peripheral nerve could be bridged between the proximal nerve and the distal stump to restore the function. Nerve conduits could eliminate tension at the healing site and induce the regeneration of axons. Nerve conduits also could permit neurobiological recovery to enhance neural regeneration and stop cells and their secretions from obstructing neural regeneration. In this study, we used poly L-latcide (PLLA), poly DL-latcide-co-glycolide 75:25 (PLGA7525) and poly DL-latcide-co-glycolide 50:50 (PLGA5050) during citric acid inducing ammonium bicarbonate gas forming process to form porous polymer film, and rolled the porous polymer film to make nerve conduits with pores and multi-layered. Electron Spectroscopy for Chemical Analyzer (ESCA) and Attenuated Total Reflectance – Fourier-Transform Infrared Spectrometer (ATR-FTIR) were employed for determining elements’ functionabilities and chemical compounds. Charge Coupled Device camera (CCD camera) and Scanning Electron Microscope (SEM) were employed for macroscopic and microscopic morphologies and structural observation. Differential Scanning Calorimetry (DSC) was employed for measuring glass-transition temperature (Tg). Nano-indentation system was employed for measuring elastic modulus and hardness. Biodegradation and water absorption ratios were measured to analyze their chemical properties and SEM was employed for microscopic morphology of the tested nerve conduit. Experiment results demonstrated that during citric acid inducing ammonium bicarbonate gas forming process, no salts (ammonium bicarbonate) remained, while Tg of PLGA5050 was lower than human body temperature. The porous structures of PLGA5050 conduit were dissolved into a condensed morphology after 28 testing days, while the material was completely degraded after 56 testing days. The degradation of PLGA7525 conduit was relatively slow, while the porous structures slightly changed their shapes after 56 testing days. Using citric acid inducing ammonium bicarbonate gas forming and unique rolling process, PLLA is relatively suitable to make multi-layered nerve conduits, which provide highly porous structures with many round openings. In addition, the porous structures with channeling characteristic can be preserved to 56 testing days.
Keywords: poly lactic acid、porous and multi-layered、poly lactide-co-glycolide、 ammonium bicarbonate、nerve conduit
陳信宏94M03:利用氣態丙烯酸為中間劑以固定幾丁聚醣於電漿活化之L型聚乳酸薄膜表面(May 2006)
中文摘要
L型聚乳酸具生物相容性、生物可降解性且具有適當的機械性質,可用於神經導管之支架。幾丁聚醣則具有細胞親和性,用以促進周邊神經的再生。本研究以電漿活化聚乳酸基材表面,產生的自由基再與通入的氣態丙烯酸單體結合;藉由羧基與胺基間產生醯胺鍵結固定幾丁聚醣於L型聚乳酸表面,期能同時結合可降解之L型聚乳酸基材及具表面功能性之幾丁聚醣兩者的優點。實驗以電子掃描式顯微鏡觀察試片表面型態變化,以減弱式全反射紅外線光譜儀及化學分析電子光譜儀分析表面鍵結結構的變化。然後,以抗菌測試及細胞貼附測試來探究具幾丁聚醣表面之試片的生物功能性。
實驗結果顯示:氣態丙烯酸單體可以接枝於L型聚乳酸薄膜上,且幾丁聚醣藉由醯胺鍵結,固定於已接枝丙烯酸單體之聚乳酸薄膜表面上。纖維母細胞型態於固定幾丁聚醣後之聚乳酸薄膜上,經培養48小時後仍然維持較圓形,推論固定幾丁聚醣後之聚乳酸薄膜將降低纖維母細胞於表面上的貼附能力。而細胞在試片上的貼附能力減低,可以降低貼附細胞增殖的速度。此結果可應用於神經導管的支架製作上,將可降低疤痕組織的發生,促進周邊神經再生的效能。
關鍵詞:L型聚乳酸、幾丁聚醣、氣態丙烯酸、周邊神經再生。
H.-H. Chen, Immobilization of chitosan on the plasma-activated poly-L-lactic acid film surface using evaporated acrylic acid as the intermediate
ABSTRACT
Poly-L-lactic acid ( PLLA ) has biodegradable , biocompatible properties and suitable mechanical character, so it can be manufactured as scaffolds for nerve conduit. Chitosan with cell affinity is used to enhance the regeneration of peripheral nerves. The study is using radicals produced on the plasma-activated PLLA film combining evaporated acrylic acid(AAc)monomers and then immobilizing chitosan on the PLLA film by amide bonding formed between carboxyl and amine group. We expect that it can combine both advantages between biodegradability of PLLA and biological functionality of chitosan. The surface morphology is observed by scanning electron microscope. The respective chemical structure change following sequential reactions were identified using Fourier transform infrared spectrometer-attenuated total reflection and X-ray photoelectron spectroscopy. Then we discover the biological functionality by antibacterial and cell attachment tests.
The results demonstrated that evaporated AAc monomers could be grafted on PLLA film and chitosan could also be immobilized on AAc-grafted PLLA film by amide bonding. The morphology of most fibroblasts cultured on the chitosan-immobilized PLLA film maintained round after 48 hours culturing. We infer that chitosan-immobilized PLLA film would reduce the attachment of fibroblasts on the surface, and therefore the proliferation rate of fibroblasts would also be repressed. The results can be applied on the manufacturing of scaffolds for nerve conduit that can decrease the appearance of scar tissues and enhance the efficacy of peripheral nerve regeneration.
Keywords:Poly-L-lactic acid, chitosan, evaporated acrylic acid, regeneration of peripheral nerves
張正宏(成大醫工共同指導):植入式多極神經銬電極表面處理(July 2005)
中文摘要
神經銬狀電極是一種被廣泛應用於神經義肢的微電極,它應用電刺激與神經訊號量測技術來恢復受損的周邊神經系統功能。當電極植入體內後,因生物分子與電極表面的作用,常造成電極阻抗上升使得電極效能不佳;我們應用微機電製程技術製造並測試新的多極式神經銬狀電極,電極由自我組成有機薄膜表面處理的微電極與聚亞醯胺基材所構成,經過處理的電極表面能在分子層級控制生物分子的沾黏附著,實驗中應用不同碳鍊長度的有機薄膜分子化學合成在電極表面來探討蛋白質吸附與細胞黏著現象。
在蛋白質吸附實驗中,自我組成有機薄膜在電極表面提供了一個疏水性的環境,可減緩蛋白質的初始吸附與後續堆疊,降低電極阻抗的上升,電極阻抗的改變主要是容抗所造成與蛋白質堆疊過程有關;表面處理能降低部分蛋白質在電極表面的吸附,此效應與薄膜分子碳鍊長度相關,在未處理金面上則緊密的吸附上蛋白質層。
在細胞黏著實驗中,自我組成有機薄膜增加了電極表面的水滴接觸角與初始電極阻抗,它提供了一個低離子強度的表面使得細胞無法完全的吸附黏著;為了探討液相環境裡的表面單細胞黏著力學,我們應用三角形懸臂樑的原子力顯微鏡探針,測試刮起細胞所需的力與工,結果顯示刮起細胞所需的力與工在未處理的金面上遠大於有機薄膜處理的金面並與薄膜分子碳鍊長度相關。
電極效能退化問題一直是影響植入系統成功與否的關鍵,在本研究中嘗試應用自我組成有機薄膜表面處理改質技術產生蛋白質與細胞難吸附的電極表面,改善植入式神經電極性能;實驗證明多極神經電極在表面處理後能降低蛋白質與細胞的沾黏吸附。
關鍵字詞:蛋白質吸附、自我組成有機薄膜、微機電、電極阻抗、原子力顯微鏡、細胞黏著、微電極。
C.-H. Chang, Surface Modification of Implantable Multi-Polar Nerve Cuff Electrode
ABSTRACT
Nerve cuff electrodes are one of the electrode types utilized in neuroprosthetic applications. The microelectrode spiraled as a cuff type can be used for restoring nerve function via electrical stimulation or nerve signal sensing on the peripheral nerve. However, an increase of electrode impedance might occur during implantation, which will decrease the electrode performance. The crucial factor comes from the interface between the biomolecule and the surface of microelectrode. A new thin film multi-polar spiral cuff electrode, composed of self-assembled monolayer (SAMs) treated electrodes and flexible polyimide substrate, was manufactured and tested. Since the gold electrodes after the SAMs treatment can control the interactions of the biomolecule-electrode surface at the molecular scale, SAMs of varied chain lengths adsorbed upon Au-coated nerve microelectrodes were employed for protein absorption and cell adhesion studying.
In protein absorption study, thin-film SAMs treatment upon Au/polyimide (PI) surface of the microelectrode provided a hydrophobic characteristic, which retarded protein adsorption at the initial stage and subsequent pile-up (or thickening) process. The protein-resistant effect exhibited comparable for SAMs of different chain lengths adsorbed upon Au/PI surfaces. The increase of electrode impedance as a function of protein deposition time was mainly correlated with the addition of reactance that was associated with the pile-up thickness of the deposited protein. Particularly the SAMs-modified surface was capable to detach a significant portion of the accumulated protein from the protein-deposited SAMs/Au/PI, whereas the protein-deposited layers exhibited firm adhesion upon Au/PI surface.
In cell adhesion study, thin-film SAMs adsorbed on Au/PI provided a passive or hydrophobic surface that increased water contact angle and initial total impedance, or therefore decreased cell coverage rate. Thin-film SAMs as a dense-packed spacer provided with a relatively low ionic strength that resulted in incomplete cell sealing. To study cell-surface interactions, cell detachment test used a triangular probe tip of AFM cantilever was experimented in medium containing a comparable single cell. Overall, both the peaks forces (Fcell) and the work required to remove a comparable single cell from the anchoring domain correspond well with the increased length of alkyl chains adsorbed upon Au/PI, which was much smaller than those of the pristine surface.
This work thus approaches to establish a consistent means to create protein-resistant and cell-repulsive characteristics on the microelectrode surface. It is therefore very promising to apply thin film SAMs adsorbed upon Au-coated surface for bio-invasive devices that have the need of functional electrical stimulations or sensing nerve signals during chronic implantation.
Keywords: MEMS, microelectrode, protein absorption, cell adhesion, AFM, impedance, self-assembled monolayers.
張家維95EM01:以金屬蒸氣真空弧離子佈植技術進行氮化鈦微結構之研究(July 2006)
中文摘要
本研究是以金屬蒸氣真空弧技術在鈦六鋁四釩基材上產生氮化鈦結構,此方法可將純鈦金屬離子化,透過電場加速使其通過充滿氮氣分子的環境中,藉由兩者互相碰撞進而轟擊鈦六鋁四釩基材,產生氮化鈦的擴散層。實驗中改變不同的加速電壓(25、50 kV)以及鈦離子植入劑量(5×1016、1×1017、2×1017 鈦離子/平方公分) 在2×10-3 Pa的艙體壓力下進行離子佈植,以期達成抗腐蝕性、抗磨耗性以及表面硬度的提升。離子佈植完成後利用小角度X光繞射分析儀進行結晶結構分析,利用X光光電子能譜儀鑑定表面化學組成,利用歐傑電子能譜儀進行縱深分析,利用接觸角量測獲得表面的親疏水性,透過電化學分析評估其抗腐蝕性,透過奈米薄膜材料試驗機評估其表面硬度,透過微振磨耗測試評估其抗磨耗性質。由結果中顯示:(1)金屬蒸氣真空弧技術能夠在具有氮氣的反應槽中之基材表面生成αTiN0.3 and TiN結晶結構;(2)其中當加速電壓為25 kV,植入劑量到達2×1017(鈦離子/平方公分)時,由表面元素分析推測其生成鈍化膜,而在抗腐蝕測試中能有效提升其抗腐蝕性;(3)鈦六鋁四釩經過鈦離子佈植2×1017(鈦離子/平方公分)後能有效提升其表面硬度,同時,其抗磨耗的特性也因此獲得強化。
關鍵詞:金屬蒸氣真空弧、鈦六鋁四釩、抗腐蝕性、抗磨耗性、表面硬度
C.-W. Chang, Study of ion-implanted titanium nitride microstructure using metal vapor vacuum arc technique
ABSTRACT
This study utilized metal vapor vacuum arc source (MeVVA) technique to prepare the Ti-N phase on the surface of Ti-6Al-4V. By this method, non-excited gaseous molecules can be saturated in the processing chamber, leading to collision with the processing ions. The extracted and accelerated metal ions are thereafter bombarded into the target substrate and formed a diffused layer. In the experiment, ion implantation was performed under a pressure of 2×10-3 Pa, then supplied with different acceleration voltages (25 and 50 kV) and titanium ion doses (5×1016, 1×1017 and 2×1017 ions/cm2) in order to improve the corrosion resistance, wear resistance and surface hardness. After ion implantation, the GIXRD was employed for determining the crystalline structure on the modified surface. The XPS was utilized for identifying the new binding species. The AES was used for profiling the treatment depth. Water droplet angle was measured to evaluate surface wetting properties. Corrosion resistance was measured by an electrochemical instrument. Surface hardness was measured by nanoindenter. Wear resistance was measured by micro-motion instrument. Experimental results demonstrated that (1) MeVVA treatment created a novel αTiN0.3 and TiN crystalline structure on the surface of Ti-6Al-4V in N2 atmosphere. (2) When the dose reached to 2×1017 Ti-ions/cm2 with acceleration voltage of 25 kV, corrosion resistance significantly improved by forming a passive film, which could be characterized by EDS detection. (3) After titanium ion implantation with the dose of 2×1017 Ti-ions/cm2, surface-hardness significantly improved; meanwhile, wear-resistance was significantly improved.
Keywords: metal vapor vacuum arc, Ti-6Al-4V, corrosion resistance, wear resistance, surface hardness.
侯孟新95M01:多孔幾丁聚醣改質膠體對於不同重金屬離子之吸附研究(July 2006)
中文摘要
本研究使用幾丁聚醣為基材,利用三聚磷酸鹽以及氫氧化鈉將其製備為膠體以及薄膜,經由冷凍乾燥後可以將膠體以及薄膜乾燥。乾燥後的幾丁聚糖膠體直徑為3 mm而薄膜的厚度為2 mm。乾燥後的膠體以及薄膜接著置於微波電漿改質機台中進行氨氣或氬氣的改質。首先,藉由化學分析電子光譜儀可以觀察到經由氨氣電漿改質的薄膜,其化學結構上的改變。接著,經由感應式偶合電漿質譜儀可以分析幾丁聚糖膠體對於低濃度的銅離子以及鎳離子的吸附特性。而完成吸附的膠體可以藉由1 M的硫酸進行脫附反應並以感應式偶合電漿質譜分析儀進行分析。最後,由以上的實驗可以得到電漿改質對於幾丁聚糖膠體在吸附以及脫附能力上的影響。實驗結果顯示以2%的幾丁聚醣-醋酸溶液滴入2 g氫氧化鈉以及2 g的三聚磷酸鹽中成形的幾丁聚糖膠體可以在較短的時間內成形。依據感應式偶合電漿質譜分析儀定量金屬吸附實驗的結果可以得到幾丁聚醣膠體對於銅離子的吸附選擇性大於鎳離子,而幾丁聚醣膠體在pH 5.1環境時的吸附量大於在pH 2.1。比較電漿改質對於幾丁聚醣膠體吸附的影響可以發現經由氨氣電漿改質後其吸附速率大於氬氣電漿改質以及未改質的幾丁聚醣膠體。由化學分析電子光譜儀可以發現幾丁聚醣在吸附金屬後,可以於金屬的束縛能位置(銅: 933.1 eV;鎳:852.5 eV)發現峰值,如此可以得知金屬被幾丁聚醣所吸附。比較氨氣電漿改質以及未改質的幾丁聚醣可以發現10秒氨氣電漿改質後的幾丁聚醣其N/C比增加10%,因此推論藉由氨氣電漿改質所增加的氮含量為促進幾丁聚醣膠體吸附速度的原因。對於完成吸附的幾丁聚醣膠體進行脫附實驗可以發現經由氨氣電漿改質與未經電漿改質之膠體均可以脫附60%以上的金屬離子。
關鍵字: 幾丁聚糖膠體、三聚磷酸鹽、電漿表面改質、金屬吸附、金屬脫附
M.-H. How,
Modified chitosan hydrogel and its characteristics on various heavy metals
ABSTRACT
In this study, chitosan was prepared in a form of hydrogel bead and of thin film using tripolyphosphate and sodium hydroxide as the cross-linking agent. The as-prepared chitosan hydrogel beads and films were then frozen and dried. Beads with a rough diameter of 3 mm and films with a thickness of 2 mm were thereafter obtained. The dried chitosan beads and films were furthermore modified by either argon or ammonia plasma. New chemical structures on the plasma-modified chitosan film were measured using XPS (X-ray Photoelectron Spectroscopy). The low concentration copper or nickel-ions containing solution was used for the evaluation of beads’ adsorption characteristic and analyzed by ICP-MS (Inductively Coupled Plasma/Mass Spectroscopy). Desorption rate of the post-adsorption beads was conducted in 1 M sulfuric acid, while the change of low concentration metal ions was also analyzed by ICP-MS. The adsorption-desorption effect of the plasma-modified chitosan-containing beads was thereafter discussed. Experimental results exhibited that the formation of hydrogel beads was completed within short preparation time using 2% chitosan-acetic acid solution in 2 g of tripolyphosphate and 2 g of sodium hydroxide. The as-prepared chitosan hydrogel beads were capable to adsorb more copper ions, in comparison with nickel ions. At the same time, the adsorption capacity exhibited higher at the pH value of 5.1 than that of 2.1, while ammonia plasma treatment is much efficient than argon plasma treatment on the adsorption rate of the plasma-modified chitosan hydrogel beads. From XPS, metallic species could be found on the chitosan hydrogel film at the binding energies of 933.1 eV for the copper-N bond and 852.5 eV for the nickel-N bond, which showed the presence of metal ions on chitosan. The N/C ratio increased 10% after 10 sec of ammonia plasma treatment. The increase of nitrogen content on the ammonia plasma treated chitosan resulted in the increase of ion adsorption rate. Desotpion rate of the ion-containing samples was capable to reach 60% by adding 1 M sulfuric acid.
Keywords: chitosan hydrogel bead, tri-polyphosphate, plasma surface modification; metal ion adsorption, metal ion desorption.
簡儀禎95M02:超薄蝕刻阻劑在金的圖形製作表面之抗蝕刻機制研究(July 2006)
中文摘要
自組裝單分子層(Self-Assembled Monolayers, SAMs)排列整齊、結構穩定且可藉由選擇不同尾端官能基的硫醇分子促使SAMs形成具特定功能性的表面。其中,長鏈烷基硫醇分子於Au表面形成SAMs時以硫端與Au產生化學鍵結而形成一具有CH3 官能基之表面。且因CH3 官能基表面具化學惰性,針對特定化學蝕刻液擁有抵抗化學腐蝕之能力,以此特性將可應用於製作微奈米等級圖案的超薄蝕刻阻劑。本研究的重點在於研究探討以SAMs作為製作Au圖案的蝕刻阻劑時,SAMs對於特定蝕刻液抗侵蝕的機制。在本研究中,首先以橢圓偏光術及原子力顯微術針對於經化學蝕刻後試片表面之Au薄膜厚度及其表面相貌而訂定Au蝕刻終點。接著以微觸壓印(Microcontact Printing, μCP)的方法,使用PDMS將含有SAMs成分之圖形轉印於Au表面,而後使用特定配方之Au蝕刻液將轉印於Au表面之圖樣進行顯影。進一步,並將此具圖案的表面以掃描式光電子顯微儀(Scanning Photoelectron Microscope, SPEM)進行表面化學元素分布分析,並使用電子顯微鏡及原子力顯微鏡作圖形表面形貌分析。進一步並針對SAMs被破壞的情形與Au圖案之間的關係進行探討。研究結果顯示,從XPS能譜結果可得知在壓印圖像中SAMs化學結構,唯有接近圖形邊界處,S 2p與C 1s才有被破壞的跡象出現。對照AFM表面相貌圖結果推測,SAMs於特定化學液相蝕刻環境下可以有效正面阻擋蝕刻液侵蝕Au,但是對於蝕刻液之側向侵蝕阻擋力較弱,故SAMs以及Au在圖像邊界皆發現被蝕刻液破壞的現象。 另外,使用μCP製作SAMs圖案時,未接觸到Au表面的軟模所吸附的硫醇分子會因擴散效應而產生非壓印圖案處有蝕刻未完全之現象,因此以未壓印SAMS的Au測得的蝕刻終點與μCP有落差,因此需以延長蝕刻時間或縮短壓印時間方可減輕因硫醇分子擴散而造成之蝕刻不完全現象。
關鍵字:自組裝單分子層、微觸壓印、掃描式光電子顯微術、金化學液相蝕刻
ABSTRACT
Self-assembled monolayers (SAMs) are capable to form a functionalized surface on a metal surface with good uniformity and stability. In this study, alkanethiolate molecules with -CH3 terminated tail group chemically adsorb upon Au substrate and form Au-S bonds, which potentially act as ultra-thin resist films with excellent uniformity in molecular order and high resistivity to chemicals. Anti-etching mechanism of the patterned self-assembled Octadecanethiol (ODT) on Au (111)-dominant surface has been mainly discussed. In the experiment, the end point of Au etching process was determined by ellipsometry and AFM. The patterned SAMs were fabricated using microcontact printing (μCP) technique and subsequent to be developed by Au etching solution. The images of element distribution on the patterned Au were investigated by SPEM. Subsequently surface morphology of the patterned Au was then characterized by AFM and SEM. At the same time, the damaged SAMs in association with the morphology of Au were discussed. Experimental results demonstrated that the damaged pattern at the boundary between the μCP SAMs and the etched part was clearly identified. The SAMs protected part was resistive to a specific etching solution, whereas SAMs at the patterned boundary exhibited weak in resisting the analogous solution. Potentially alkanethiols adsorbed on PDMS stamp tend to diffuse away from the region of contact; thereafter the residual Au in the non-contact region is unable to be removed completely during the etching process. It is suggested to reduce the effect of incomplete etching process by shortening the printing time or extending the etching time.
Keywords: Self-assembledmonolayers, Microcontact printing, Scanning photo-electron microscopy, Au etchant.
潘冠廷95M03:多功能微波電漿處理系統之電漿診斷及光阻去除的研究(July 2006)
中文摘要
本研究藉由電漿診斷技術,以Langmuir probe量測在輝光放電區域改變功率和量測位置等參數對電漿狀態的影響,作為評估及調校機台的測試法,並使用光學放射光譜儀進行電漿清除光阻時物種變化的線上即時監測,來探討多功能微波電漿處理系統在進行光阻去除時電漿對試片的反應機制及處理效率。電漿處理後的試片則以場放射型掃描式電子顯微鏡(FE-SEM)來觀察其表面形貌,並使用能量分散式X-光儀(EDS)及X光光電子能譜儀(XPS)進行表面化學組成的分析。實驗結果顯示: 在激發氣體源為O2,壓力控制在0.2 Torr,施加功率為600~1200 W的參數設定下,電漿密度範圍在1010~1011 N/cm3間,而電子溫度約為7~9.7 eV,屬於高密度電漿,在接近輝光放電區域的位置,光阻可以被電漿清除。以X光光電子能譜儀分析試片表面的化學鍵結,可得知未處理時光阻包含C、S、F、O等元素,經由電漿處理後,S、F等元素於60 sec電漿處理後即由表面移除,C元素之特性峰值面積亦隨電漿處理時間增加而下降,對應於Si基材之特性峰値的發現,則顯示光阻層經電漿處理後移除而使Si基材露出。本研究使用光學放射光譜儀對CO (265.9 nm及482.3 nm)特性峰的監測,作為即時診斷電漿灰化反應的方法,並藉由CO特性峰值的相對強度變化,來評估電漿處理成效及判定實驗的終止點。
關鍵字:電漿診斷、Langmuir 探針、光學放射光譜儀、X光光電子能譜儀、去光阻
G.-T. Pan: The study of plasma diagnostics and photo-resist stripping using multi-functional microwave plasma system
ABSTRACT
This study utilized Langmuir probe as a plasma diagnostic tool to monitor the effect of plasma generation depending on several parameters such as the generation power and the distance along with the glow discharge region. Optical Emission Spectrometry (OES) was also employed to carry out on-line measurement on the released species in association with photo-resist stripping. Surface morphologies were observed using Field-Emission Scanning Electron Microscopy (FE-SEM), while the changes of chemical compositions and structures owing to plasma treatment were characterized by Energy Dispersive X-ray Spectrometer (EDS) and X-ray Photoelectron Spectroscopy (XPS). Under the condition of O2 plasma, 0.2 torr and 600~1200 W with two specified after-glow positions, experimental results demonstrated that plasma density of current treatment system was in the range of 1010~ 1011 N/cm3, comparable with the electron temperature of 7.0~9.7 eV. Photo-resist stripping could be mostly completed at the position close to the glow-discharge region. Surface analyses using XPS revealed that plasma treatment on the surface containing C, F, S and O elements tended to reduced firstly the content of S and F elements, followed by C element. The photo-resist was highly stripped as the Si element was found. The emission intensities of CO at 265.8 nm and 482.3 nm supported the photo-resist stripping reactions that was likely to provide the information on the released rate of the associated chemical species from the photo-resist.
Keywords: Plasma diagnostics, Langmuir probe, Optical Emission Spectroscopy, X-ray Photoelectron Spectroscopy and Photo-resist stripping.
張志仲96M01:可降解及多孔性之適強度幾丁聚醣薄膜膠體(July 2007)
中文摘要
幾丁聚醣是天然的高分子聚合物,其分子結構具有胺基官能基,能與金屬離子產生鍵結而形成穩定的錯合物,適合用來去除重金屬廢液。本研究以未交聯與經0.25 wt%三聚磷酸鹽溶液交聯後的幾丁聚醣薄膜膠體做為研究的材料。首先,探討未交聯與交聯的幾丁聚醣薄膜膠體在機械、含水、溶解性質上的差異,接著,分析未交聯與交聯幾丁聚醣薄膜膠體在吸附銅離子前後變化的情形,最後,利用NH3和NH3/N2電漿改質未交聯與交聯幾丁聚醣薄膜膠體,並觀察對銅離子吸附量及表面成份元素變化的情形。實驗結果顯示:幾丁聚醣薄膜膠體交聯後,其機械性質會有所提升且在酸性溶液中的溶解率會降低。利用掃描式電子顯微鏡觀察出未交聯與交聯的薄膜膠體表面皆有孔洞的分佈,水分子會藉由孔洞擴散進入薄膜膠體內部,所以含水率高。使用能量散佈X光譜儀可以測得兩組薄膜膠體吸附銅離子後,有銅元素訊號產生。以原子吸收光譜儀可以得知交聯後的薄膜膠體對銅離子的吸附量並未因交聯而減少,對照溶解測試結果推測,在酸性溶液中,交聯的幾丁聚醣薄膜膠體比未交聯的溶解率低,所以對銅離子吸附量並沒有明顯地減少。以傅立葉轉換紅外線光譜儀和X光光電子能譜儀分析結果得知,銅離子會與幾丁聚醣分子上的胺基產生了鍵結而吸附,所以屬於化學性吸附。從原子吸收光譜儀和X光光電子能譜儀得知,NH3電漿改質未交聯薄膜膠體,其N/C比減少6.5 %,故對銅離子吸附量減少,而NH3/N2電漿改質未交聯薄膜膠體,其N/C比增加12 %,故對銅離子吸附量增加;若分別以NH3和NH3/N2電漿改質交聯薄膜膠體,其N/C比分別增加4.5 %和16.2 %,故對銅離子吸附量分別增加,因此推論藉由電漿改質所增加氮的含量為促進幾丁聚醣薄膜膠體銅離子吸附量的原因
關鍵字: 幾丁聚醣、電漿改質、原子吸收光譜儀、傅立葉轉換紅外線光譜儀、X光光電子能譜儀
Abstract
Chitosan is a nature polymer which can form stable complexes with metal ions by using the amine group of its molecular structure. Therefore, it is suitable to remove heavy metal-containing wastewater. In this study, two methods were employed to prepare two kinds of films which were non-cross-linked and cross-linked chitosan films by using 0.25 wt% tripolyphosphate solution. At first, the mechanical property, water absorption and solubility of non-cross-linked and cross-linked chitosan films were discussed. Then copper ion adsorption test were analyzed. At last, two kinds of films were modified by using ammonia and ammonia/nitrogen plasma. After that, the capability of copper ions adsorption and chemical bonding species on plasma-modified films were investigated. Experimental results demonstrated that the mechanical property of cross-linked chitosan film was improved and its solubility ratio in acid solution was decreased. Porous structure was uniform spread on the chitosan films detected by Scanning Electron Microscope (SEM), which resulted in high water absorption. The signal of copper was detected on copper ions adsorption of films by Energy Dispersive X-ray Spectrometer (EDS). From Atomic Absorption Spectrometry (AAS), the copper ions adsorption capacity of cross-linked chtiosan film was comparable to that of non-cross-linked chitosan film because cross-linked chitosan had low solubility ratio in acid solution. From Fourier Transform Infrared Spectrometer (FTIR) and X-ray Photoelectron Spectroscopy (XPS), copper ions formed chemical adsorption with amine group on chitosan films. From AAS and XPS, for non-cross-linked chitosan film, the N/C ratio decreased 6.5 % after ammonia plasma treatment, so the capability of copper ions adsorption was decreased. On the other hand, the N/C ratio increased 12 % after ammonia/nitrogen plasma treatment, so the capability of copper ions adsorption was increased. In respect of cross-linked chitosan film, the N/C ratio increased 4.5 % and 16.2 % respectively after ammonia and ammonia/nitrogen plasma treatment, so the capabilities of copper ions adsorption were increased. Therefore, the increase of nitrogen content on the plasma treated chitosan films resulted in the increased capabilities of copper ions adsorption.
Keywords: chitosan, plasma modification, Atomic Absorption Spectrometry, Fourier Transform Infrared Spectrometer, X-ray Photoelectron Spectroscopy.
謝易達96M02:低能量電子束照射之烷基硫醇自組裝單分子層化學吸附於金面做為微影製程之抗蝕刻阻劑(July 2007)
中文摘要
長鏈烷基硫醇自組裝單分子層(Alkanethiol self-assembled monolayers, AT-SAMs)對於特定化學蝕刻液具特定抵抗性;同時,其與物理源(X-ray、離子束、電子束)具有誘導發生反應的作用而形成負/正型阻劑(resist)。因此,本研究企圖使用低能量(E<1 keV)電子束微影術(Low energy electron beam lithography, LE-EBL)作為微影技術,並於微影後使用濕式蝕刻方式進行顯影來進行圖案的製作。首先,在矽晶圓上使用電子束蒸鍍5 nm Ti層,隨後在其上蒸鍍50 nm Au膜得到以Au(111)面為主的表面,同時將蒸鍍好的Au膜及對排列於Au膜面上之正十八硫醇(Octadecanethiol, ODT)試片進行濕式蝕刻分別得到兩種試片Au之蝕刻終止點,以確認ODT排列於Au膜上後對Au蝕刻液的抗蝕效果。接著,以靜態水滴接觸角分析50eV低能量電子束照射不同劑量並曝露於大氣後ODT/Au試片表面親疏水性的改變,以決定微影照射劑量;再將ODT/Au試片經所選擇的劑量照射並曝露於大氣後進行表面元素分析,最後以Au蝕刻液進行顯影。結果發現:以50 eV 低能量電子在照射劑量7.04 mC/cm2微影並曝露於大氣後,受到來自於ODT/Au碳鏈間的交聯、部分的S-Au鍵結破壞以及照射後立即曝露大氣所吸附於表面的碳氧化物種的共同影響下,ODT SAMa於Au膜基材上將形成更緊密複雜的結構而作為負型阻劑,經後續濕式蝕刻15分鐘後將顯影出來Au的負型圖案;當提升照射劑量至64.06及128.13 mC/cm2後,由於ODT/Au上碳鏈及S-Au鍵結的大量破壞,將使ODT/Au結構不能穩固且緊密地排列於Au膜基材上,顯影時Au蝕刻液將容易穿過ODT SAMs抵達S/Au界面而移除Au,而形成正型圖案。由此,ODT/Au可在控制不同LE-EBL照射劑量並曝露大氣後將可分別作為負型阻劑及正型阻劑,於Au蝕刻液中顯影出Au的負型圖案與正型圖案。
關鍵字: 正/負型阻劑、化學濕式蝕刻、低能量電子束微影術、自組裝單分子層
Abstract
Alkanethiol self-assembled monolayers (AT-SAMs) have good resistance for specific wet-etching solutions and behave as negative/positive resists after irradiated by physical sources such as X-ray, ion beams, and electron beam. The aim of this study is to fabricate gold pattern via the low energy (E<1 keV) electron beam lithography (LE-EBL) followed by exposing to air, then developing with gold-etching solutions for octadecanethiol (ODT) on the substrate. The substrate is prepared by first electron-beam evaporating a thickness of 5 nm titanium on the silicon wafer, and followed evaporating 50 nm thickness of gold on the titanium layer. Subsequently, immersing of the gold substrate and ODT/Au samples into the gold-etching solution in order to find out the end time point of gold layer of which, leading to understanding of the resistivity of ODT/Au in the etching solution. Also, the process doses of LE-EBL are determined from the dose-static contact angle relation, followed by HRXPS analysis. Finally, the gold patterns are obtained by gold-etching solution development. Concluded from the analyses of negative-positive resist transformation, the experimental procedure of ODT/Au was first irradiated by 50eV LE-EBL with three specific doses, after that proceeded to exposed to air. With the dose of 7.04 mC/cm2, ODT/Au will become a more strengthened structure and then form a negative resist in the correlation with cross-linking from alkyl matrix, partial breakdown of S-Au bonding and surface adsorption by air-borne species. Thus, it can obtain a gold pattern via gold-etching process. Besides, as a result of massive breakdown of alkyl matrix and S-Au bonding from ODT/Au under irradiation with doses of 64.06 and 128.13 mC/cm2, ODT SAMs would form a loose-packed structure on the gold substrate. The ODT/Au becomes less resistive for gold-etching and a positive gold pattern would form after gold-etching. By controlling LE-EBL doses and being exposed to air at the following step, ODT/Au could behave either as negative or positive resists. Finally, it will perform the negative and positive gold patterns after gold-etching process.
Keywords: self-assembled monolayers、low energy electron beam lithography、chemical wet-etching、positive/negative resist
蔡世群97M01:藉由順流式微波電漿在自組裝單分子層上進行圖案轉移並應用於微影製程及分子的置換(May 2008)
中文摘要
自我組裝單分子層(self-assembled monolayers, SAMs)受X-ray、電子束或離子束等物理源照射後可呈現負型或正型阻劑的特性;且利用電子束照射可促進SAMs分子的置換反應;除了前述的物理源之外,順流式微波電漿也是一種對SAMs改質的方法。因此,本研究利用順流式微波氮氣電漿對以化學吸附於金面上的octadecanethiol (ODT) SAMs進行改質,ODT/Au以金網遮罩後暴露於電漿進行圖案轉移,接著利用金蝕刻液進行蝕刻反應使轉移後的圖案顯影;隨後利用Mercapto-undecanoic acid (MUA)的酒精溶液進行置換反應測試電漿處理過的ODT/Au,觀察是否存在來自MUA的新S-Au鍵結及COOH尾端官能基來識別置換反應的發生。藉由同步輻射高解析X光光電子能譜術及掃描式光電子顯微術分析各個不同階段的表面鍵結變化,以探討兩個主題:形成負型或正型阻劑的可能機制,以及隨著電漿處理後進行的置換反應發生程度。
實驗結果顯示,藉著控制不同電漿處理時間,可使電漿改質後的ODT/Au呈現出負型或正型阻劑的特性,造成此現象的可能效應有:頭端分子、碳鏈層及尾端官能基的氧化及脫附而破壞SAMs在金面上的結構,還有碳鏈的交錯鏈結而強化分子的結構。經電漿處理過的ODT分子則會因MUA而發生脫附與置換。基於這些研究結果,利用電漿在SAMs上進行圖案轉移並結合分子的置換反應,未來可應用於製作微米/奈米等級元件如微流道、微型生物感晶片等。
關鍵字:順流式微波電漿、掃描式光電子顯微術、自組裝單分子層、負型或正型阻劑、置換反應同步、輻射高解析X光光電子能譜術
Abstract
Self-assembled monolayers (SAMs) can behave as negative or positive resist after irradiated by physical sources such as X-ray, electron beam or ion beam. As well, the electron beam irradiated SAMs can thereafter promote exchange reactions with other SAMs molecules. In addition to the mentioned physical sources, the downstream microwave plasma can provide an alternative method to modify SAMs. In this study, we applied the downstream microwave nitrogen plasma for the modification of the octadecanethiol (ODT) SAMs chemically adsorbed on Au. The ODT/Au was masked by Au mesh and patterned by the exposure of plasma. The patterned ODT/Au was then developed by Au etching process. Subsequently the plasma-exposed ODT/Au was particularly examined by the molecular exchange reaction with Mercapto-undecanoic acid (MUA) in ethanol. The exchange reaction on the plasma-exposed ODT/Au was distinguished by the presence of newly formed S-Au bonds and the COOH tail group from MUA. Synchrotron-based high resolution X-ray photoemission spectroscopy and scanning photoelectron microscopy were applied to characterize the surfaces prepared in different stages. Two topics were discussed: a possible mechanism that formed a negative or positive resist and an extent of subsequent exchange reaction on the plasma-exposed ODT/Au. Experimental results demonstrated that by controlling the plasma exposure time, the modified ODT/Au was competent to behave as negative or positive resist. The most probable process is related to the oxidization or molecular desorption (i.e. with the tail group, alkyl chains, and the head group) that tends to damage SAMs structure adsorbed on Au as well as cross-linking among alkyl chains (i.e. with a significant amount of lasting S-Au bonds) that tends to enhance the molecular configuration. The plasma-exposed ODT molecules on Au could also be desorbed and exchanged by MUA. Based on these findings, it is promising to apply the plasma-patterned SAMs combined with the molecular exchange reaction for making the variety of micro/nano devices such as micro-fluid channels and micro-scale bio-chip.
Keywords:synchrotron-based high resolution X-ray photoemi 、scanning photoelectron microscopy 、molecular exchange 、negative or positive resist 、downstream microwave plasma 、self-assembled monolayers.
謝旻昌97M02:多孔幾丁聚醣薄膜對銅離子的吸附與脫附機制之研究(June 2008)
中文摘要
幾丁聚醣為一種價格便宜且可廣泛的被應用的的天然高分子,胺基可以與重金屬離子形成鍵結而吸附,因此本研究利用冷凍乾燥製程並使用酒精取代氫氧化鈉來將薄膜內的醋酸置換出來。採用掃瞄式電子顯微鏡觀察表面形貌及拉伸試驗機檢測製程時不同階段的機械性質;以三聚磷酸鈉為交聯劑增加對不同化學環境的抵抗能力,並探討在不同pH值或溫度對於吸附和脫附銅離子的影響,利用硝酸進行脫附試驗,使用原子吸收光譜儀檢測銅離子吸附和脫附之間的效率轉換情形;再搭配X光光電子光譜儀及傅立葉轉換紅外光譜儀對化學鍵結變化情形做分析。
實驗結果顯示:使用酒精置換醋酸的幾丁聚醣薄膜可以讓薄膜孔洞直徑約170~240 μm,並在三聚磷酸鈉交聯後平均仍有190 μm。加上交聯劑後的幾丁聚醣薄膜的機械和化學性直接有明顯的變化。從化學分析知,幾丁聚醣對於銅離子的吸附是由於上面的胺基的存在造成,而本製程置備出來的幾丁聚醣薄膜擁有適當的孔洞大小可以讓銅離子輕易的擴散於其中。銅離子以40 oC、pH=5環境下的吸附量最多,吸附量達52.41 mg/g。
由實驗結果推論幾丁聚醣吸附或脫附銅離子的機制如下:(1) 乾燥後由XPS發現大量的Cu-O鍵結和Cu2+訊號,和胺基產生庫倫靜電力相互吸引;(2) 當pH值降低,會造成胺基質子化程度增加而減少用來吸附銅離子的負電荷位置;(3) 脫附則是發生於幾丁聚醣的胺基吸引氫離子或是螯合。然而,幾丁聚醣膜的第一次脫附效率約為75 %,而第二次則為60%。顯示出這樣的環境處理可以使幾丁聚醣於銅離子吸附更為實用。
關鍵字:銅離子吸附、幾丁聚醣薄膜、胺基、脫附
Abstract
Chitosan is an inexpensive and a widely available nature polymer; its amine group is usually competent to bind with heavy metal ions. In this study, chitosan films were prepared by freeze-drying procedure, and replaced sodium hydroxide by using alcohol to metathesis acetic acid inner the thin film. Morphologies and mechanical properties of the as-prepared chitosan films in different processing stages were measured by Scanning Electron Microscope and MTS. In addition, the chitosan films were purposely cross-linked with tripolyphosphate to increase the resistance of chemicals in different processing stages, such as the pH values and the temperature for copper ion adsorption/desorption. Desorption rate of copper ions was tested by nitric acid solution and measured by Atomic Adsorption spectrometry. Chemical structures of the tested chitosan films were characterized by Fourier Transform Infrared Spectrometer and X-ray Photoelectron Spectroscopy. The proposed mechanism for copper ion adsorption and desorption was thereafter studied.
Experimental results demonstrated that the pore sizes of the pristine and the cross-linked chitosan films were about 170~240 and 190 μm, respectively. Mechanical and chemical properties of the cross-lined chitosan film were significantly enhanced. From the chemical analyses, the adsorption of copper ions was resulted by the presence of amine group in chitosan and enhanced by the easily-diffusion (or the appropriate porosity) of copper ions in the chitosan matrix. The adsorption capacity was maximized at 52.41 mg/g under 40 oC and the pH value of 5.
The apparent mechanism of the copper ion adsorption/desorption can be proposed as: (1) The bonding of copper-oxygen and copper ion attract amine group each other with electrostatic attraction in the dryied thin film and find copper-oxygen was the mainly bonding from XPS; (2) As decreased the pH value in solution, the protonation of the amine group also increases, leading to the rise of the negatively-charged sites for binding with copper ions; (3) The desorption occurs when the amine group is attacked and chelated by H+. Moreover, the first and second desorption efficiencies were estimated as 75 % and 60 %, which is still promising for the preliminary treatment on the copper ions adsorption.
Keywords:amide group、desorption、adsorption of copper ion、Chitosan film
陳冠名97M03:氬氣或氮氣微電漿系統對光阻去除作用之評估(June 2008)
中文摘要
本實驗欲開發之微電漿系統為可在大氣壓力下作用之開放式處理技術,並通入氬氣或氮氣為工作氣體用以進行光阻去除。實驗中將藉由光學放射式光譜儀以及示波器觀測即時電漿狀態,以判斷電漿中的激態物種及評估能量傳遞的效率;電漿處理過之試片則以表面粗度儀掃描光阻清除區來得到蝕刻的深度,並以X光光電子能譜儀掃描試片表面之化學元素變化以推測其可能產生的化學反應;此外亦嘗試將單元電極陣列化,期望能增加光阻去除之效能。
由示波器量測電性的結果顯示氮氣微電漿對於能量的需求相較氬氣微電漿要高,因此實驗中使用40 W於氬氣微電漿、100 W於氮氣微電漿以維持穩定電漿狀態。量測處理深度可推算出氬氣微電漿及氮氣微電漿在去除80 %光阻層的速率為404 nm/min及81.7 nm/min;X光光電子能譜儀所得到的表面化學分析結果證明了氬氣微電漿處理過的試片表面並沒有明顯形成新的化學鍵結,而氮氣微電漿處理則會造成表面形成氧化物及C-NO鍵結,這些結構可能阻礙電漿進一步的對光阻層進行清除;從光學放射式光譜儀的觀測結果亦可輔助說明在氬氣微電漿系統中產生的激發物種是以氬氣的衍生物為主,而氮氣微電漿系統中則以激態的氮氣分子及NO為主。綜合以上結果可推論,氬氣微電漿對光阻去除的作用主要是以物理性的轟擊為主,速度較快;而氮氣微電漿則多以化學性的斷鍵作用為主,並由於光阻結構複雜、C=O鍵結殘留以及部分NO打斷碳氫鍵結後附著於光阻層,減緩了光阻去除的效應,造成處理效率的下降。此外,建構陣列式的微電漿系統並在氬氣中混入0.5 %的氧氣,亦證實其確有光阻去除的效用,速率為120 nm/min。
從上述的結果我們可以發現,氬氣及氮氣微電漿系統對於光阻去除皆具有一定的成效,但後者可能會產生一些阻礙光阻去除的化學因素而減緩去除速率。因此若能加以調整工作氣體的成份比例,降低作業成本而實際應用到線上製程是可以期待的。
關鍵字:光阻去除、微電漿、激發物種、光學放射式光譜儀
Abstract
In this work, photo-resist stripping effects were evaluated by micro-plasma system. Argon or nitrogen was employed as the working gas under atmospheric pressure. Optical Emission Spectroscopy (OES) with oscilloscope was utilized for detecting real-time excited species and measuring energy transmission efficiency. Plasma-induced stripped depth was determined by α-step scanning, while chemical composition of treated surface was characterized by X-ray Photoelectron Spectroscopy (XPS). Furthermore, an array micro-plasma system was designed for comparing with single micro-plasma system and for the enhancement of the photo-resist stripping effect. Energy requirement for nitrogen micro-plasma system was relatively high in comparison with argon micro-plasma system, characterized by the oscilloscope. A power of 40 W was applied for argon micro-plasma system and 100 W for nitrogen micro-plasma system to maintain a stable plasma state. Experimental results demonstrated that a stripping rate of 80 % photo-resist was 404 nm/min and 81.7 nm/min for the respective system. Surface analyses by XPS revealed that no obvious chemical composition occurred in the argon-plasma treated photo-resist surface, whereas new chemical bonding such as oxide and C-NO were formed on the nitrogen-plasma treated surface and probably reduced furthermore stripping effect on the surface. From OES spectra, argon-derivatives were dominant as the excited species in argon micro-plasma system, while nitrogen and nitrogen-oxygen species were mainly found in nitrogen micro-plasma. To sum up, physical bombardment dominated photo-resist stripping effect in argon micro-plasma system, and resulted in higher stripping rate than nitrogen micro-plasma system within chemical bond breakage dominated stripping effect. Retardation of stripping in nitrogen-plasma were resulted from complicated molecular structure of photo-resist, C=O residues and part of NO bonded to photo-resist. In addition, for the array micro-plasma system with the addition of 0.5 % oxygen into argon exhibited effective in photo-resist stripping process with a stripping rate of 120 nm/min. Base on these findings, both argon and nitrogen micro-plasma systems are effective in photo-resist stripping. The latter may create stripping-prohibited bonding and retard the stripping process. It is therefore promising to adjust the ratio of the gases to reduce the overall cost and to apply array micro-plasma system for in-line processing.
Keywords: excited species、optical emission microscopy、photo-resist stripping、micro-plasma
楊嘉芬97M04:探討微米尺度之鍍金粒幾丁聚醣膜表面對3T3纖維母細胞的貼附與生長的反應(June 2008)
中文摘要
幾丁聚醣由於具有無毒性、生物可降解性、生物相容性和價格便宜等優點,被視為優越的可運用於組織工程的生醫材料。雖然幾丁聚醣是一合適的支架材料,但對纖維母細胞幾乎沒有促進生長的效果。此外,由於細胞形貌與細胞和表面的作用息息相關,培養纖維母細胞在幾丁聚醣上,細胞型態多呈球狀。而細胞受生物基材表面的物理化學訊號影響,主要可分為三類:化學、形貌和機械性質,本研究以修飾特別製備的幾丁聚醣膜表面性質來改善細胞親和性。以電子束蒸鍍技術搭配蒸鍍罩,於幾丁聚醣膜表面蒸鍍上有圖案狀的微尺度金群。蒸鍍上的金群直徑約150 μm,厚度約20 nm。在幾丁聚醣膜上金群彼此間距1000 μm。以掃描式電子顯微鏡和共軛焦 3D 光學表面形貌量測儀來分析表面形貌。能量散佈光譜儀、光電子化學光譜儀和接觸角量測儀來分析化學性質。以薄膜壓痕試驗機的動態接觸模組作金群和幾丁聚醣基材的奈米尺度機械性質分析。實驗結果證明相較於幾丁聚醣基材,蒸鍍上的金群和金群附近的區域,具有較合適的聯合性質,去促進纖維母細胞的貼附性、攤開和生長狀況。且可觀察到細胞多聚集在此金群和金群附近的區域上。特別的是奈米尺度的表面機械性質在這些區域都有增進的效果。由金群造成的結合適當的化學及機械性質,在幾丁聚醣膜上創造一適宜纖維母細胞選擇性生長的表面,期望在組織工程的應用上可在引導細胞生長的影響多提供一種可能的方法。
關鍵字:奈米尺度機械性、纖維母細胞、蒸鍍上金群、幾丁聚醣
Abstract
Chitosan is classified as an excellent biomaterial owing to the advantages of non-toxicity, biodegradation, biocompatibility, and low cost. Though chitosan is regarded as a suitable scaffold material, it shows almost no promotion effect on the growth of cultured fibroblast cells. Besides, cell shapes induced by cell–surface interactions tend to become round. Cells on a biomaterial surface usually respond to three main categories of physicochemical cues: chemically, topographically, and mechanically. In this study, mechanical property of a particularly-prepared chitosan film was modified to improve its cell affinity. Micro-scale Au clusters were patterned and seeded on the chitosan film using a shadow mask and electron beam evaporator. The dimension of the evaporated Au cluster was 150 μm in diameter and 20 nm in thickness. They were separated at a distance of 1000 μm on the chitosan film. Scanning Electron Microscope and 3D Confocal Microscope were used to characterize their surface morphologies. X-ray Photoelectron Spectroscopy, Energy Dispersive Spectrometer, and water contact angles were employed to examine their chemical structures. Nano-indenter with dynamic contact module was applied to measure their nano-mechanical properties surrounding Au cluster and the chitosan matrix. Experimental results demonstrated that as compared with the chitosan matrix, the patterned Au clusters and their neighboring area exhibited a suitable and combined property to promote cell adhesion, spreading, and growth. Fibroblast cells were found accumulated surrounding Au clusters and their neighboring area. In particular, nano-mechanical properties in this domain significantly enhanced. In combination with the possible chemical and mechanical changes caused by Au cluster, a selectively-enhanced chitosan surface for fibroblast cells was created, which is promising for enabling a cells-guidable effect in tissue engineering.
Keywords:Chitosan film、nano-mechanical、fibroblast cell、evaporated Au cluster
謝瑞夫97M05:添加甲烷或乙炔於氬氣電漿中對於非平衡磁控濺鍍沉積含氫非晶質碳膜性質之影響(June 2008)
中文摘要
本研究將以非平衡磁控濺鍍法在矽晶圓上沉積含氫非晶質碳膜,各別將甲烷與乙炔以不同通量混入固定通量(25 sccm)的氬氣,以直流電源激發氣體產生電漿,沉積時間固定為120分鐘。在濺鍍製程中,同時以光學放射光譜儀(OES)透過真空腔體窗口記錄電漿內激發物種的種類與強度。以拉曼光譜儀(Raman)與傅立葉轉換紅外光譜儀(FTIR)來量測含氫非晶質碳膜表面的結構並作定性分析。以奈米壓痕機量測碳膜的硬度、楊氏係數、抵抗側向刮痕的能力與表面的摩擦係數。掃瞄式電子顯微鏡量測膜厚與觀察表面形貌;高阻抗電阻儀量測碳膜電阻值。由OES光譜可知,Hα與Hβ的強度在甲烷/氬氣電漿隨流量變化程度比乙炔/氬氣電漿大,從流量增加來觀察激發物種強度變化,Hα與Hβ比CH*與C2*更容易受到電漿激發。隨流量增加單位氣體分子獲得能量降低,推測甲烷主要解離成CH3而乙炔主要解離成C2H。從Raman與FTIR光譜結果得知,當甲烷或乙炔流量增加,碳膜表面的sp3 CH3與sp3 CH2鍵結增加,使碳膜的sp3/ sp2比增加,此外sp2結構將從苯環狀碳環轉變成烯烴碳鏈;乙炔碳膜的sp3/ sp2比增加幅度比甲烷碳膜小,因為甲烷直接解離成CH3即可形成sp3 C-H結構,但乙炔解離成C2H後需要再進一步反應才能形成sp3 C-H結構。氫在碳膜中阻擋碳碳原子間形成sp3 C-C並且形成sp3 C-H,造成碳膜硬度隨C-H鍵結增加而下降,10 sccm的甲烷碳膜與乙炔碳膜硬度降至2.75 GPa與5.86 GPa。由於C-H鍵結將鈍化碳膜表面,使甲烷與乙炔碳膜的摩擦係數隨著表面C-H結構增加而降低。由於碳膜的表面sp3 C-H鍵結增加與sp2結構從碳環轉變成碳鏈,導致甲烷碳膜電阻值隨流量而劇烈增加而乙炔碳膜電阻值則隨流量而緩和增加。由激發氣態物種觀察與碳膜性質比對,沉積後的碳膜機械性質主要是受到表面形成的sp3 C-H結構影響,sp3 C-H結構的形成則與甲烷/氬氣和乙炔/氬氣電漿的解離效率有密切關聯。
關鍵字:含氫非晶質碳膜、光學放射光譜儀、甲烷/氬氣、乙炔/氬氣、非平衡磁控濺鍍
Abstract
Hydrogenated Amorphous Carbon (a-C:H) films was deposited on the silicon substrate by unbalanced magnetron sputtering with the addition of methane (CH4) or acetylene (C2H2) and the variation of flowing rates from 2 to 10 sccm into argon plasma. The flowing rate of argon was constant at 25 sccm and the deposition time was fixed at 120 min. Optical Emission Spectrometer (OES) was employed in analyzing the excited species in methane or acetylene/argon plasma through a view port of the processing chamber. The quality of a-C:H films, including their chemical structure, nano-hardness, friction coefficient, and surface resistance, was examined. From OES spectra, the emission intensity of atomic hydrogen Hα and Hβ for methane/argon plasma was found higher than that for acetylene/argon plasma. In addition, by increasing the flowing rate of methane or acetylene, the intensity of Hα, Hβ, CH*, C2* significantly changed. The excitation of Hα and Hβ were relatively simple, in comparison with that of CH* and C2*. It is assumed that CH4 and C2H2 were firstly ionized into CH3 and C2H, respectively. From Raman and FTIR spectra, as increased the flowing rate of methane or acetylene, sp3 CH3 and sp3 CH2 structure increased on surface that caused sp3/sp2 ratio of a-C:H films increased; in addition, sp2 structure transformed from aromatic rings into olefinic chains. Owing to the varied lengths of pathway to ionize the hydrocarbon species, methane was more affected than acetylene by the formation of sp3 C-H on the a-C:H surface. Hydrogen in a-C:H films blocked carbon atoms to form the sp3 C-C (cross-linking) and formed sp3 C-H instead which caused nano-hardness of a-C:H films decreased with the increased flowing rate of methane or acetylene. Nano-hardness of a-C:H films decreased to 2.75 GPa and 5.86 GPa at the flowing rate 10 sccm of methane and acetylene. Due to sp3 C-H increased and sp2 structure transformed, the resistance of a-C:H films increased with the flowing rate of methane or acetylene. From the observations of the excited gaseous species and the quality of a-C:H films, the mechanical properties of a-C:H films were most probably affected by the formation of sp3 C-H structure, which was closely associated with the efficiency of ionization from methane/argon or acetylene/argon plasma.
Keywords:optical emission spectrometer、unbalanced magnetron sputtering、methane/argon、acetylene/argon、hydrogenated amorphous carbon
翁志強96D01:自由基為主順流式微波電漿處理自組裝單分子層反應機制的研究(Jan 2007)
中文摘要
本研究以自製順流式微波電漿機台(downstream microwave plasma, DMP)作用於以化學吸附方式固定於Au(111)或Ag(111)的自組裝分子層Self-assembled monolayers, SAMs),結合同步輻射高解析X光光電子能譜(synchrotron-based high resolution X-ray photoelectron spectroscopy, HRXPS ),即時探討DMP、SAMs以及金屬基材界面的反應機制。
以Langmuir probe對所設計的DMP進行電子密度及電子溫度的量測,所得電漿密度約為106 n/cm3,電子溫度約為0.5 eV,此可証實研究所使用的DMP系統其具高能量的物種少,經順流後主要的作用物種應為以存活期較長的自由基等活性物種為主,因此將本DMP系統定義為以自由基為主的電漿處理系統。
以此定義的電漿系統處理不同SAMs以及不同基材的分子層,其結果顯示,SAM分子以及其頭端硫-金屬的介面反應與電漿的組成相關,尤其以氧的相關物種為主要反應物種。主要的電漿誘導反應為脫氫、碳鍊以及含硫物種的脫附效應、碳鏈層以及硫-金屬介面的氧化效應。而整體反應速率正比於氧的含量,也就是與電漿整體反應性相關。
在探討微量氧於氮氣以及氬氣的反應性差異的實驗中,則顯示在氮氣為主的電漿中,氧的反應性較氬氣電漿顯著,而電漿的反應性以氧相關的物種為主,而氮氣電漿所產生的氮相關物種其能量傳遞的效能優於氬氣電漿。此外,具長碳鏈的SAM分子固定於Ag(111)表面,其可抵抗電漿處理的程度優於固定於Au(111)面的SAM分子。
藉由上述理論的探討,使用此以自由基反應為主的DMP電漿系統於SAMs/Au表面製作圖樣,並以掃描式光電子顯微術(Scanning photoelectron microscopy, SPEM)分析電漿處理後表面鍵結變化。研究結果顯示,藉由電漿處理時間的控制,使SAM分子產生負型或正型光阻的效能,而此效能主要與SAM分子與電漿的反應隨時間變化相關。而藉由蝕刻程序,可證實圖樣轉印的效果。藉由此測試,顯示本系統具有製作微米/奈米等及元件例如微流道、生感測器或者提供微電漿製作的可行性。
關鍵字:順流式微波電漿、自組裝分子層、同步輻射高解析光電子能譜術、掃描式光電子顯微術、圖樣轉印工具
Abstract
In this work, we applied custom-made downstream microwave plasma (DMP) upon self-assembled monolayers (SAMs) chemically adsorbed on Au or Ag (Metal). The pristine and plasma-modified SAMs/Metal substrates were then characterized by synchrotron-based in-situ high resolution X-ray photoelectron spectroscopy. Their reaction mechanisms at the plasma/SAMs/Metal interfaces were studied.
The diagnosis of the DMP system was performed by custom-made Langmuir probe. Plasma density of the DMP system was estimated as 106 particles/cm3 or correlated with an electron temperature of around 0.5 eV. Plasma state of current DMP system was thus considered as low content of energetic species, whereas only long-lives free radicals were possible to survive in the course of traveling a distance. A free radical-dominant DMP system was then provided for the subsequent studies.
This defined plasma system was employed to react with various SAMs/Metal. The SAM molecules and head-group S-Metal bonds were sensitive to plasma composition, in particular, the oxygen-derivative species. The primary plasma-induced processes were dehydrogenation, desorption of hydrocarbon and sulfur-containing species, and the oxidation of the alkyl matrix and S-Metal interface. The reaction rates of all major plasma-induced processes were found to be directly proportional to the oxygen content in the plasma, which can be correlated with the measurement of plasma reactivity.
In the study of minor oxygen content in non-oxygen plasma, it was found that oxygen/nitrogen plasma was much reactive in comparison with oxygen/argon plasma. The minor content of oxygen-derivative species played an important role in plasma reactivity, while nitrogen-derived species were relatively efficient in energy transfer. In addition, SAM molecules with long alkyl chains and S-Ag bonds, compared with S-Au bonds, were much resistant to an analogous plasma treatment owing to the characteristic of low-density plasma.
Based upon these fundamental studies, we applied this technique to make a defined pattern on SAMs/Au using the analogous free radical-dominant DMP system and a particular synchrotron-based scanning photoelectron microscopy. By controlling the plasma exposure time, the modified SAMs/Au exhibited as a respective negative or positive resist, which was mostly related to plasma reaction with SAM molecules. After etching on the modified SAMs/Au, a clear pattern was exactly developed. From this frequently-used example, it is therefore very promising to apply this patterning method for the making of micro/nano devices such as micro-fluid channels, very small scale bio-chip, micro-discharges for novel micro-plasma system.
Keywords: Downstream microwave plasma, self-assembled monolayers, synchrotron-based high resolution X-ray photoelectron spectroscopy, plasma reactivity, patterning method.
吳宜蓁 93_01:生醫金屬表面佈植TiO2結構之抗菌抑菌性質研究
(Jan 2005)
93年度國科會大專生專題研究計畫研究創作獎
93年度國科會大專生專題研究計畫(93-2815-C-006-006–E)
謫要
在本計畫中,將採用輕金屬做為生醫應用的基材。先利用電漿沈積Ti鍍膜,再利用O2電漿離子佈植以加速撞擊處理,使產生植入基材之TiOx漸進層。以表面微結構分析方法,如:低掠角X光繞射儀、歐傑電子能譜儀、及原子力顯微鏡等,研究修飾後基材表面的微結構,以對應其表面抗菌抑菌的特性。在TiO2光觸媒的效能評估方面,利用TiO2對亞甲基藍溶液之吸收光譜強度改變的方法、以及TiO2的薄膜上進行抗菌測試步驟,比較其間光觸媒誘導抗菌效果的差異。擬經由這些的結構分析與功能性測試,調整Ti鍍層與O2電漿離子佈植的製程,完成製備輕金屬表面特殊的微結構,使同時具有質輕、高強度、及光觸媒生醫金屬表面的性質。
林穎宜94_01:經化學修飾的生物可降解材料表面之的細胞親和性 研究(Jan 2006)
國科會大專生專題研究計畫(94-2815-C-006 -089 –B)
謫要
L型聚乳酸具生物相容性、生物可降解性且具有適當的機械性質,可用於神經導管之支架。幾丁聚醣則具有細胞親和性,用以促進周邊神經的再生。本研究以電漿活化聚乳酸基材表面,產生的自由基再與通入的氣態丙烯酸單體結合;藉由羧基與胺基間產生醯胺鍵結固定幾丁聚醣於L型聚乳酸表面,期能同時結合可降解之L型聚乳酸基材及具表面功能性之幾丁聚醣兩者的優點。實驗以共軛焦3D光學表面形貌量測儀(Nano Focus)觀察試片表面型態變化,以減弱式全反射紅外線光譜儀及化學分析電子光譜儀分析表面鍵結結構的變化。然後,以抗菌測試及細胞貼附測試來探究具幾丁聚醣表面之試片的生物功能性。
實驗結果顯示:氣態丙烯酸單體可接枝於L型聚乳酸薄膜上,並可避免熱裂解方式造成試片機械性質下降。並藉由表面化學分析方法印證幾丁聚醣藉由醯胺鍵結,固定於已接枝丙烯酸單體之聚乳酸薄膜表面上。纖維母細胞型態於固定幾丁聚醣後之聚乳酸薄膜上,經培養36小時後其伸展程度比純聚乳酸薄膜小,推論固定幾丁聚醣後之聚乳酸薄膜將降低纖維母細胞於表面上的貼附能力。而細胞在試片上的貼附能力減低,可以降低貼附細胞增殖的速度。此結果可應用於神經導管的支架製作上,將可降低疤痕組織的發生,促進周邊神經再生的效能。
關鍵詞:L型聚乳酸、幾丁聚醣、氣態丙烯酸、周邊神經再生。
張純菁94_02:生醫用非金屬表面經TiO2離子佈植之抗菌性研究
(Jan 2006)
國科會大專生專題研究計畫(94-2815-C-006-056–E)
謫要
離子佈植方法是物理的技術、其能夠在基材表面產生一擴散漸進層。金屬蒸氣真空弧技術則是將純金屬離子化至氣態並與反應槽中特殊氣體分子反應,進而轟擊基材。此種表面改質技術可在表面形成數百奈米深的處理層。然而,本研究擬利用金屬蒸氣真空弧技術在鈉玻璃表面上進行改質,藉由鈦金屬離子加速撞擊氧分子而植入玻璃基材中形成光觸媒結構。由實驗中顯示:經過金屬蒸氣真空弧技術進行表面改質後,透過亞甲基藍測試可以發現其氧化能力約15~20%;透過UV/VIS 測試可以發現其穿透率下降約40%;同時,藉由細菌實驗發現明顯的抑菌圈,顯示出其抗菌效果。因此可說明光觸媒的植入可以明顯的看出其對有機物的降解能力,即可達到自潔的效果;另外,可藉由穿透率的下降來達到遮光的效果。未來,更期望能針對定性測試部分進行更深入的分析,進而能控制其有效結構。
關鍵詞:金屬蒸氣真空弧、表面改質、光觸媒、降解。
黃偉欽94_03:添加傷口癒合藥物SULBOGIN於生物可降解材料(PLGA)的控釋型生醫敷料研究(Jan 2006)
謫要
為免除患者於換藥時所產生的痛苦,本研究以生物可降解材料:聚乳酸聚甘醇酸共聚物(PLGA50:50)為基材製作傷口敷料薄膜,且於薄膜內包埋傷口癒合藥物Sulbogin,以促使傷口快速癒合,並藉由控制PLGA薄膜之製程以控制釋放Sulbogin之速率。經由掃瞄式電子顯微鏡(SEM)及能量分散光譜儀(EDS)觀察結果可知,經由本研究之製程而得的PLGA/Sulbogin薄膜,具有一側藥物較為緻密而另ㄧ側含藥量較低的偏析現象,由此特殊設計,可使藥物均勻釋放,避免產生藥量傾釋的現象。
將PLGA/Sulbogin薄膜置於恆溫37℃下進行體外藥物釋放量測,並以Sulbogin 之主成分:沒食子酸鉍(Bismuth Subgallate)作為藥物釋放檢測的目標, Bismuth Subgallate以UV光譜儀檢測出之吸收峰位置在327nm ,換算得到每日的藥物釋放量皆為一穩定值,且於體外釋放21天後,釋放藥量約可達0.3mg。
關鍵詞:生物可降解、聚乳酸聚甘醇酸共聚物、藥物控制釋放、沒食子酸鉍、龍腦、偏析。
王儒揚95_01:以金屬蒸氣真空弧技術進行透明導電薄膜之電性及光學分析(Jan 2007)
國科會大專生專題研究計畫95-2815-C-006 -050 –E
謫要
透明導電氧化物薄膜在許多光電元件的製造上扮演不可或缺的角色,氧化鋅(ZnO)因物性佳,生產成本低廉,成為最具開發潛力之透明導電薄膜材料,應用範圍極為廣大。氧化鋅其本質上是一個N型的半導體材料,有許多的研究對於如何將氧化鋅基材經由適當的摻雜將其轉變為P型的半導體做了許多的探討;除了傳統的摻雜技術,近日來我們發現,離子佈植技術( ion implantation )是一個很好的摻雜的新方法。
在半導體工業中,離子佈植技術常被廣泛地用來作為摻雜三五族雜質原子;近年來更被應用於材料表面性質的改質上,藉以改變材料表面的外觀、導電性、以及硬度、強度和抗腐蝕性等機械性質,藉以得到最佳化表面性質。而其改變性質的微觀機制還在不斷的研究當中,但主要的機制有損傷強化、析出強化、珠擊強化,以及壓縮強化等等。在離子佈植的過程中,雜質原子或分子係以一個帶電離子的形式被加速至一特定能量,直接撞擊靶材而進入其內。因此,佈植離子於靶材內的縱深分佈可由精確的控制離子能量來得到,而佈植離子的劑量則可由佈植的時間以及離子束的電流得到良好的控制。除了可有效地控制佈植離子的縱深分佈及劑量,利用離子佈植的方法可以得到較均勻分佈及較高純度的摻雜物,且可利用光罩(mask)來選擇所欲佈植的區域。由前面可知離子佈植可以改變材料的許多性質,本實驗主要是比較傳統的磁控濺鍍與金屬蒸氣真空弧佈植法電性與光性的差異。在金屬蒸氣真空弧製程中改變不同的劑量與頻率來探討會改善何種性能。
姚智凱95_02:聚乳酸多孔型神經再生導管製程改良與性質評估(Jan 2007)
謫要
神經系統為人體中最為精細複雜的構造,如果受到損傷,輕則使部份連接組織器官無法運作,嚴重甚至可造成全身癱瘓。人體的神經系統由兩個部分組成:周邊神經系統(peripheral nervous system,PNS)負責接收外在環境的刺激訊息,將之傳送到由腦及脊髓構成的中樞神經系統(central nervous system,CNS),再經由周邊神經系統將中樞神經系統所下的反應訊息傳送到目的器官,以使人體做出對外在環境刺激下的反應。無論在周邊或中樞神經系統中,神經組織創傷的復原比起人體中其他各種組織創傷的復原過程要複雜許多,因為成熟的神經細胞不會再進行細胞分裂,然而在適當的條件下,神經細胞的軸突卻可以延伸穿越神經受損區段,重新連接斷裂的兩端並恢復原有功能。
因此,神經損傷後的再生一直是神經醫學研究的一個重要課題。目前神經重建技術的重點在於神經導管接合術的研究,而神經導管之材料以研發生物可降解性(biodegradable)神經導管為目前之研究趨勢。本專題嘗試改良多孔型神經導管之製程,並藉由不同種類之鹽類顆粒,以及不同發泡條件之控制,以生物可降解性材料-左旋聚乳酸為基材,檸檬酸誘發碳酸氫銨發泡之氣泡成型法搭配氯化鈉之鹽析法製造出不同的孔隙分佈型態,並進行各項性質分析。
成份分析與化學元素測定方面,以電子能譜化學分析儀及減弱式全反射-傅立葉轉換紅外線光譜儀來測定其化學成分,以確認製程中無鹽類殘留;孔隙型態觀察方面,以掃描式電子顯微鏡觀察其孔徑分佈及表面型態,;力學性質量測方面,將利用奈米壓痕試驗機(Nanoindenter XP)來模擬神經導管在體內所受各種應力;化學性質部份,首先將製備完成之多孔型神經導管進行體外降解量測,並總結以上各種評估結果,研發適用於周邊神經再生之多孔型神經導管。
柯志諭96_01:新型奈米結構化之神經導管的製備(Jan 2008)
國科會大專生專題研究計畫(96-2815-C-006-048-E)
謫要
在生物可吸收的材料表面,欲固定特定的生物分子,多以物理吸附的方式,如:靜電作用,將特定生物分子「黏附」。此表面後續與細胞培養液接觸,並浸泡一段時間後,原表面所黏附的生物分子將可能會脫落而溶於液相環境中;經過長時間的細胞培養觀察,可能會產生實驗上的誤差。本專題研究計畫使用具有生物可吸收性之幾丁聚醣材質為薄膜基材,利用電子束蒸鍍技術,在材料表面佈植金的島狀物。為比較與一般蒸鍍金薄膜的表面差異,另外準備一個對照組,此對照組使用矽基板為基材,同樣使用電子束蒸鍍的技術,在基板表面蒸鍍單層金薄膜;之後,以表面微結構分析方法,如:掃瞄式電子顯微鏡觀察材料表面形態,研究兩組基材表面的微結構,並比較其差異。再分別於兩組基材表面利用自我組裝單分子膜技術(self-assembled monolayers , SAMs),在基材表面形成不同分子鏈長、不同尾端官能基的分子,並比較兩種基材表面改質的狀況優劣。而後,對兩組完成表面修飾的基材,進行一連串細胞培養及相關之生化分析測試,擬經由這些功能性測試,可以知道SAMs對細胞培養的成效,並可比較兩組不同基材的細胞親合度等生物性質差異;最後,預期可將幾丁聚醣薄膜基材利用於生醫植入材,如:捲成導管的基材做成神經組織工程的支架,同時具有生物相容性、生物可吸收性、細胞可辨識的特性。
關鍵詞:幾丁聚醣、電子束蒸鍍、自組裝單分子膜。
翁逸真96_01:新型非對稱孔隙結構之傷口敷料製備(Jan 2008)
謫要
人體的上皮組織具有自行修復(re-epithelialization)的功能,傷口會逐漸癒合而不需要進行皮膚移植手術,為了減低傷口感染、加速傷口的癒合,在癒合的過程中在傷口處敷蓋ㄧ層適當的敷料是必要的處理方式。從早期傳統的紡織敷料到最近的生物性敷料,許多研究人員都投注心力在發展出更理想的傷口敷料。「非對稱傷口敷料」即為上下結構不同的敷料,有別於傳統的均勻敷料,經改良後的非對稱傷口敷料能夠對傷口的照顧帶來更大的效益,所以非對稱結構薄膜的製備與應用是近幾年來許多人研究的目標。
生物可吸收性材料植入人體後可為人體分解,並經由體內代謝作用將分解後的分子排到體外,不需日後再施以手術將之取出,就其基本需求而言,必須具備裂解物無毒性、有良好的生物適應性等等條件。天然高分子如:幾丁聚醣具有高度生物適應性的特質,且幾丁聚醣
具有強吸濕性,保濕效果相當好,分子在自然的狀態下不易斷裂,也不易變性,具有良好的機械性質;幾丁聚醣的分子構造與人體組織親合性相當良好,作為傷口敷料覆蓋在傷口上不會造成排斥的現象,且其被酵素分解後之寡聚合物具有活化表皮細胞而促進組織之再生、分化與傷口的收縮癒合,可加速患部癒合的時間,此外,幾丁聚醣還具有抗菌的能力,綜合以上的優點,幾丁聚醣在生醫材料上被廣泛的應用,是製備傷口敷料之優良材料。
本專題研究是用新的方法製備幾丁聚醣膜,製備出來的膜呈現上下不對稱的結構,上層是緻密層,用來保護傷口不被外界的微生物感染且可避免水氣散失太快造成傷口脫水,下層是多孔層,提供細胞生長的空間,且具有良好的氧氣通透性和吸收傷口流出液的功能。預熱時間的長短可用來控制緻密層和多孔層的厚度,製備出來的膜再去做多種分析,如:用掃瞄式電子顯微鏡(SEM)觀察材料表面形貌、用全反射傅立葉轉換紅外光光譜儀(ATR-FTIR)觀察材料的化學結構等,並作多種測試,如:水氣穿透測試(WVTR)、水分吸收測試(Water Absorption test)和抗菌測試等,找出幾丁聚醣薄膜最適於做為傷口敷料的製程參數。
關鍵詞:幾丁聚醣、非對稱傷口敷料、生物可吸收性材料。