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系統識別號 U0026-3107201416151800
論文名稱(中文) 利用UV光改善鈦金屬生物活性之研究
論文名稱(英文) The study of UV light to improve the biocompatibility of titanium
校院名稱 成功大學
系所名稱(中) 口腔醫學研究所
系所名稱(英) Institute of Oral Medicine
學年度 102
學期 2
出版年 103
研究生(中文) 吳政勳
研究生(英文) Chang-Syun Wu
學號 t46991076
學位類別 碩士
語文別 中文
論文頁數 71頁
口試委員 指導教授-李澤民
口試委員-林睿哲
口試委員-陳炳宏
中文關鍵字 光催化  生物時效老化  光功能化 
英文關鍵字 Photocatalytic reaction  Biological aging  Photofunctionalization 
學科別分類
中文摘要 植牙為以手術方式將經過特別設計之鈦金屬人工牙根植入到缺失牙的齒槽骨內並與顎骨緊密連結形成錨定作用(anchorage),但若植體在空氣中久置或儲存方式不當,其隨著時間生物時效老化(biological aging)的因素將會降低骨整合,導致植體鬆脫的風險,故在2008年就有學者研究UV-二氧化鈦光催化反應使鈦金屬表面能提高對細胞貼附、增生和骨整合的影響,讓其老化表面再具活性,稱為UV光功能化(photofunctionalization)。但多數學者大多討論不同表面處理試片在大氣下光催化的影響,而甚少提到在特定條件下對兩性氫氧基含量的消長關係。故本研究探討拋光(Polish) 、吹砂酸蝕(SLA)、微弧氧化(MAO)、二氧化鈦奈米管(ATO)、四種不同試片在大氣、真空、氧氣、水氣四種不同條件,其生物活性的表現,並予以浸泡模擬人體體液(SBF)分析其鈣磷化合物析出情形。
光催化反應產生的超氧離子(‧O2-)及氧化分解力很高的‧OH- 這兩種高活性物質,最終使表面產生大量的Ti-OH官能基,在此協同作用(synergistic effect)下,提供鈣磷核種(nucleus)良好的高能量異質成核(heterogeneous nucleation)位置及成長所需的驅動力。以SEM觀察鈣磷化合物分佈及其表面形態,XPS分析兩性氫氧基含量,接觸角判斷其表面能大小,XRD得知其相組成。以Polish、SLA、MAO試片在水氣條件下,兩性氫氧基含量有顯著增加的趨勢,其中又以SLA在浸泡SBF7天後,其鈣磷化合物析出在表面脊狀隆起及內部凹蝕的空腔中最為明顯。實驗結果驗證了結構不同的試片在特定的光催化環境產生高活性大量的兩性氫氧基,有利於成核與成長所需克服的活化能障。
英文摘要 SUMMARY

For tooth implantation, the specially designed titanium dental implant is embedded into the alveolar bone of the missing tooth to closely connect with the jawbone, which generates the anchoring effect. Nevertheless, if the implant is placed in air for a long time or with inappropriate storage method, it will age biologically with time, and osseointegration will lessen, resulting in the risk of implant loosing. Consequently, with utilization of UV-titanium dioxide photocatalytic reaction, this research has raised the titanium surface for re-activation, called photofunctionalization. Additionally, bioactivity performance of four specimens— Polish, SLA, MAO, and ATO— in four conditions—atmosphere, vacuum, oxygen, and vapor—have been explored. The four specimens have further been soaked in SBF to analyze their calcium-phosphate compound precipitation outcomes. It is found that under vapor condition, the content of amphoteric hydroxyl group in Polish, SLA, and MAO has increased significantly. That is to say, the experimental results have verified that the specimens with different structures in specific photocatalytic environment generate great amount of amphoteric hydroxyl group with high activity, which is beneficial for overcoming the activation energy barriers in nucleation and growth.

INTRODUCTION

Dental implantation refers to implanting a specially designed titanium artificial tooth root into the alveolar bone of the missing tooth surgically to closely connect and anchor the jawbone. With this dental technology, the patient can not only speak normally as he or she used to do, but also regain the appearance and quality of a healthy tooth. However, if the implant is exposed to the air too long or stored in an inappropriate way; due to biological aging, the implant itself might lower the osseointegration extent, and causes the implant to loosen. Therefore, in the year of 2008, some scholars researched that UV- titanium dioxide photocatalytic reaction used to enable titanium surfaces to enhance the influence of cell adhesion, cell proliferation, and osseointegration in order to make the aged surface active again, which is called photofunctionalization. Unfortunately, when facing certain conditions, most scholars merely discuss the influence of specimen with different surface treatments under atmospheric photocatalytic reaction, but rarely mention the growth and declination of the amphoteric hydroxyl group content.
Under this context, this research explores the biological activities of the four different specimen, including Polish, SLA (sandblasted, large-grit, acid-etched), MAO (micro arc oxidation), ATO (anodic titanium oxide) under four conditions involving atmosphere, vacuum, oxygen, and vapor. These four specimens have been soaked in SBF (simulated body fluid) to analyze its calcium-phosphate compound precipitation scenarios.
The super oxygen ion (‧O2 -) and‧OH-generated by photocatalytic reaction have shown high resolving power. The highly active substances finally trigger great amount of Ti-OH functional groups to be created by surfaces. And, with this synergistic effect, the calcium-phosphate compound nucleus are provided excellent high energy heterogeneous nucleation sites and growth-driving force. Using Polish, SLA, and MAO specimens under vapor conditions, amphoteric hydroxyl group content shows the tendency of significant increase. Moreover, SLA has also been soaked in SBF for 7 days, causing calcium-phosphate compound to separate out the most obviously at the spinal area bumps and empty cavity where the internal has etched back. The results of the experiment prove that the specimens with different structures under specific photocatalytic environment may create many highly active amphoteric hydroxyl, which is also beneficial to overcome the active energy barrier in nucleation and growth.

MATERIALS AND METHODS

The experimental material was commercial pure titanium grade 2 F67 cp Ti, and the experiment flow is shown in Fig. 3-1. The Control Group was pure titanium without UV light treatment, while the Contrast Group was UV-vacuum, UV-O2, and UV-H2O proceeded reaction in self-made stainless steel chamber, as shown in Fig. 3-2. In process of photocatalytic experiment, according to Beer's law, the intensity of UV transmission light declined exponentially with the increase of the optical path length. Therefore, in order to achieve good photocatalytic effect, the specimens were placed in parallel to the direction of UV light tubes, and on the same plane of the incident light source, so that the optimal illuminance could be obtained. After the experiment, the specimens were soaked in SBF for 1, 3, and 7 days to complete coating for the subsequent analysis.
FE-SEM was used to observe the shape of the specimens’ surfaces, and EDS to determine the elements the specimens contained and conduct semi-quantitative analysis. On the other hand, XRD was exerted to analyze the phase composition, while XPS to analyze the chemical state and valence number of the compound. Finally, we observed the surface energy change by contact angle.

RESULTS AND DISCUSSION

From Table 4.1, we can learn that the contact angle of all the specimens after UV light treatment is smaller than 100, signifying superhydrophilicity. Besides, in XPS analysis of high resolution O 1s spectra, the content of amphoteric hydroxyl group is higher in the specimens of Polish, SLA, and MAO, and such functional group has provided good nucleation site to induce apatite precipitation. As in high resolution C 1s spectra, from Fig. 4-15 to Fig. 4-18, it is learned that C 1s peak tends to decline with regard to Polish, MAO, and ATO under the vacuum condition. From Fig. 4-24 to Fig. 4-27, the morphology of calcium-phosphate compound precipitation phase change, the apatite is precipitated as heterogeneous nucleation site by means of Ti-OH functional group; and, with even higher multiplying factor, the precipitated apatite is represented as ball-shape, proving it is consistent with our proposed hypothesis. Moreover, in Fig. 4-25, the apatite precipitated in SLA group is the densest—agglomeration even took place, and the precipitated particle size on the ridge and in the internal etch-back holes is the biggest.

CONCLUSION

1.This thesis primarily articulates the application of UV photocatalytic reaction in specific environments as Vacuum, O2, and H2O. Particularly, for Polish, SLA, and MAO specimens, H2O is the best condition that can foster the apatite to be precipitated.
2.Under such synergistic effect, when surfaces with different structures are connected with Ti-OH functional group, the high surface energy helps overcome the activation energy barriers in nucleation. Also, it serves as a good heterogeneous nucleation site, and the energy it releases can re-assist the sites with low energy to continue to nucleate.
3.Among the shapes with the fixed volume, the area of the sphere is the smallest. The precipitated apatite is a globe, which has the least total surface energy.
論文目次 摘要 I
AbstractII
總目錄 V
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1-1 前言 1
1-2 理想生醫材料要件 1
1-3 生醫材料的分類 2
1-4 植牙技術簡介 4
1-5 人工牙根發展演進 4
1-6 影響骨整合的因素 5
1-7 輻射技術在生物材料領域的應用 6
1-8 研究目的與動機 7
第二章 基礎理論與文獻回顧 9
2-1 紫外光應用 9
2-2 光催化反應誘導生物活性研究背景介紹 9
2-2-1 表面有機汙染物及靜電性對細胞反應之影響 10
2-2-2 體內動物實驗生物力學之影響 11
2-3 鈦時效(aging)降低生物活性 11
2-4 鈦表面處理技術簡介 12
2-4-1電漿熔射(plasma spray) 12
2-4-2吹砂酸蝕(SLA,Sand-blasting Large-grit Acid-etching) 13
2-4-3 微弧氧化(MAO,Micro Arc Oxidation) 13
2-4-4 二氧化鈦奈米管(ATO,Anodic Titanium Oxide) 14
第三章 實驗材料與研究方法 15
3-1實驗流程與材料 15
3-1-1實驗材料 15
3-1-2 實驗儀器 15
3-2 試片前處理 16
3-3 微弧氧化處理 16
3-4 二氧化鈦奈米管陣列試片之製備 17
3-5 吹砂酸蝕試片之製備 17
3-6 光催化實驗 17
3-7 模擬人體體液(SBF)之製備 18
3-8表面性質分析 18
3-8-1接觸角實驗 19
3-8-2 X-光繞射鑑定相組成 19
3-8-3 X-光光電子能譜(XPS)分析表面元素成分及化學態 21
第四章 結果與討論 22
4-1表面形態觀察 22
4-2接觸角分析 22
4-3 ESCA分析 23
4-4 XRD鑑定相分析 25
4-5 模擬體液鈣磷析出相變化之分析 26
第五章 結論 30
參考文獻 31
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