584557 【發明所屬之技術領域】 本發明是有M於—種在金屬基材表面層形成有麵、磷及氧元 素之活性複合層的生醫植入材料，特別關於一種鱗、詞及氧等元素 擴散進入金屬基材表_氧化闕，並在該氧化崎結構的格隙中 形成強力鍵結而構成-含骨質元素的活性複合層之生醫植入材料， 以及利用加熱活化技術製造該生醫植人材料的方法，和—種對生醫 植入材料之金屬基材進行表面處理的方法。 、_ 【先前技術】 關於骨路重建材料，例如人工關節或内固定器等用於牙科、顧 骨、顏面、脊柱或上、下肢整形重建用的骨質植入物，除了應具有 生物相容性之外，尚須具有特定的機械和耐耗要求。目前醫^所 使用之骨科植入物係將例如經基磷灰石(hydroxy_apati㈣等之具有生 物相容性的雌_，以電化學魏法、化學氣相沈積法，魏衆 炫射法等被覆於基材上而形成；此外，為了促進植人物與周圍組織 間的骨整合侧，以提高植人系統的骨整合成辨，而需要增加植584557 [Technical field to which the invention belongs] The present invention is a biomedical implant material having an active composite layer of a surface, phosphorus and oxygen elements formed on a surface layer of a metal substrate, and particularly relates to a scale, a word, and oxygen. Elements diffuse into the surface of the metal substrate, osmium oxide, and form a strong bond in the lattice of the oxidized silicon structure to form a biomedical implant material containing an active composite layer containing bone elements, and use heat activation technology to manufacture the biomaterial A method for planting human materials, and a method for surface treating a metal substrate of a biomedical implant material. _ [Previous technology] Regarding bone reconstruction materials, such as artificial joints or internal fixators, bone implants used in dental, bone care, facial, spine, or upper and lower limb plastic reconstruction, except that they should be biocompatible In addition, there must be specific mechanical and wear resistance requirements. Orthopedic implants currently used in medical care will be covered with basic biocompatible females such as hydroxy_apati, etc., which will be covered by electrochemistry, chemical vapor deposition, Weizhongxuan, etc. In addition, in order to promote the osseointegration side between the implanted person and the surrounding tissues to improve the osseointegration of the implanted system, it is necessary to increase the
入物之接觸表面， 其手段則包括在才直入物的活性陶絲面形成具有 微米級孔洞(micro-pitted)的表面，例如usp 4,33〇,㈣?虎專利說明書The contact surface of the object includes means to form a micro-pitted surface on the surface of the active ceramic wire that is directly inserted, for example, USP 4,33, ㈣ Tiger patent specification
賴；或者進-步使難陶絲_細再長出二層或或更多層的 複式孔洞結構者，例如本案發明人等於中華民國專利公告第你· 號中所揭露之技術；或以生物可降解組成物對植人物的有孔表面做 處理，例如USP 5,947,893號專利說明書所載；或藉控制被覆層的預 設溶解速率，例如US 6,419,7G8 B1所教示者，以促進植人物和周圍 組織間的骨整合。 再者，除了植入物與周圍組織間之整合作用以外，植入物之基 5 584557 材與活性喊層間的結合強度亦為植人物是否能符合所錢械強纟 ， 與耐耗性要求之重點。然而，以電化學電锻法所形成之錢層，其& · /P比不易控制’且因鍍層與植入材表面間之鍵結力量十分脆弱，導 至鍍層易脫附斷裂；以化學氣相沈積法被覆經基敵石之類的活性 陶兗鑛層者，健層賴之Ca/P比接近L67，且與基材之鍵 — 結為凡得瓦力，當植入材承受植入過程中所施加的多軸應力時，易 - 發生破裂；而利用電漿溶射技術，將溶融的經基磷灰石顆粒以高壓 氣體喷發錢鑛方式被覆至基材表面的噴塗層，雖具有高附著強度， 惟受電漿溶射之高溫影響，其與植入材表面發生相變態而改^械 · 性質，近年來臨床實驗上已證實其整體艘膜在植入人體後會發生鏡 膜脫附斷裂的情形。 【發明内容】 本發明即是為解決習知技術之祕問題而經多方研究所完成者 。亦即’本發明之目的在於提供—種邊界斷裂及缺乏強度等問題獲 得明顯改善之生醫植入材料。 依據本發明之生醫植人㈣係於金屬基材表面形成有含转、鱗 ^氧等骨質元素之活性複合層；尤其是使填、與及氧離子擴散參人 · 金屬基材表面之氧化層結構，並在其袼隙中產生強力鍵結而形成之 衣囬法'性;^合。 本發明之另-目的在於提供一種生醫植入物，特徵係在金屬基 材表層开>成舞、碟成分比接近人骨組織之活性複合層。 本發明亦提供-種利用加熱活化技術以製造生醫植入物的方法 、 。_本發明之該生醫植入物的製造方法，主要係藉加熱活化技術 使A #5、氧等軒擴散進人—生醫植人物的金屬基材表面之氧化 6 584557 層膜，藉以製造-在表層形成有含碟、約、氧等骨質元素的活性複： 合層之生醫植入物。 另本毛月又目的係為提供—種生醫植入材料之金屬基材的 表面處理方法’藉以使詞、魏氧等骨質元素渗進金屬基材的表面 而形成一活性複合層；尤其是利用加熱活化處理，賴、磷及祕 一 子擴散進入金屬基材表面的氧化膜層結構中，並在其中產生強鍵結 力的表面處理方法。 依據本發明之生醫植入物的金屬基材之表面處理方法主要係使 骨質元素利用加熱擴散原理擴散進入金屬基材的表層；例如麟離子 # 儀藉熱化學擴散原理，而_子則是利用温度擴散方式進入金屬基 材的表面。 本毛月所使用之月貝元素中，磷離子的來源係先將含構的氧化 酸或氧化驗，透過加熱、溶解或融溶程序使元素分離而形成含離子 之處理溶液。當金屬騎表面触處理驗在加齡化的條件下接 觸時，初期因熱化學擴散反應之進行，基材表面隨著溫度上昇而活 化，處理溶液中大量的離子競爭吸附於該活化的基材表面上；此時 ，透過在表面上的化學反應之催化，部分構成基材的金屬原子被釋 · 出’與處理溶液中之離子進行交換，離子逐漸擴散置換進入基材結 構中。 上述離子擴散置換過程中，氫離子受到加熱溫度的影響，率先 自晶界逐漸擴散進入基材表面的氧化膜層結構中，而鱗離子亦隨著 ' 溫度的上幵終於越過活化能障而擴散進入該氧化膜層中。 、 接著在基材表面的金屬離子和氧離子與溶液發生交互反應，大 量的離子擴散進入基材的狀態下，實施鈣離子之溫度擴散。此階段 7 584557 係以含鈣化合物經加熱、溶解或融熔程序造成元素分離而得之含離 子的水淬液，配合溫度的急劇變化，將所有的離子封入表層中，並 使其等隨著溫度調節表面應力而擴散進入基材中。過程中，鈣離子 逐漸擴散置換進人基材結構，並隨著溫度上昇逐漸致使氧離子亦越 過活化能障而擴散進入基材中。 更詳細地說，本發明之前述表面處理方法中，當以浸潰或喷塗 法，使金屬紐表Φ與含軒之處理溶紐生觸時，由於鱗離子 半控僅0·35Α，故先行透過熱化學擴散反應過程中之激烈的熱化學作 用而擴散進人金屬基材表面的氧化蘭，形成—複合層結構；而氧 化膜層亦因_子擴散進人的影響，内部結構應力增高，為調節該 内部應力，乃於表面出現裂紋。 她其後，透過冷淬收縮方式被封入結構中之離子半徑099入_ 二』’⑽熱下彻溫度擴散方式迅速擴散進入該複合層結構中； j離子半赠1.32A之氧軒亦隨著溫度上昇，終致越過活化 月巨p早而擴散進入該複合層結構中。 、来透顧上之處理’藉熱擴散進人金屬基材表關氧化膜層之約 V及氧等離子’於冷雜溫過程迅速地被封人經熱活化的氧化膜 2，並擠進該氧化層格隙中，故可形成—具有強力鍵結之 素的活性複合層。 此外Lai; or those who make it difficult to make the pottery silk_then grow two or more layers of double-hole structure, for example, the inventor of this case is equivalent to the technology disclosed in the Republic of China Patent Bulletin No. ·; or biological The degradable composition treats the perforated surface of the planting character, such as contained in USP 5,947,893 patent specification; or by controlling the preset dissolution rate of the coating layer, such as taught by US 6,419,7G8 B1, to promote the planting character and the surrounding Tissue osseointegration. Furthermore, in addition to the integration between the implant and surrounding tissues, the strength of the bond between the implant's base 5 584557 and the active shout layer is also whether the implanted person can meet the requirements for strength and wear resistance. Focus. However, the coin layer formed by the electrochemical electroforging method has a & · / P ratio that is not easy to control ', and the bonding force between the plating layer and the surface of the implant material is very weak, which leads to the plating layer being easily desorbed and broken; Vapor deposition methods covering active pottery ore layers such as base enemy stones, the Ca / P ratio of the healthy layer is close to L67, and the bond with the substrate is the result of van der Waals force. When the multi-axial stress is applied during the process, fracture easily occurs; and the plasma spray technology is used to coat the molten apatite particles on the surface of the substrate with a high-pressure gas eruption money deposit. Although It has high adhesion strength, but it is affected by the high temperature of plasma spraying. It changes its mechanical properties with the surface of the implant material. In recent years, clinical experiments have confirmed that the overall membrane of the ship ’s membrane will be removed after implantation in the human body. Case of fracture. [Summary of the Invention] The present invention is completed by various research institutes in order to solve the secret problem of the conventional technology. That is, the object of the present invention is to provide a biomedical implant material that has significantly improved the problems such as boundary fracture and lack of strength. The biomedical planting plant according to the present invention is formed on the surface of a metal substrate with an active composite layer containing bone elements such as oxygen, scale, oxygen, and the like; in particular, the filling, and oxygen ion diffusion participates in the oxidation of the surface of the metal substrate. Layer structure, and a strong bond formed in its crevice to form the clothes back to the law; Another object of the present invention is to provide a biomedical implant, which is characterized by being active on the surface of a metal substrate and having an active composite layer with a composition ratio close to that of human bone tissue. The invention also provides a method for manufacturing a biomedical implant by using a heating activation technology. _The method for manufacturing the biomedical implant of the present invention is mainly to oxidize A # 5, oxygen, etc. into the surface of the metal substrate of the human-biomedical plant by heating activation technology 6 584557 layer film to manufacture -Formed on the surface layer is an active compound containing bone elements such as dishes, cavities, and oxygen: a layered biomedical implant. In addition, the purpose of this month is to provide a surface treatment method of metal substrates for biomedical implant materials, by which bone elements such as Ci and Wei oxygen penetrate into the surface of metal substrates to form an active composite layer; especially A surface treatment method in which heating, activation, and diffusion of Lai, Phosphorus, and Sebastian are diffused into the oxide film structure on the surface of a metal substrate, and a strong bonding force is generated therein. The surface treatment method for the metal substrate of the biomedical implant according to the present invention is mainly to diffuse bone elements into the surface layer of the metal substrate using the principle of thermal diffusion; for example, the Lin ion # 仪 borrows the principle of thermal chemical diffusion, and _ 子 is The temperature diffusion method is used to enter the surface of the metal substrate. Among the scallop elements used in this month, the source of phosphorus ions is the structure-containing oxidizing acid or oxidation test, and the elements are separated by heating, dissolving or melting processes to form an ion-containing treatment solution. When the contact surface of the metal riding surface is tested under aging conditions, the initial stage is due to the thermochemical diffusion reaction. The surface of the substrate is activated as the temperature rises. A large number of ions in the processing solution compete to adsorb on the activated substrate. On the surface; at this time, through the catalysis of a chemical reaction on the surface, part of the metal atoms constituting the substrate are released and released 'and exchanged with the ions in the processing solution, and the ions gradually diffuse and displace into the substrate structure. During the above ion diffusion replacement process, hydrogen ions are affected by the heating temperature, and they are the first to gradually diffuse from the grain boundaries into the oxide film structure on the surface of the substrate, and the scale ions also diffuse along with the temperature rise and finally cross the activation energy barrier. Into the oxide film layer. Then, on the surface of the substrate, metal ions and oxygen ions interact with the solution, and a large number of ions diffuse into the substrate, and the temperature diffusion of calcium ions is performed. At this stage 7 584557 is an aqueous quenching solution containing ions obtained by calcium-containing compounds separated by heating, dissolving or melting procedures. With the rapid change of temperature, all ions are enclosed in the surface layer, and so on. Temperature regulates surface stress and diffuses into the substrate. During the process, calcium ions gradually diffused into the structure of the human substrate, and as the temperature increased, oxygen ions also diffused into the substrate through the activation energy barrier. In more detail, in the aforementioned surface treatment method of the present invention, when the metal button surface Φ is brought into contact with the treatment solution containing Xuan by the dipping or spraying method, the scale ion is half-controlled only at 0.35A, so Oxidation blue that diffuses into the surface of human metal substrates is formed by the intense thermochemical action in the process of thermochemical diffusion reaction, forming a composite layer structure; and the oxide film layer is also affected by the diffusion of ions into the human body, which increases the internal structural stress. In order to adjust the internal stress, cracks appear on the surface. After that, the ion radius enclosed in the structure by cold-quenching shrinkage method was 099. The rapid diffusion under the heat and temperature diffused into the composite layer structure; the oxygen ion of 1.32A, which is a half gift of j ion, also followed As the temperature rises, it eventually diffuses into the composite layer structure beyond the activated moon giant p. To deal with the above, the 'V and oxygen plasma of the oxide film layer by heat diffusion into the surface of the metal substrate by heat diffusion' was quickly sealed by the thermally activated oxide film 2 in the cold and mixed temperature process, and squeezed into the The oxide layer is in the gap, so it can form an active composite layer with a strong bonding element. Besides
入味㈣本1係细升溫與化學活化表面的方式使骨f元素擴散進 0生西植人㈣的表層，故可在_離子莫耳濃度、溫度等參數之 氧離^速t仃Μ降溫操作’將擴散進人金屬基材表層之碌、詞及 封人糾加熱活化之氧化膜層，並進人氧化層格隙中， 而控制離子在所形成之活性複合層中的比例與擴散深度 8 透過進-步加織經過冷淬降溫之金屬紐，可以錄封入之各離 子在4/錄複合層結構巾繼續擴散仙，進人適當的 結構的安定化。 、 、另’本發明之生醫植人物的金屬基材之表面處理方法中，可 γ直接使A 及氧轉子擴散滲人金屬基材表面所具有的氧 +、亦可豸丨先對金屬基材施以陽極氧化處理 基材表面以增顧化職，顧_榻處理。u 本毛月中所使用之含碟的氧化酸或氧化驗，只要是能夠透過加 熱、溶解或騎程序而達到缝分離，以提絲面處理所需之構、 乳專離子成分者，並她则，惟以醫療上所相者，例如醫療 =酉夂為S ’本發崎使狀麵化合物只要是能夠透過加熱 ^解或賴程相_元素分離，以提絲面處輯需之約和氣 —子者，亦無特殊限制，惟以㈣級之各 ，峨彻_。 本务明所獅之加熱活化技術，溫度侧m坑至⑽。c左 =為宜’而以赋至175t之間較佳。#加熱溫度傭⑽時， ίΓΓΓ介柯魏細反應、，加熱溫度若超過赋則可能 务生孟屬基材尺寸變化的不利結果。 入^^所製成之生醫植人物，其金屬基材表_性複合層所 二a Ρ”於U至2·2,而含有近似人骨織織成分’亦即Ca/P比 接近L67H,_^排斥賴，最為合適。 【實施方式】 將以下列較佳實施態樣並配 本發明之技術内容、特點與優點 合圖式進一步闡明。 以下實施例將採用符合ASTM規範之醫療用g2純鈇棒做為本 發明之生醫植入物的金屬基材。進行各項試驗前，先將G2純鈦棒切 成直徑0.5公分，厚度L0公分之試片，並且先以超音波清洗試H 面，再用清水洗淨後備用。 t ESCA檢測 本發明中所採用之ESCA檢測係使用Mg dual an〇de，最大能量 15kV，400 Watt，Mg dual anode 為 1253.6eV。分析區為 1;1 咖直捏 之圓。全區測試範圍0至115〇eV，Pass Energy 89.45eV。離子搶錢Into the miso Ben 1 series, the method of finely warming and chemically activating the surface allows the bone f element to diffuse into the surface layer of the unripe phytoplankton, so it can be operated at the oxygen ionization rate t 仃 M of the _ ion mole concentration, temperature and other parameters. 'Will diffuse into the surface layer of the human metal substrate, and the heat-activated oxide film layer will be incorporated into the gap of the oxide layer, and the proportion of the ions in the active composite layer formed and the diffusion depth 8 will be controlled. By further weaving the metal buttons that have been cold-quenched and cooled, you can record the enclosed ions in the 4 / record composite layer structure to continue to spread the fairy, and enter the appropriate structure stability. In addition, in the surface treatment method of the metal substrate of the biomedical planting person of the present invention, γ can directly diffuse A and the oxygen rotor to infiltrate the oxygen on the surface of the metal substrate. Alternatively, the metal substrate can be first treated. Materials are anodized to treat the surface of the substrate in order to increase the number of jobs and processes. u The oxidized acid or oxidation test containing the dish used in this hair month, as long as it can achieve seam separation by heating, dissolving or riding procedures, and raise the structure and milk ion components required for silk surface treatment, and her Then, only those who are medically relevant, for example, medical treatment = 酉 夂 is S 'Benfasaki, as long as the compound can be separated by heating ^ solution or Lai Cheng phase_elements, in order to improve the reconciliation at the silk surface. —Children, there are no special restrictions, except for each class of ㈣, Echer_. The heating activation technology of the lion of this business, the temperature side m pit to ⑽. c left = is preferred 'and it is better to give between 175t. # Heating temperature commissioning, ΓΓΓΓ introduces Ke Weiwei reaction, if the heating temperature exceeds the limit, it may cause adverse results of the size change of the substrate. The biomedical planting figure made by entering ^^ has a metal substrate with a superficial composite layer of 2 a P ”between U and 2.2, and contains approximately human bone weaving composition, that is, the Ca / P ratio is close to L67H, _ ^ Rejection is the most appropriate. [Embodiment] The following preferred embodiments will be further clarified with the technical content, features and advantages of the present invention and the drawings. The following examples will use medical pure g2 in accordance with ASTM specifications. The rod is used as the metal substrate of the biomedical implant of the present invention. Prior to each test, a G2 pure titanium rod is cut into a test piece with a diameter of 0.5 cm and a thickness of L0 cm, and the H surface is first cleaned by ultrasonic cleaning. After washing with water, it is ready for use. T ESCA detection The ESCA detection used in the present invention uses Mg dual an〇de, the maximum energy is 15kV, 400 Watt, and Mg dual anode is 1253.6eV. The analysis area is 1; 1 The pinch of the circle. The test range of the whole region is 0 to 115 eV, Pass Energy 89.45 eV. Ion grabs money
蝕每次錢钱深度約10至100A ;每個樣品之濺蝕深度在1〇〇至2〇〇 A 間。 SEM顯撒照相 本舍明係採用日立公司製S-4100機型之SEM，以25°C、10至 9torr ’加速電壓20kV的操作條件進行顯微照相。 空白試驗 1 將洗淨之試片沒入純度95%鱗酸（Merck製）溶液中，不予加 熱即取出，然後以化學分析電子光譜儀（ESCA54〇〇)進行材料表面 組織形恶及化學結構分析，得到如第2圖所示之表層1〇〇人深度範圍 的元素含量分布狀態。 第2圖顯示·，洗淨之鈦金屬試片雖以95%磷酸溶液浸潰，在表 層100A範圍内並未發生磷離子擴散現象；而，氧、鈦離子的分布情 形亦顯示氧化膜集中於最表層部分。 擅厚氧化膜層 將沒入95%石粦酸溶液再取出之試片分別施以3〇v、6〇v及9〇v 之陽極氧化處理，使氧進入基材表層以增厚氧化膜層。以ESCA量 10 584557 測元素含量之結果示於第3〜第5圖。 將第3圖至第5圖與第2圖對照比較發現，利用陽極氧化處理 ，隨著電流強度增強，氧化賴德材表層1GGA喊目内逐漸增厚 ，尤以9〇 (v)的電、流強度處理時效果最為顯著。同日寺，碟離子亦有少 量擴散進入氧化膜層中。 形成活性福合層 實施例1 取9 g醋酸鹤溶入1〇〇 ml之純水中，在室溫下擾掉做為水泮溶 液備用。 將洗淨之試片完全浸入25〇ml之95%純_中，一邊以授掉機 加以混合，-邊加熱至175t，同時抽去反應所產生之氣體。 前述95%純麟酸在加熱過程中形航素分離之處理溶液，而試 片之表層亦在加熱下被活化後，使該試片在丨机的反應溫度下留置 於該處理溶液中約15秒，待反應更形激烈，並且自該試片溶出部分 藍色離子時，迅速將其移入醋酸鈣水淬溶液中。 過程中，將經過碟酸溶液加熱處理之試片以SEM照相，結果 不於第6(a)圖及帛6(b)圖；由倍率5_之第6⑻圖清楚得見試片表 面發生破裂，齡試丨在鱗子驗發生交互反應下，離子逐散進 入基材中造成結構應變，並為調節應力而在表面發生破裂。由倍率 6000之第6(b)®I ’進-步發現試片表面有微細突起。 接著，將經過水淬之試片以靜置於該醋_水泮溶液的狀態， 緩慢加熱㈣騰2小時後，制水冷卻至室溫。將試片取出並以加 熱爐加熱至150°C，維持恆溫6小時後再予以爐冷。 將爐冷後之試片以ESCA進行分析其表層〇A至⑽A區間内 11 584557 之元素含量分布狀態，得到如第7圖所示之結果。 根據第7圖所示之結果可知，經過處理之試片，Ή含量由外側 向内部遞增，〇含量則在5〇Α左右的深度達到最高的5248重量％， 和不於第2圖之未處理試片的量測值相較，可以確知大量的氧離子 擴散進入氧倾層巾。此外，Ca含量㈣側向内靖遞增至⑽入 的深度時之8.58重量％，顯示Ca離子亦有效地擴散進人試#之氧化 膜層中，1¾ P含量則是在·左右的深度達到最高，測得有314% ’使得Ca / P比在該深度達到18〇。 以上結果顯示，依據本實施例將可使磷和鈣等元素有效地擴散 進入鈦金屬基材表層，並形成—具有適#的Ca/p比之活性複合層 〇 實施例2 除水淬溶液改以6 g檸檬酸弓溶於100 ml純水取代以外，盆餘 條件和操俩和實補1 _。ESCA制絲祕第8圖。’、、 實施例3 除將％擰檬酸於100 ml純水做為水淬溶液以外，其餘條 件和操作均和實關丨相同。ESCA制結果示於第9圖。 實施例4 、以乳酸約取代實施例3之檸檬酸約，其餘操作相同；ESCA量 測結果示於第10圖。 趙敢Ιί磷、鈣互氩藤子的擔散情形 根據第7圖至第1()圖之p、Ca%，顯示試片經過本發明之方法 處理後，在金屬基材表面所形成之活性複合層中，p含量並不因紐 所分離出之酸根不同而降低，且由外向内遞增，尤以q至姐左右 12 584557 含量最高，顯示此活化層在反應触巾引發大量的p離子擴散進入 ’而由於P離子半徑僅0.3认，故推測應是擴散進入結構中填入晶體 格隙。 此外’ Ca含夏亦呈現由外向内遞增的狀態，尤其在〇至別入 左右達到最高，顯示Ca離子在反應過程中亦大量擴散進入，惟因The depth of each etch is about 10 to 100A; the depth of the etch of each sample is between 100 and 2000A. SEM Display Photo This photomicrograph was taken using an SEM of Hitachi S-4100 model, and the photomicrograph was taken under the operating conditions of 25 ° C and an acceleration voltage of 10 to 9torr '20kV. Blank test 1 The cleaned test piece was immersed in a solution of 95% linolenic acid (Merck), which was taken out without heating, and then the surface texture and chemical structure of the material were analyzed by a chemical analysis electron spectrometer (ESCA 5400). , To obtain the element content distribution state in the depth range of 100 people in the surface layer as shown in FIG. 2. Figure 2 shows that, although the cleaned titanium test piece was impregnated with a 95% phosphoric acid solution, phosphorus ion diffusion did not occur within 100A of the surface layer; and the distribution of oxygen and titanium ions also showed that the oxide film was concentrated on The topmost part. The oxide film is good at thickening. The test pieces that are not immersed in the 95% lysinic acid solution are subjected to anodizing treatments of 30v, 60v, and 90v, respectively, so that oxygen enters the surface layer of the substrate to thicken the oxide film layer. . The results of measuring the element content with the ESCA amount 10 584557 are shown in FIGS. 3 to 5. Comparing Fig. 3 to Fig. 5 with Fig. 2 and found that with the anodizing treatment, as the current intensity increases, the surface of the oxidized Ryder material 1GGA gradually thickens, especially the electric and current strength of 90 (v). The effect is most significant when treated. At the same temple, a small amount of dish ions diffused into the oxide film. Forming an active fusing layer Example 1 Take 9 g of crane acetate and dissolve it in 100 ml of pure water, and stir it at room temperature as a leech solution for later use. The cleaned test piece was completely immersed in 25 ml of 95% pure _, while mixing with a dispenser,-while heating to 175 t, the gas produced by the reaction was removed at the same time. The aforementioned 95% pure linoleic acid is a treatment solution for isomorphic separation during heating, and after the surface layer of the test piece is also activated under heating, the test piece is left in the treatment solution for about 15 at the reaction temperature of the machine In seconds, when the reaction becomes more intense, and when some blue ions are dissolved from the test piece, it is quickly transferred into a calcium acetate water quenching solution. During the process, the test piece subjected to the heat treatment of the dish acid solution was photographed by SEM, and the results are not shown in Fig. 6 (a) and Fig. 6 (b); from the sixth picture of magnification 5_, it is clear that the surface of the test piece is cracked. Age test 丨 Under the interactive reaction of the scale test, the ions diffuse into the substrate to cause structural strain, and the surface breaks in order to adjust the stress. From step 6 (b) ®I of 6000 magnification, it was found that there were fine protrusions on the surface of the test piece. Next, the test piece subjected to water quenching was left in the state of the vinegar-water solution, and was slowly heated for 2 hours, and then the water was cooled to room temperature. The test piece was taken out and heated to 150 ° C in a heating furnace, and the furnace was cooled after maintaining a constant temperature for 6 hours. After the furnace-cooled test piece was analyzed by ESCA, the element content distribution state of 11 584557 in the surface layer OA to ⑽A range was obtained, and the result shown in FIG. 7 was obtained. Based on the results shown in Figure 7, it can be seen that after the treated test piece, the content of radon increased from the outside to the inside, and the content of 0 reached a maximum of 5248% by weight at a depth of about 50A, and the untreated was less than that in Figure 2. Compared with the measured value of the test piece, it can be confirmed that a large amount of oxygen ions diffused into the oxygen tilt layer towel. In addition, the Ca content ㈣ laterally inwardly increased to 8.58% by weight at the depth of penetration, showing that Ca ions also effectively diffused into the oxide film layer of the human test #, and the 1¾ P content reached the highest depth around the · It was measured that 314% 'caused the Ca / P ratio to reach 180 at this depth. The above results show that according to this embodiment, elements such as phosphorus and calcium can be effectively diffused into the surface layer of the titanium metal substrate, and an active composite layer having an appropriate Ca / p ratio is formed. Example 2 Replace 6 g of citric acid bow in 100 ml of pure water and replace the remaining conditions and practices and supplements. Figure 8 of the ESCA Secrets. ′, Example 3 The conditions and operations are the same as the actual conditions, except that 100% pure citric acid is used as the water quenching solution. The results of the ESCA system are shown in FIG. 9. In Example 4, lactic acid was used to replace the citric acid in Example 3. The rest of the operations were the same; the results of the ESCA measurement are shown in Figure 10. Zhao Ganyi ί The dispersive situation of phosphorus and calcium mutual argyle According to p and Ca% of Fig. 7 to Fig. 1 (), it shows that the active compound formed on the surface of the metal substrate after the test piece is treated by the method of the present invention In the layer, the p content does not decrease due to the different acid radicals separated by the button, and it increases from the outside to the inside, especially the highest content of q to the left and right 12 584557, indicating that this active layer causes a large number of p ions to diffuse into the reaction towel. 'Because the P ion radius is only 0.3, it is speculated that it should diffuse into the structure and fill the crystal lattice. In addition, the Ca-containing summer also shows a state of increasing from the outside to the inside, especially reaching the highest level from 0 to the other, indicating that Ca ions have also diffused into the reaction process.
Ca離子半錢_ A，其擴散進入將造成結構應變增加，推測亦應 是填入晶體格隙並與金屬基材緊密結合。 另，〇含量雖亦呈現顯示反應過程中有大量氧離子纖進入之 由外向内遞增的趨勢，惟因氧離子半徑高達⑶人，其擴散進入將會 · 造成結構應變大幅增加，故在1GA以後，氧含量即逐漸降低。 ^再者’將實施例4所獲得之試片以SEM照相發現，第n(a)及 第ll(b)_示’試片在鱗離子擴散進人氧化膜層後，表面雖產生裂 縫以調節大録子溶液發生交互反應下，離子逐龍散置換進入金 屬基材結構巾所累積的_應力，但是經過封孔後，則是在表面上 生成相互交錯之針狀與板條狀結構。11刚更顯示㈣表面之活化 複合層的最終表面錢聚現象而形成-如縮晶狀物的表面。 上述結果顯示’依據本發明之金屬基材的表面處理方法，確實 · 可以使麟、舞、氧等離子透過熱化學擴散或加溫擴散的方式進入金 屬基材表層的氧倾層巾，有效地形成—個含有舆人倾織接近之 骨質成分的活性複合層。 骨整合效果- 將未經活性複合層處理之鈦金屬原材與利用實施例4的條件處 〜 理過之生醫植人物植人12個月大，重5 Kg之紐西献白兔的腔骨 ，觀察植入八週後之骨組織生長情形。結果示於第12(&)及12(b)圖之 13 584557 組織切片的顯微照片中。 由第12(a)®!可以清楚看見未形成活性複合層之鈦合金原材植入 物在經過八週後與骨基質之間仍有一明顯縫隙，第12 (b)圖則顯示以 實施例4所製成之表面形成有活性複合層的生醫植入物經過八週之 後，與骨基質之間無缝隙產生，證實骨組織成功地與植人物整合。 如上所述，本發明之生醫植入物由於金屬基材的表面上所形成 之活性複合層中，罐、舞、氧等骨質元素實質地擴散進入氧化膜層 的格隙中，而且在水淬處理中被包封，因此，與金屬基材之間不但 形成強力鍵結，而且二者之間無明顯的層間界面，故相較於習知之 電化學統、化學氣相沈積或電漿炫射等方法所形成的活性喊鑛 層或喷塗層，因係以薄弱的機械力或物理力與金屬基材的界面結合 ’而易脫瞒裂或受錄應力而破裂，本發明之生紐人物錄I 效果上明顯可以大幅減少脫附斷裂與受多轴應力而破裂的情形。 此外’由於本發明之生醫植入物在金屬基材表層形成有針狀社 構或收縮晶狀物團聚，為-非綺表面，有利於倾織之修復與整 合’相對於習知技術藉由在金屬基材表面形成孔隙以促進骨整合的 方式，非但製程精簡，且骨整合效果更為全面有效。 —以上所述者’僅為本發明之較佳實施祕，非職蚊本發明 員> >範目大凡依个發B月申請專利範圍及發明說明書内容所揭示 之技術思想而為之簡單的等效變化與修部，皆應仍屬本發明專利涵 蓋之範圍内。 【圖式簡單說明】 第1(a)圖〜第l(e)圖為依據本發明之生醫植人物的金屬基材之表 面處理方法中，相關的離子擴散示意圖； 乂 14 584557 .第2 ’未經處理之醫療用G2純轉表層的元素含量分布圖Ca ion is half a coin _ A, and its diffusion and entry will cause an increase in structural strain. It is speculated that it should also fill the crystal lattice and tightly bond with the metal substrate. In addition, although the content of 〇 also shows that a large number of oxygen ion fibers enter from the outside to increase during the reaction process, but because the oxygen ion radius is as high as 3 people, its diffusion will cause a significant increase in structural strain, so after 1GA The oxygen content gradually decreases. ^ Further, the SEM photograph of the test piece obtained in Example 4 was found to show that the test piece n (a) and ll (b) _ shows that after scale ions diffused into the human oxide film layer, cracks appeared on the surface. After the interaction of the large recording solution is adjusted, the ions that accumulate in the metal substrate structure are replaced by the ions, but after sealing, a staggered needle-like and lath-like structure is generated on the surface. 11 just showed that the final surface of the composite layer on the surface of the activated fluorene aggregates-such as the surface of crystallites. The above results show that according to the surface treatment method of the metal substrate of the present invention, it is possible to make the linoleum, dance, and oxygen ions into the oxygen tilting towel of the surface layer of the metal substrate through thermochemical diffusion or thermal diffusion, effectively forming -An active composite layer containing bone components that are closely related to each other. Osseointegration effect-Treating titanium raw material without active composite layer and using the conditions of Example 4 ~ Treated biomedical planting figures were 12 months old and weighed 5 kg. Bone, observe the growth of bone tissue eight weeks after implantation. The results are shown in photomicrographs of 13 584557 tissue sections in Figures 12 (&) and 12 (b). From Figure 12 (a) ® !, it can be clearly seen that there is still a clear gap between the titanium alloy raw material implant without the active composite layer and the bone matrix after eight weeks. Figure 12 (b) shows an example 4 After eight weeks, the biomedical implant with an active composite layer formed on the surface produced a seamless gap with the bone matrix, confirming that the bone tissue was successfully integrated with the implanted character. As mentioned above, in the biomedical implant of the present invention, due to the active composite layer formed on the surface of the metal substrate, bone elements such as cans, dances, and oxygen diffuse substantially into the gaps of the oxide film layer. It is encapsulated during the quenching process. Therefore, not only a strong bond is formed with the metal substrate, but there is no obvious interlayer interface between the two. Compared with the conventional electrochemical system, chemical vapor deposition or plasma plasma, The active shouting layer or spray layer formed by spraying and other methods is easily combined with the interface of the metal substrate with weak mechanical or physical forces, and it is easy to be cracked or cracked by recording stress. Biographical Records I significantly reduce the number of desorption fractures and fractures caused by multiaxial stress. In addition, 'Because the biomedical implant of the present invention has a needle-like structure or agglomerated crystals formed on the surface of the metal substrate, it is a non-smooth surface, which is conducive to the repair and integration of the weaving.' By forming pores on the surface of the metal substrate to promote osseointegration, the process is streamlined and the osseointegration effect is more comprehensive and effective. —The above mentioned ones are only the best practice secrets of the present invention. The non-employee mosquito inventors > > Fan Mu Dafan is simple according to the technical ideas disclosed in the scope of patent application and the contents of the invention specification. The equivalent changes and repairs should still fall within the scope of the invention patent. [Brief description of the drawings] Figures 1 (a) to l (e) are schematic diagrams of related ion diffusion in the surface treatment method of a metal substrate for a biomedical plant figure according to the present invention; 乂 14 584557. 2 'Element content distribution of untreated medical G2 pure to surface
J 圖為、、、工過3G (v)陽極氧化處理之氧化膜層元素含量分布圖 j 第圖為、、、二過60 (v)陽極氧化處理之氧化膜層元素含量分布圖 y 第5圖為㈣9G (v)陽極氧化處理之氧賴層元素含量分布圖 j 第6(a)圖及第6(b)®分別為磷酸溶液加熱處理之試片的5〇〇〇及 6000倍率SEM顯微照片。 第7圖為依據本發明實施例丨之生醫植入物的金屬基材表層之 元素含量分布圖； 第8圖為依據本發明實施例2之生醫植入物的金屬基材表層之 元素含量分布圖； 第9圖為攸據本發明實施例3之生醫植入物的金屬基材表層之 元素含量分布圖； 第10圖為依據本發明實施例4之生醫植入物的金屬基材表層 之元素含量分布圖； 第11(a)、11(b)、11(c)圖為本發明實施例4所獲得之試片的 SEM顯微照片； 第12(a)圖及第12(b)圖為本發明之生醫植入物在動物體内的骨 修復與整合情形示意圖。 15J is the distribution diagram of the element content of the oxide film after the 3G (v) anodizing treatment j The graph is the distribution diagram of the element content of the oxide film layer after the 3, 60, (v) anodizing treatment The picture shows the distribution of element content of oxygen layer in 赖 9G (v) anodization. Figures 6 (a) and 6 (b) are the SEM and 6000 magnification SEM results of the test piece heat treated with phosphoric acid solution, respectively. Micro photo. FIG. 7 is an element content distribution chart of a metal substrate surface layer of a biomedical implant according to Example 丨 of the present invention; FIG. 8 is an element content of a metal substrate surface layer of a biomedical implant according to Example 2 of the present invention Content distribution diagram; FIG. 9 is an element content distribution diagram of a metal substrate surface layer of a biomedical implant according to Embodiment 3 of the present invention; FIG. 10 is a metal of a biomedical implant according to Embodiment 4 of the present invention Element content distribution of the surface layer of the substrate; Figures 11 (a), 11 (b), and 11 (c) are SEM micrographs of the test piece obtained in Example 4 of the present invention; Figure 12 (a) and Figure 12 (b) is a schematic diagram of the bone repair and integration of the biomedical implant in the animal. 15