201119692 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種人工植體之表面處理方法，特別是 一種鈦人工植體之表面處理方法。 【先前技術】201119692 VI. Description of the Invention: [Technical Field] The present invention relates to a surface treatment method for artificial implants, and more particularly to a surface treatment method for titanium artificial implants. [Prior Art]
人工植體係經遜精密設计加工之材料，用以模擬人體 缺損部位’以期將該人工植體植入人體中取代人體缺損之 部位。植入後的人工植體將與宿主的組織直接接觸，因此 其材質的選用以及表面的生物相容性便相當重要。 一般而言，以金屬材質製成之人工植體植入人體後， 人體内之版基酸或7C蛋白質等物質會加速人工植體的腐餘 ，導致金屬離子連續的釋放至周圍組織，而可能造成人工 植體附近組織的不良反應，進而導致人工植體與生物體整 合不易，造成手術的失敗。 然而，由於金屬氧化層可以阻擔金屬離子釋出的情妒 ，可避免人工植體附近組織的不良反應’進而增進該人二 植體之生物相容性，甚至影響到生物體内的蛋^質:收、 骨組織聚合或生物親合等特性。因此，於金屬材質之人工 植體表面形成金屬氧化層，以增進生物相容性之二究方= 已受到相當大的重視。例如人工植體本身材料的特^^ 成物特性、表φ粗糙度或表面型態都是非常重要的參考因 素。 少 細胞和人工植體 象產生，接著是 其中，於人工植體植入人體的初期， 材料之表面接觸，細胞會有貼附和黏附現 201119692 細胞散佈和細胞遷移現象。 例如細胞研究顯示若力的因素很多， 導骨向内生長n ± 有大0孔洞能有效的引 易於表面开^ 植體為例，由於鈦合金在氧氣令 衣面I成-穩&的二氧化鈦氧 :=相容性及•性佳。隨著該二:化=::: •附著能力，生物;:二:更一:的::，到骨 顯示二氧化鈦镇胺^ u此更好。此外’亦有研究 越佳。 版上之孔徑孔洞越小幫助細胞增殖的效果 在自氧化_化層具有上述之許多優點，但 5〜1〇^ 化所產生的二氧化欽氧化層之厚度只有 nm，並不足以阻擋金屬離子的釋出。 ，了改良上述缺點，習知欽人工植體之表面處理方法 二增_56號「鈦合金人工關節表面製 欽原子離子化，經由加速器使㈣子加速後直接^The artificial planting system is designed to simulate the defect of the human body by the precision design and processing of the human body implant in order to implant the artificial implant into the human body to replace the defect of the human body. The implanted implant will be in direct contact with the host's tissue, so the choice of material and the biocompatibility of the surface are important. In general, after the implants made of metal are implanted into the human body, substances such as basal acid or 7C protein in the human body accelerate the decay of the artificial implants, resulting in continuous release of metal ions to the surrounding tissues, and possibly The adverse reactions caused by the tissues near the artificial implants, which lead to the integration of artificial implants and organisms, are not easy, resulting in the failure of surgery. However, since the metal oxide layer can block the release of metal ions, the adverse reactions of the tissue near the artificial implant can be avoided, thereby improving the biocompatibility of the human implant and even affecting the eggs in the living body. Quality: characteristics of harvest, bone tissue polymerization or biological affinity. Therefore, the formation of a metal oxide layer on the surface of a metal implant to enhance biocompatibility has received considerable attention. For example, the characteristics of the material of the artificial implant itself, the surface roughness or the surface type are very important reference factors. Less cells and artificial implants are produced, and then, in the early stage of implanting the artificial implant into the human body, the surface of the material is in contact, and the cells will adhere and adhere to the present 201119692 cell dispersion and cell migration. For example, cell research shows that there are many factors in the force, bone conduction ingrowth n ± large hole 0 can effectively lead to easy surface opening, for example, because titanium alloy in the oxygen to make the surface I into - stable & titanium dioxide Oxygen: = compatibility and • goodness. With the two: chemistry =::: • adhesion ability, biology;: two: one more:::, to the bone shows titanium dioxide an amine ^ ^ this is better. In addition, there is also a better study. The smaller the pore size of the plate, the effect of cell proliferation in the auto-oxidation layer has many of the above advantages, but the thickness of the dioxide oxide layer produced by 5~1〇 is only nm, which is not enough to block the metal ion. Released. In order to improve the above-mentioned shortcomings, the surface treatment method of the conventional artificial implants is added. _56 "The surface of the titanium alloy artificial joint is made by ion atomization, and the (four) sub-acceleration is accelerated by the accelerator directly ^
Tl_6AMV人工_表面，使得加速的輯子與鈦合金人工 關節表面原子產生作用，而導致晶格上的原子相互撞離其 平衡位置’進而產生晶格缺陷，進而形成非晶質結構，如 ，即可在鈦合金人工關節表面形成奈米非晶質薄膜。再經 氧化該奈米非晶質薄膜便可形成二氧化鈦氧化層。 而該中華民國公告第^262956號發明專利所使用 之加速益設備價格較為昂貴，因此具有製作成本較高之缺 點；再且:其加速電壓輯1MeV以上，能量f求較高，' 使- v、有鬲耗此之缺點；再且，由於受限於加速器之加速 201119692 面積較小，因此該法僅可小面積地對人丄植體進行表面處 理，而無法大_進行表面處理；其非晶質結構厚度僅約 5〇〇nm，表示其進—步透過氧化所形叙金躲化層亦相 對較薄，並不足以阻擋金屬離子的釋出；再且，其僅可單 向性地對該人工植體進行表面處理，而無法同時對多個表 面進行表面處理，因此具有製程錢之缺點，且結 不規則狀。 'Tl_6AMV artificial _ surface, so that the accelerated series and the titanium alloy artificial joint surface atoms act, causing the atoms on the lattice to collide with each other at their equilibrium position', thereby generating lattice defects, thereby forming an amorphous structure, such as A nanocrystalline amorphous film can be formed on the surface of the titanium alloy artificial joint. The titanium oxide oxide layer is formed by oxidizing the nanocrystalline amorphous film. The accelerating equipment used in the invention patent No. ^262956 of the Republic of China is relatively expensive, so it has the disadvantage of high production cost; and further: its acceleration voltage is above 1 MeV, and the energy f is higher, 'make-v In addition, due to the limited acceleration of the accelerator 201119692, the method can only surface the human body implants in a small area, but can not be large surface treatment; The thickness of the crystal structure is only about 5 〇〇 nm, which means that the gold immersion layer is relatively thin, which is not enough to block the release of metal ions; further, it can only be unidirectionally The artificial implant is subjected to surface treatment, and it is impossible to surface-treat a plurality of surfaces at the same time, so that it has the disadvantages of the process money and has irregular knots. '
另-習知鈦人工植體之表面處理方法，如中華民國公 告第1244958號「骨材植入體之表面處理方法」發明專利 所述，其係先將純鈦製成之植入體以〇 25_〇 5〇咖的从加 進行噴砂1分鐘，錢難人體之表㈣絲糙度 謂™ =手段照射3·5次，以形成更粗糙的表面狀 悲、’接者泡人浪度為40-60%之硫酸溶〉夜中，於7〇_9〇。〇⑺ 度環境下加熱襲分鐘；最後純人濃度為25_35%之^ 酸溶液中，於溫度7〇鐵溫度環境下加熱㈣分鐘了 便可對該些祕之表面孔洞進行_，進㈣❹孔性的 金屬氧化層結構。 然而，該中華民國公告第124侧號專利由於先對該 植入體表面進行噴砂再進行雷射處理，因此其所形成之孔 洞孔徑駿十，，使其具有孔_大及結财規則之缺 點，且比表_亦不足；再且，其以f射進行處理，亦具 有處理面積較小及設備成本昂貴之缺點；再且，$法需要 經過噴砂、雷射及祕等步驟方可完成對植人體表面:處 理’因此具有製程步驟繁複之缺點。 另一習知鈦人工植體之表面處理方法，如美國公告第 —5 — 201119692 5,863,201 號「Method of treating the surface of titanium」發 明專利所述，其中鈦合金植入管之表面係為光滑的，透過 以一種含水氫氟酸移除該鈦合金植入管表面之氧化物，並 且由含硫和鹽酸混合物產生隨機的表面蝕刻過程，以使該 鈦合金植入管之表面形成粗糙表面。 然而，由於氫氟酸之腐蝕性較強，可能造成蝕刻過度 之情況，製程可控性不佳；再且，進行上述蝕刻反應所產 生之孔洞通常係大於3 Am，使其亦具有孔徑過大及結構不 規則之缺點；再且，其表面產生粗糙化後，比表面積不足 ，即使於自然環境中氧化產生金屬氧化層，該金屬氧化層 之厚度亦不足。 曰 基於上述原因，其有必要進一步改良上述習用鈦人工 植體之表面處理方法。 【發明内容】 本發明目的乃改良上述缺點，以提供一種鈦人工植體 之，面處理方法，使該鈦人卫植體表面形成具有奈米/次奈. 米管之陣列結構的二氧化鈦氧化層為目的。 本發明次一目的係提供一種鈦人工植體之表面處理 方法，以增加二氧化鈦氧化層之比表面積者。 本發明再-目的係提供—種欽人工植體之表面處理 方法，以降低二氧化鈦氧化層表面孔徑。 本發明又-目的係提供一種欽人工植體之表面處理 方法，以簡化製程。 本發明又一目的係提供一種鈦人工植體之表面處理 201119692 方法’以增加製程可控性。 本發明又-目的係提供—齡、人 方法，以降低設備成本。 版之表面處理 本發明又一目的係提供一種鈦 方法^多向性的對人工植體進行表面處理體之表面處理 乂艮據本發明的鈦人工植體之表面 二，理步驟以清潔溶劑清潔該錄人工植=係包=·· 將該鈦人工植體及—陰極 &、面，一置 電解峡中，該鈦人工植體與一陽；入:陽極氧化反應 驟將蕾#请# a 电極相連接；一反應步 表面“氧極及陽極電極’使該鈦人工植體之 表面清、先㈣r·^生’進師成二氧化銀氧化層；及一 【實施方式Γ 清洗該反應後域人工植體。 易懂及，_ 作詳細說明如下： 例，並配合所附圖式， 凊翏照第1圖所示’本發明之鈦人工植體之表 步驟^佳包含—前處理步驟8卜—置人步驟S2、一反應 i且右及—表面清潔步驟S4,使該鈦人工植體之表面开： 表?積、小孔徑及高厚度之二氧化鈦氧化: ^ j二氧化鈦氧化層之細胞相容性及細胞貼附,=。 潔溶人圖戶^示’本發明之前處理步驟S1係以清 依序；=::t面。更詳言之’本實施例係 r私及去離子水作為清潔溶劑清洗該鈦人工 201119692 植體’且於清洗同時進行超音 如此，透過以哼呙而 辰盪，以提升清潔效果。 之表面，可避醇及去離子水清潔該鈦人工植體 =質殘留於該鈦人工植體之表面。 工植體置放;ΐ 步驟S1後，健將該欽人 後，再，於75〜1耽之溫打進行洪烤 人工植體置放於氮氣#下H5，本貫施例係將該鈦 。軌㈣之溫度下進行烘烤 氧二了避免該鈦人工植體於供烤過程中產生 。士成後#、t仃、〃烤係為了使該鈦人31植體表面完全乾燥 兀成後再進行該置入步驟S2。 糾Γ參照第1及2圖所示’本發明之置入步驟S2係將 …植體1及—電極組3之陰極電極3!置入一陽極氧 中’且該欽人工植體1與該電極組3之陽 =1 32相連接。更詳言之，本實施例進行陽極氧化處理 之裝置如第2圖所示’該裝置係包含該陽極氧化反應電解 液2 Λ極組3及一容器4。該陽極氧化反應電解液2係容 置於4w 4内’該陽極氧化反應電解液2係可選擇為重 量百^比濃度為（U至1Gwt%的氟聽_4F)或氫氟酸（ HF)溶液，由於氟化録溶液之反應速度不會過於劇 烈，進行反應之可控性較高，因此本實施例之陽極氧化反 應電解液2較佳係選擇為氟化銨(NH4F)溶液，該陽極氧化 反應電解液2巾係另包含—供氧源，該供氧源係可選擇為 乙一醇（Ethylene glycol )、甘油（GiyCerin )或水；該電極 組3係包含該陰極電極31及陽極電極32.，且分別與一電 源相連接，該陰極電極31及陽極電極32係選擇為碳電極 201119692 極選擇固定於-载具上與該陽極電 鐵氣龍裁Λ 將該敍人工植體1固定於: 避免氣泡產生。k入麵極氧化反應電解液2,以 請參照第1至4圄郎- 丄 電荷導入該陰極電極= 應步驟幻係將 之表面進行陽極氧化反庫，淮：丄’使錢人工植體I 更詳言之，接著⑴“上進而形成二氧化鈦氧化層U。 及陽極電極32 ^ 電源’使電荷導人該陰極電極3】 ，反應時間係介㈣.K；Tf Γ卜於15〜⑽伏特㈣ 心之表面形成二氧化此’便可於該鈦人工植 U係為夺米/-欠太平&、 θ 且6亥一氧化鈦氧化層 讀二氧結構，如第4圖所示。其中， 次奈米管之孔徑係介於：度:;於。:〜25·7㈣ 綠之電壓及反應時間，'二1人5麵。如此，透過控制該電 米/次奈米管之陣列姓構之二工植體1之表面形成該奈 讀鈦人工植體！之比^㊉—減鈦减層11，以大幅提昇 史孔徑及管長（即-ί ^適縣米/次奈米管 e Μ即―乳化鈦氧化層11之厚度）。 請蒼照第1及4闰ή匕-, 係以清洗溶劑清洗該反:不:：明之表面清洗步驟S4 本實施例競擇依如_、曱·絲子水 :劑清洗該反應後之銥人工植…，清洗同時較佳;二洗 =波震Α。如此’便可將殘留之陽極氧化反應電解液订2 201119692 凡成该表面清洗步驟S4後，較佳係於氮翁 =〜峨之溫度下進行烘烤。舉例㈣，本實施例係將 以太人工植體1置放於氮氣環境下，於】〇〇1之严戶下進 行供烤。魏氣環祕為了職誠人=烤過 程:產生氧化現象，進行烘烤係為了使該鈦人工植體i表 面乾燥。完成後便可避免該些清洗溶劑殘留於該鈦: 工植體1之表面。 如上㈣，本發明透觸極氧化處理可於舰人工指 、面形成奈米/次奈米管之陣列結構之二氧化欽氧介 :，因此可大幅提昇該二氧化鈦氧化層u之比表㈣ 有助於細胞於該鈦人I植體i上之貼附性。 =照第5&及513圖所示，其係為本發明第一實施例 化鈦氧化層11的上視圖及截面圖。本實施例 氧化反庫麵=減，並魏蝴NH4F)調配成該陽極 反肩】f ㊉度係為α29Μ，再於15伏特之電堡下 及^吾Γ 了便可形成如第化及分圖所示具有孔徑50nm 化層ι^Γ氧化鈦氧化層11之厚度）5GG麵之二氧化鈦氧 所製：：:⑽及65圖所示’其係為本發明第二實施例 係以甘油績切11的上棚及❹®。本實施例 氧化反應電解^㈣，並與氟化罐明調配成該陽極 電解液2中Y 且該氟化叙(NH4F)於該陽極氧化反應 反應1 5 士莫耳;辰度係為0.29M，再於20伏特之電壓下 寸便可形成如第6a及6b圖所示具有孔徑5〇nm 201119692 0_8/zm以上之二氧 及g長（二氧化鈦氧化層11之厚度） 化欽氧化層π。 请麥照第7a&7b圖所示，其係為本發 所製成之-竿/丨 q +私η矛一男、她例 ，、—虱化鈦氧化層11的上視圖。本實施例係以乙二 共氧源，並與氧化銨卿)調配成該陽極氧化反 ;j 2,且該氟化敍(NH4F)於該陽極氧化反應電解液2 之重里百分比濃度係為0.3wt%，再於20伏特之電壓下In addition, the surface treatment method of the conventional titanium artificial implant is as described in the invention patent of "The Surface Treatment Method of the Aggregate Implant" of the Republic of China Announcement No. 1244958, which is first made of an implant made of pure titanium. 25_〇5〇 的 从 从 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加40-60% sulfuric acid dissolved in the night, at 7〇_9〇. 〇(7) degree heating in the environment; in the last pure human concentration of 25_35% of the acid solution, heating at a temperature of 7 〇 iron temperature for (four) minutes, the surface holes of the secret can be _, into (four) pupillary Metal oxide structure. However, the Republic of China Announcement No. 124 side patent firstly performs sandblasting on the surface of the implant and then performs laser treatment, so that the hole formed by the aperture is a ten-hole, which has the disadvantage of a hole_large and a wealth-saving rule. And the ratio _ is also insufficient; furthermore, it is processed by f-ray, which also has the disadvantages of small processing area and expensive equipment; further, the $ method needs to be sandblasted, lasered and secreted to complete the pair. Planting the surface of the human body: processing 'has the disadvantage of complicated processing steps. Another conventional surface treatment method for titanium artificial implants, as described in the "Method of treating the surface of titanium" invention of the U.S. Patent Publication No. 5, 2011, 1969, No. 5,863, 201, wherein the surface of the titanium alloy implant is smooth. The oxide of the surface of the titanium alloy implant is removed by an aqueous hydrofluoric acid, and a random surface etching process is produced from the sulfur-containing and hydrochloric acid mixture to form a rough surface on the surface of the titanium alloy implant. However, due to the corrosive nature of hydrofluoric acid, it may cause excessive etching, and the process controllability is not good. Moreover, the holes generated by the above etching reaction are usually larger than 3 Am, so that the pore diameter is too large. The disadvantage of structural irregularity; furthermore, after the surface is roughened, the specific surface area is insufficient, and even if the metal oxide layer is oxidized in the natural environment, the thickness of the metal oxide layer is insufficient.曰 For the above reasons, it is necessary to further improve the surface treatment method of the above-mentioned conventional titanium artificial implant. SUMMARY OF THE INVENTION The object of the present invention is to improve the above disadvantages, and to provide a titanium artificial implant surface treatment method for forming a titanium oxide oxide layer having an array structure of nano/secondary nanotubes on the surface of the titanium human implant. for purpose. A second object of the present invention is to provide a surface treatment method for titanium artificial implants to increase the specific surface area of the titanium oxide oxide layer. A further object of the present invention is to provide a surface treatment method for a plant artificial implant to reduce the surface pore size of the titanium oxide oxide layer. Still another object of the present invention is to provide a surface treatment method for artificial implants to simplify the process. A further object of the present invention is to provide a surface treatment of titanium implants 201119692 Method ' to increase process controllability. The present invention is also directed to providing age- and human methods to reduce equipment costs. Surface treatment of the present invention Another object of the present invention is to provide a titanium method for the surface treatment of a surface treatment body of an artificial implant. According to the surface of the titanium artificial implant of the present invention, the cleaning step is cleaned with a cleaning solvent. The recorded artificial planting = system package =·· The titanium artificial implant and the cathode and the surface, the one set in the electrolytic gorge, the titanium artificial implant and one yang; the: anodizing reaction will be bud #请# a The electrodes are connected; the surface of the reaction step "oxygen electrode and anode electrode" makes the surface of the titanium artificial implant clear, first (four) r · ^ raw 'into the silver oxide oxide layer; and one [embodiment Γ wash the reaction Posterior domain artificial implants. Easy to understand, _ is described in detail as follows: Example, and with the accompanying drawings, referring to Figure 1 of the present invention, the steps of the titanium artificial implants are preferably included. Step 8 - placing step S2, a reaction i and right and - surface cleaning step S4, opening the surface of the titanium artificial implant: titanium oxide of surface, small pore size and high thickness: ^ j titanium oxide oxide layer Cytocompatibility and cell attachment, =. Prior to the invention, the processing step S1 is followed by clearing; =::t surface. More specifically, 'this embodiment is a private cleaning solution and deionized water as a cleaning solvent to clean the titanium artificial 201119692 implant' and supersonic while cleaning In this way, through the simmering, to improve the cleaning effect. The surface can be cleaned with alcohol and deionized water to clean the titanium artificial implant = the residue remains on the surface of the titanium artificial implant. After step S1, after the Qin people are trained, the boiled artificial implants are placed at a temperature of 75~1 置 to be placed under nitrogen #H5, and the present embodiment is baked at a temperature of the titanium (four). The oxygen is added to prevent the titanium artificial implant from being produced during the roasting process. The Shicheng Hou #, t仃, and the grilling system are carried out in order to completely dry the titanium human implant surface and then perform the placing step S2. Referring to FIGS. 1 and 2, 'the implantation step S2 of the present invention places the implant 1 and the cathode electrode 3 of the electrode group 3 into an anodic oxygen' and the artificial implant 1 and the The anode group of the electrode group 3 is connected to each other. In more detail, the apparatus for performing anodizing treatment in this embodiment is as shown in Fig. 2' The apparatus comprises the anodizing reaction electrolyte 2, the drain group 3 and a container 4. The anodizing reaction electrolyte 2 is housed in 4w 4 'the anodizing reaction electrolyte 2 can be selected as a weight ratio For (U to 1 Gwt% Fluoride _4F) or hydrofluoric acid (HF) solution, since the reaction rate of the fluorination recording solution is not too severe, the controllability of the reaction is high, and thus the anodic oxidation of the present embodiment The reaction electrolyte 2 is preferably selected from the group consisting of ammonium fluoride (NH4F) solution, and the anodizing reaction electrolyte 2 includes an oxygen supply source, and the oxygen supply source may be selected from Ethylene glycol and glycerin. The electrode group 3 includes the cathode electrode 31 and the anode electrode 32. The cathode electrode 31 and the anode electrode 32 are respectively connected to a power source. The cathode electrode 31 and the anode electrode 32 are selected as the carbon electrode 201119692. The pole is selectively fixed to the carrier. The upper and the anode electric iron dragon are cut to fix the artificial implant 1 to: to avoid bubble generation. k into the surface of the extreme oxidation reaction of the electrolyte 2, please refer to the first to fourth 圄 - - 丄 charge into the cathode electrode = should step the magical surface of the anodizing anti-bank, Huai: 丄 ' make money artificial implant I More specifically, then (1) "up and further form the titanium oxide oxide layer U. And the anode electrode 32 ^ power supply 'charges the cathode electrode 3", the reaction time is (4). K; Tf Γ 15 15~(10) volts (four) The surface of the heart is formed to be oxidized. This can be used to read the dioxostructure of the titanium implanted by the titanium, and as shown in Fig. 4. The pore size of the secondary nanotubes is between: degrees:; in::25.7 (four) Green voltage and reaction time, 'two ones and five sides. Thus, by controlling the array of electric meters/minor tubes The surface of the second implant 1 forms the titanium implant artificial implant! The ratio of the ten-tenth reduction layer 11 is used to greatly increase the pore size and length of the tube (ie - ί ^ Shixian meters / sub-nano tubes e Μ That is, the thickness of the emulsified titanium oxide layer 11. Please wash the first and fourth 闰ή匕-, and clean the reverse with a cleaning solvent: No:: Surface cleaning step S4 The embodiment is based on _, 曱 丝 丝 水 : : : : : : : : : : : : : : : 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗2 201119692 After the surface cleaning step S4, it is preferably baked at a temperature of nitrogen = 峨. For example (4), in this embodiment, the artificial implant 1 is placed under a nitrogen atmosphere, 〇1 is used for roasting under the strict household. Wei Wei ring secret for the job of honest people = roasting process: oxidation phenomenon, baking in order to dry the surface of the titanium artificial implant i. After the completion of the cleaning solvent can be avoided Titanium: the surface of the planting body 1. As shown in the above (4), the translucent polar oxidation treatment of the present invention can form the oxidized oxygen channel of the array structure of the nano/secondary tube in the artificial finger and the surface of the ship: The ratio of the titanium oxide layer u (Table 4) contributes to the adhesion of the cells to the titanium human implant i. = As shown in Figures 5 & and 513, it is the first embodiment of the present invention. 11 is a top view and a cross-sectional view. In this embodiment, the oxidation anti-causal surface = minus, and Wei butterfly NH4F) Formulated into the anode back shoulder] f ten degrees is α29Μ, and then under the electric volt of 15 volts and ^ Γ 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 便可 如 如 如 如 如 如 如 如 如The thickness of 11) is made of titanium oxide of 5GG surface::: (10) and 65 are shown in the figure of the second embodiment of the present invention, which is a top shed and a ruthenium® of glycerin. 11. Oxidation reaction electrolysis of the present embodiment (4) And the fluorination tank is clearly adjusted to form Y in the anolyte 2 and the fluorination reaction (NH4F) is 15 ohms in the anodic oxidation reaction; the elongation is 0.29 M, and then the voltage is 20 volts. The inch can be formed as shown in Figures 6a and 6b with a pore diameter of 5 〇 nm 201119692 0_8/zm or more of dioxine and g length (thickness of the titanium oxide oxide layer 11). Please refer to the photo of the photomicrographs 7a & 7b, which is a top view of the oxidized titanium oxide layer 11 made by the 竿/丨 q + private η spears. In this embodiment, the bismuth co-oxygen source is combined with ammonium sulphate to form the anodizing reaction; j 2 , and the concentration of the fluorination (NH4F) in the anodic oxidation reaction solution 2 is 0.3. Wt%, then at a voltage of 20 volts
反2 2小時，可形成如第乃及7b圖所示具有孔徑6$腿 及官長（二氧化鈦氧化層n之厚度）2 37 氧化層11。 乳化欽 ^叫麥照第8a至8c圖所示，其分別為第四、五及六實 %例所製成之二氧化鈦氧化層的截面圖。i 8c圖皆 2以刖述以甘油為供氧源，氟化銨(NHj)濃度為之 办液作為陽極氧化反應電解液2，並於20伏特之電壓下進 仃反應，其中，第8a圖之反應時間係為1小時，管長係為 4.nmn;第8b圖之反應時間係為ι.5小時，管長係為趵 ，第8C圖之反應時間係為20小時，管長係為1779.8nm。 ^印芩照第9圖所示，其係為反應時間相對管長之相對 =化，’可觀察到隨著反應時間的增加，該二氧化鈦奈米 s之官長亦隨之增加。可驗證本發明之鈦人工植體之表面 處理方法透過調整不同之反應賴，可精確控制該 鈦氧化層11之厚度。 5月苓照第10圖所示，其係為電壓相對孔徑之相對變 =圖可觀祭到隨著該電源電壓的增加，該二氧化鈦奈米 &之孔徑亦隨之增加。可驗證本發明之鈦人工植體之表面 201119692 可精確控制該二氧化 處理方法透過調整不同之反應電壓 鈦氧化層11之孔徑。 凊麥照第11圖所示 於反應時間之變化圖 〃糸為不同供氧源下，孔徑相對 第B细仫 目中第A組係以甘油作為供氧源， 供氧源，可得知以乙二醇作為供氧 t；：r 之厚餘厚，甚至可達％㈣以 與可可驗證本發明之鈦人4體之表面處理方法確 貝可k升该二氧化鈦氧化層u之厚度。 =日⑽提供-種鈦人工植體之表面處理方法，透過 二 之表面進行陽極氧化處理，以增加二氧化 鈦氧化層厚度。 兮本發日㈣提供—種鈦人王鋪之表域理方法，透過 错植體之表面形成具有奈米7次奈米管之陣列結 、-乳化鈦氧化層’以增加該二統鈦氧化層之比表面 本發明係提供-種鈦人工植體之表面處理方法，以降 低二氧化鈦氧化層表面之孔徑。 ;本發明係提供-種鈦人讀體之表面處理方法，其係 •子乂鈦人工植體之表面進行陽極氧化處理，因此可降低製 程設備成本、提升製程可控性及簡化製程。. 、a本發明係提供—種鈦人讀體之表Φ處理方法，以透 過陽極氧化反應，多向性且大面積地對鈦人王植體進行表 面處理。 雖然本發明已利用上述較佳實施例揭示，然其並非用 以限定本發明，任何熟習此技藝者在不脫離本發明之精神 —12 — 201119692 和範圍之内，相對上述實施例進行各種更動與修改仍屬本 發明所保護之技術範疇，因此本發明之保護範圍當視後附 之申請專利範圍所界定者為準。For a period of 22 hours, an oxide layer 11 having a pore diameter of 6$ and a length (thickness of the titanium oxide layer n) 2 37 can be formed as shown in Figs. The emulsified crystals are shown in Figs. 8a to 8c, which are cross-sectional views of the titanium oxide oxide layers produced in the fourth, fifth and sixth examples, respectively. i 8c is 2 to cite glycerol as the oxygen source, ammonium fluoride (NHj) concentration as the anodizing reaction electrolyte 2, and the enthalpy reaction at a voltage of 20 volts, wherein, Figure 8a The reaction time was 1 hour, and the tube length was 4. nmn; the reaction time in Fig. 8b was ι. 5 hours, the tube length was 趵, the reaction time in Fig. 8C was 20 hours, and the tube length was 1779.8 nm. According to Fig. 9, it is the relative reaction time of the reaction time with respect to the length of the tube, and it can be observed that as the reaction time increases, the official length of the titanium dioxide nano-s increases. It can be verified that the surface treatment method of the titanium artificial implant of the present invention can precisely control the thickness of the titanium oxide layer 11 by adjusting different reaction. In May, as shown in Figure 10, it is the relative change of the voltage relative aperture. The figure shows that as the power supply voltage increases, the pore size of the titanium dioxide nanometer & The surface of the titanium artificial implant of the present invention can be verified. 201119692 The oxidation treatment method can be precisely controlled by adjusting the pore diameter of the titanium oxide layer 11 by different reaction voltages. The change of reaction time shown in Figure 11 is the different oxygen supply source. The pore size is relative to the B group. The glycerin is used as the oxygen source and the oxygen source. Ethylene glycol as the oxygen supply t;: r thick thickness, even up to (4) to verify the thickness of the titanium oxide layer u with the surface treatment method of the titanium human body 4 of the present invention. = (10) provides a surface treatment method for titanium implants, which is anodized through the surface of the second surface to increase the thickness of the titanium oxide oxide layer.兮本发日(4) provides a method for the surface of Titanium Wangpu, forming an array of nano 7th nanotubes, an emulsified titanium oxide layer through the surface of the wrong implant to increase the oxidation of the titanium oxide. Specific Surface of Layers The present invention provides a surface treatment method for titanium implants to reduce the pore size of the surface of the titanium oxide oxide layer. The invention provides a surface treatment method for a titanium human body, which is anodized on the surface of the titanium-germanium implant, thereby reducing the cost of the process equipment, improving the controllability of the process, and simplifying the process. A. The present invention provides a Φ treatment method for a titanium human body, which is subjected to anodization, omnidirectional and large-area surface treatment of Titanium. Although the present invention has been disclosed by the above-described preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make various modifications with respect to the above embodiments without departing from the spirit of the invention - 12 - 201119692. The modifications are still within the technical scope of the present invention, and the scope of the present invention is defined by the scope of the appended claims.
[s] —13 — 【圖式簡單說明】 第1圖：本發明之鈦人工 植體之表面處理方法的流程 圖 =2圖♦本發明進行陽極氧化反應之裝置示意圖。 第3圖：本發明之反應步驟的示意圖。' 第4圖：本發明完成反應步驟後的二氣 結構示意圖。 〜礼亿層表面 第5a圖··本發明第一實施例所製得 的上視圖。 一虱化鈦氧化層 第5b圖：本發明第，實施例所製得之 # 的截面圖。 軋化鈦軋化層 第6a圖：本發明第二實施例所製 ^ 的上視圖。 于之—乳化鈦氧化層 第6b圖：本發明第二實施例所製得之 的截面圖。 虱化鈦氧化層 第7a圖：本發明第三實施例製一 的上視圖。 魏鈇氧化層 第7b圖：本發明第三實施例所製 & · 的上視圖。 一虱化鈦氧化層 •氧化鈦氧化層 第8a圖：本發明第四實施例所製得之 的截面圖。 層 第8b圖：本發明第五實施例所製得之二& 的截面圖。 一虱化鈦氧化 第8c圖：本發明第六實施例所 & 的截面圖。 一氣化鈦氧化層 一 14〜 201119692 _ 第9圖：本發明之反應時間相對管長之變化圖。 第10圖：本發明之電壓相對孔徑之相對變化圖。 第11圖：本發明於不同供氧源下，孔徑相對反應時間 之變化圖。 【主要元件符號說明】 〔本發明〕[s] - 13 - [Simplified description of the drawings] Fig. 1 is a flow chart showing the surface treatment method of the titanium artificial implant of the present invention. Fig. 2 is a schematic view showing the apparatus for performing anodization in the present invention. Figure 3: Schematic representation of the reaction steps of the invention. Fig. 4 is a schematic view showing the structure of the second gas after completion of the reaction step of the present invention. ~ yiyi layer surface Fig. 5a is a top view of the first embodiment of the present invention. Titanium Oxide Oxide Layer Figure 5b is a cross-sectional view of # in the present invention. Rolled titanium rolled layer Fig. 6a: A top view of the second embodiment of the present invention. Herein, the emulsified titanium oxide layer Fig. 6b is a cross-sectional view of the second embodiment of the present invention. Titanium Oxide Oxide Layer Fig. 7a is a top view of a third embodiment of the present invention. Wei Wei Oxide Layer Fig. 7b is a top view of a third embodiment of the present invention. Titanium Oxide Oxide Layer • Titanium Oxide Oxide Layer Fig. 8a is a cross-sectional view of a fourth embodiment of the present invention. Layer Figure 8b is a cross-sectional view of a second & One titanium oxide oxidation Fig. 8c is a cross-sectional view of the sixth embodiment of the present invention. A vaporized titanium oxide layer - 14 to 201119692 _ Figure 9: A graph showing the change in reaction time versus tube length of the present invention. Figure 10 is a graph showing the relative change in voltage versus aperture of the present invention. Figure 11 is a graph showing changes in pore size versus reaction time for different oxygen supply sources of the present invention. [Description of main component symbols] [Invention]
欽人工植體 11 二氧化鈦氧化層 陽極氧化反應電解液 3 電極組 陰極電極 32 陽極電極 容器Artificial planting body 11 titanium oxide oxide layer anodizing reaction electrolyte 3 electrode group cathode electrode 32 anode electrode container
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