TWI361230B - Electrochemical process of forming ha/tio2 double layers coating on pure titanium metal - Google Patents

Description

1361230 f、發明說明： 【發明所屬之技術領域】 本發明係_-種在金屬表面形成氫氧基 ，(HA/Ti02)雙層塗層的方法，特別是—種利 純鈦金屬表面形成HA/Ti02生醫陶瓷雙層塗層之方 1 \積法在 【先前技術】1361230 f, invention description: [Technical Field] The present invention is a method for forming a hydroxyl group, (HA/Ti02) double layer coating on a metal surface, in particular, forming a HA on a pure titanium surface /Ti02 biomedical ceramic double-layer coating square 1 \ accumulation method in [prior art]

a =科技醫療的進步，現在的社會日益趨向 =，在老⑽雜巾’可能由驗牙、餘疾病或是 ^ ，牙齒喪失。因此免;f 了需要—些替代性晴料。牙^雖 =人，堅硬的身體構造，但仍不能抗拒長期的摧殘而级至^ ί ί由於牙#上附著牙菌斑(Dental P1_1，ip 3細菌j口水中_性蛋白f等作用，附著在牙齒表^ 石’ ίΓ著f間及水中礦物質的累積而触，即所謂的牙結 藉。么表面粗繞’使牙菌斑更容易附著，隨著時間的累 殘餘物’逐漸在口腔的溫床:牙縫間、牙齦溝内 =周:ί進破壞來滋長，最後造成牙齒鬆a = advances in science and technology, the current society is increasingly trending =, in the old (10) shawl 'may be caused by dental examination, residual disease or ^, tooth loss. Therefore, it is exempted; f needs some alternatives. Teeth ^ Although people, hard body structure, but still can not resist the long-term destruction of the level to ^ ί ί due to the tooth attached to the plaque (Dental P1_1, ip 3 bacteria j mouth water _ sex protein f, etc., attached In the dental table ^ stone ' Γ Γ f f 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿 矿Hotbed: between the teeth, in the gingival sulcus = week: ί into the destruction to grow, and finally cause the tooth loose

卜療期長：-般而言’植入人工牙根後，下顎須四個月以上， 在上顯須六個月以上，才能再進行假牙的製作。假如合併有骨 =移植手術(補骨量之不足）’那至少還要再加上6個月因此 前後一年的療程可說是司空見慣。 2、表面呈生物鈍性，不易與活體骨組織直接鍵結易生成纖 維組織(Fiber tissue): Ti及Ti合金表面呈現生物鈍性，當 體本身不具生物活性時，易產生活體組織排斥而以纖維組 織隔離，造成獻材無法餘财_直接_喊成植入體 3 1361230 鬆脫。 3、 細菌感染：人工植牙本身都是金屬成品，絕對不會蛀牙， 但當口腔衛生不良時，往往會導致細菌黏附在金屬植牙體表 面，最後導致植牙體與骨頭間的結合受到破壞而失敗。HA的 喷漿技術始終無法克服剝落的發生及在發炎組織中被溶解，當 基材裸露時表面易被細菌污染，最後導致植牙體與骨頭間的結 合失敗。 4、 金屬離子釋出：Ti離子：根據研究得知鈦及鈦合金植入人 體三年後在肺、脾、腎、肝及植入材附近的淋巴結都有Ti離 I 子濃度增加的現象’較嚴重會引起肝退化❶雖然Ti離子濃度 在0.01-100 ng/ml的範圍内不會對人體造成決定性的傷害， 但其會抑制血球凝結素(phytohemagglutinin)誘導T細胞及 脂肪醣（liposaccharide)誘導B細胞之增殖。 5、 過多的生物機械負荷：咬合負荷過大的臨床跡象是螺絲鬆 脫’贗復體組成斷裂，牙脊骨散失及植體周圍被纖維或表皮細鲁 胞包圍。咬合受力主要集中於植體與皮質骨嵌合處，或是以螺 絲固定植體與假牙連接處’可能導致微細骨折 (Microfracture) °The length of the treatment period: - Generally speaking, after the artificial root is implanted, the lower jaw must be more than four months, and it takes more than six months to be used for the production of the denture. If there is bone = transplant surgery (insufficient bone supplement), then at least 6 months will be added. Therefore, the course of treatment for a year and a year can be said to be commonplace. 2, the surface is biologically blunt, not easy to directly bond with living bone tissue to form fibrous tissue (Fiber tissue): Ti and Ti alloy surface is biologically blunt, when the body itself is not biologically active, it is easy to produce living tissue rejection Isolation of fibrous tissue, resulting in the lack of resources for the contribution _ direct _ shouted into the implant 3 1361230 loose. 3, bacterial infection: artificial implants are all metal finished products, absolutely no tooth decay, but when the oral hygiene is poor, it often causes bacteria to adhere to the surface of the metal implant, and finally the joint between the implant and the bone is damaged. And failed. HA's shotcreting technology has never been able to overcome the occurrence of flaking and is dissolved in inflamed tissues. When the substrate is exposed, the surface is easily contaminated by bacteria, which eventually leads to failure of the joint between the implant and the bone. 4, metal ion release: Ti ion: According to research, titanium and titanium alloy implanted in the human body three years after the lung, spleen, kidney, liver and implants near the lymph nodes have a phenomenon of increased Ti ion concentration I Severe severity can cause liver degeneration. Although Ti ion concentration does not cause decisive damage to the human body in the range of 0.01-100 ng/ml, it inhibits phytohemagglutinin-induced T cell and liposaccharide induction. Proliferation of B cells. 5. Excessive biomechanical load: The clinical sign of excessive occlusion load is the loosening of the 赝 赝 complex, the loss of the vertebral bone and the surrounding of the implant surrounded by fibers or epidermal cells. The occlusal force is mainly concentrated on the chimerism of the implant and the cortical bone, or the screw is fixed at the junction of the implant and the denture. It may cause microfracture (Microfracture)

Ti02具有二種主要的結晶相’分別為銳欽礦（Anatase)、 板鈦礦(Brookite)及金紅石結構(Rutile)，其中以rutile結 構的堆積密度最好且最穩定。根據Huang等人的研究指出 4 anatase結構的二氧化鈦可有效的提高蛋白質的吸附，而減少 纖維組織的生成。若二氧化鈦的結構由anatase轉換成穩定的 mtlle結構時’更能提高其生物相容性;且rutile結構的Ti02 薄膜在避免金屬離子釋出的比率上比anatase結構更具成 效。另外’ Ti02薄膜有助於提高骨骼與植入材間之鍵結，且 在人體模擬體液中會引導HA生成。 目前已有許多方式被應用來披覆生物相容性佳的二氧化 鈦薄膜於金屬植入材上’其包括了 ：熱氧化（thermal oxidization)、物理氣相沉積（physical vapor deposition PVD)、離子束輔助沉積（i〇n beam enhanced deposition IBE1D)、溶夥-凝膠法（sol-gel method)、化學氣相沉積 (chemical vapor deposit ion)、蒸鍵(evaporation)、反應陰 極電弧沉積(reactive cahodic arc deposition method)及陰 極電合成法(cathodic electrosynthesis method)等。 雄酸i弓(calciumphosphate)陶曼最早在1920年由Albee 與Morrison提出作為生醫應用，他們發現三的麟酸鹽 (tricalcium phosphate)注入缺陷（defects)中顯現出較快速 的骨成長。DeJong在1926年最早鑑定出氫氧基磷灰石 (hydroxyapatite, HA)是骨路中的礦物成分’可是一直到25 年後合成的氫氧基磷灰石才被接受為使用於整型外科 (orthopaedics)、骨移植（bone graft)及牙科醫術 1361230 (dentistry)中具有潛力的生醫材料。 目前已經有許多方法被應用來被覆生物活性陶瓷於金屬 植入材上’包括·熱均壓（h〇t isostatic pressing)、電装或 火焰喷塗（plasma or flame spraying)、離子束濺射沈積 (ion-beam sputter d印osition)、電泳沈積(eiectroph〇retic d印osition)、溶膠-凝膠沈積（sol-gei dep〇siti〇n)與射頻 (RF)磁控藏射（radio-frequency (RF)magnetron sputtering) 等。但這些方法中所報導的結果是難以同時產生含有〇H基之 平滑敏也、的純HA結晶相及良好的附著力。其中以電衆喷塗法 最廣受應用與研究’可是電漿喷塗的主要缺點為在高溫喷塗過 程中會造成分解（decomposition)與相變化（phase transformation)，且塗層與基材間主要靠機械咬合 (mechanical interlocking)鍵結，而非化學鍵結，其附著性 不佳。且在塗層本身或界面處常有微裂縫或缺陷導致塗層 剝離。剝落的HA碎片堆積於周圍組織中，可引起周圍骨質溶 解(osteolysis)，造成金屬基材直接暴露接觸身體組織，增加 金屬離子釋出（metal ion release) ’甚至因HA塗層剝離引 起植入材鬆脫（loosening)。 HA陶瓷的生物活性與生物相容性受到大家的注意，但是 植入材需要能承受高負荷，而HA的機械性質不佳，如低破斷 強度（fracture strength)、低耐疲勞性（fatigue resistance) 6 等’因而限制了應用範圍雖已在臨床應用於人體非荷重承受區 (non-load-bearingareas)，若能提昇機械強度，定能大大地 增加應用範圍。因此，若能以二氧化鈦作為與基材間的熱 轉換層（thermal transformation) ’降低熱膨脹係數差異且減 少HA相變定能有效的提高其附著性，進而加速骨復原速 率，減短療程。 因此極需開發一種能以低溫製程進行表面改質且具備極 佳附著強度及表面生物活性之技術。以解決人工植牙療期長、 HA與金屬基材間附著不良所導致之細菌感染及減少金屬離子 釋出之問題。 【發明内容】 有鑑於此，本發明利用電解沈積方法先被覆二氧化鈦薄 膜，再披覆生物活性陶瓷HA於Ti基材上以期提昇ha與基材 之附著力並縮短植牙療期’二氧化鈦陶瓷薄膜不僅與基材有絕 佳的附著力，同時能保護金屬基材，提昇其抗腐蝕及抗高溫氧 化的能力。由於利用低溫製程完成，可獲得高生物活性及機械 強度的表面鍍層。 因此，為達上述目的，本發明所揭露之在，純鈦金屬表 面形成HA/Ti02雙層塗層的方法中，其係分別利用四氣化鈦 (TiC14)酒精溶液’以及Ca(N03)2. 4H20與NH4H2P04混合水溶 液’以電解沉積方式分別形成氫氧化鈦(Ti〇(〇H)2 H2〇)介面層 1361230 及CalO(P〇4)6(〇H)2層’再經過低溫燒結後形成HA/Ti02雙層 塗層。 在本發明的方法裡’先將純鈦金屬基材置於四氯化鈦 (TlC14)甲進行電解沉積’再置入Ca(N03)2.4H20與NH4H2P04 混合溶液t進行電解沉積。所形成之鍍層經過緩慢乾燥後，係 以去除大部分水分’避免進行燒結時產生裂痕。之後再以400 它的溫度進行燒結，以形成HA/Ti02雙層鍍層於純鈦金屬基材 表面上，其中在燒結過程中的溫度係以階段式升溫以避免鍍 層容易產生剝離。 利用本發明的方法，一方面提昇純鈦金屬的表面活性， 另-方面又可增加HA_械強度及崎力，充分結合此兩種 材料之優點來_單—材料本身之缺點，提高騎料在生醫應 用方面的效能。 【實施方式】 第一圖係緣示本發明製備M/Ti〇2雙層鍍層方法之流程 ，。其中’軸在本具體實施例裡係以純鈦金屬作為基材，但 是可應用本發明製備HA/Ti〇2雙層塗層之方法於其它基材上。 本發明是叫解簡方式先於四祕鈦⑽⑷酒精溶液，再於 Ca(N03)2.4H20與咖2p〇4混合水溶液中，以電解沉積方式在 純鈦金屬表面形成HA/Ti02雙層鍍層。 8 本發明方法主要包括依序形成TiO(OH)2及cal〇(p〇4)6 (OH) 2於純鈦基材上’然後進行燒結。 首先’將純鈦基材置入〇· 01M四氯化鈦(TiC14)酒精溶液中 進行1. OmA、1200S電解沉積，其反應機制主要如下：Ti02 has two main crystalline phases, namely Anatase, Brookite and Rutile, in which the packing density of the rutile structure is the best and most stable. According to Huang et al., 4 anatase structure of titanium dioxide can effectively increase protein adsorption and reduce fiber formation. If the structure of titanium dioxide is converted from an anase to a stable mtlle structure, the biocompatibility is improved; and the rutile structure of the TiO2 film is more effective than the anatase structure in avoiding the release rate of metal ions. In addition, the 'Ti02 film helps to improve the bonding between the bone and the implant, and guides the formation of HA in the human body fluid. At present, there are many ways to apply the biocompatible titanium dioxide film on metal implants, which include: thermal oxidization, physical vapor deposition (PVD), ion beam assist (i〇n beam enhanced deposition IBE1D), sol-gel method, chemical vapor deposition ion, evaporation, reactive cahodic arc deposition Method) and cathodic electrosynthesis method. The malephosphate i Tauman was first proposed by Albee and Morrison in 1920 as a biomedical application, and they found that the tricalcium phosphate injection defects showed faster bone growth. DeJong first identified in 1926 that hydroxyapatite (HA) is a mineral component in the bone path. However, the hydroxyapatite synthesized up to 25 years later was accepted for use in whole surgery ( Orthopaedics), bone graft (bone graft) and potential medical materials in dentistry 1361230 (dentistry). Many methods have been applied to coat bioactive ceramics on metal implants, including h〇t isostatic pressing, plasma or flame spraying, and ion beam sputtering deposition. Ion-beam sputter d osition), electrophoretic deposition (eiectroph〇retic d osition), sol-gel deposition (sol-gei dep〇siti〇n) and radio frequency (RF) magnetron storage (radio-frequency (RF) ) magnetron sputtering) and so on. However, as reported in these methods, it is difficult to simultaneously produce a pure HA crystal phase containing a 〇H group and a good adhesion. Among them, the electric spray method is the most widely used and research'. However, the main disadvantage of plasma spray is that it will cause decomposition and phase transformation during high temperature spraying, and between the coating and the substrate. Mainly by mechanical interlocking bonding, rather than chemical bonding, its adhesion is not good. There are often micro-cracks or defects at the coating itself or at the interface that cause the coating to peel off. Exfoliated HA fragments accumulate in the surrounding tissue, causing osteolysis, causing direct exposure of the metal substrate to contact with body tissue, increasing metal ion release 'even by the peeling of the HA coating. Loosening. The bioactivity and biocompatibility of HA ceramics have received attention, but implants need to withstand high loads, while HA has poor mechanical properties such as low fracture strength and fatigue resistance. 6 et al. This limits the scope of application to clinical applications in non-load-bearing areas. If mechanical strength is increased, it will greatly increase the range of applications. Therefore, if the difference in thermal expansion coefficient is reduced by using titanium dioxide as a thermal transition layer between the substrate and the HA phase is reduced, the adhesion can be effectively improved, thereby accelerating the bone recovery rate and shortening the course of treatment. Therefore, it is highly desirable to develop a technique capable of surface modification by a low temperature process and having excellent adhesion strength and surface biological activity. To solve the problem of bacterial infection caused by long period of artificial dental implant, poor adhesion between HA and metal substrate, and reduction of metal ion release. SUMMARY OF THE INVENTION In view of the above, the present invention utilizes an electrolytic deposition method to first coat a titanium dioxide film, and then coat a bioactive ceramic HA on a Ti substrate in order to enhance the adhesion of ha to the substrate and shorten the dental treatment period of the titanium dioxide ceramic film. It not only has excellent adhesion to the substrate, but also protects the metal substrate and improves its resistance to corrosion and high temperature oxidation. Due to the low temperature process, surface coatings with high bioactivity and mechanical strength can be obtained. Therefore, in order to achieve the above object, the present invention discloses a method for forming a HA/Ti02 double-layer coating on a surface of a pure titanium metal, which utilizes a titanium tetrachloride (TiC14) alcohol solution and a Ca(N03)2, respectively. . 4H20 and NH4H2P04 mixed aqueous solution 'electrolytic deposition method to form titanium hydroxide (Ti〇(〇H)2 H2〇) interface layer 1361230 and CalO(P〇4)6(〇H) 2 layer' after low temperature sintering A HA/Ti02 double layer coating is formed. In the method of the present invention, a pure titanium metal substrate is first placed in a titanium tetrachloride (TlC14) for electrolytic deposition, and then a Ca(N03)2.4H20 and NH4H2P04 mixed solution t is placed for electrolytic deposition. The resulting coating is slowly dried to remove most of the moisture' to avoid cracking during sintering. Thereafter, sintering is carried out at a temperature of 400 to form a HA/Ti02 double-layered coating on the surface of the pure titanium metal substrate, wherein the temperature during the sintering is temperature-increased in stages to avoid easy peeling of the plating layer. By using the method of the invention, on the one hand, the surface activity of the pure titanium metal is improved, and on the other hand, the HA_mechanical strength and the sacrificial force can be increased, and the advantages of the two materials are fully combined to the disadvantages of the material itself, and the riding material is improved. Effectiveness in biomedical applications. [Embodiment] The first figure shows the flow of the method for preparing the M/Ti〇2 double-layer plating layer of the present invention. Wherein the 'axis is a pure titanium metal as the substrate in this embodiment, but the method of preparing the HA/Ti〇2 double layer coating of the present invention can be applied to other substrates. The invention is a method for solving the simple method of forming a HA/Ti02 double-layer coating on the surface of a pure titanium metal by electrolytic deposition in a mixed aqueous solution of Ca(N03) 2.4H20 and coffee 2p〇4. 8 The method of the present invention mainly comprises sequentially forming TiO(OH)2 and cal〇(p〇4)6(OH) 2 on a pure titanium substrate and then sintering. First, the pure titanium substrate was placed in a 〇· 01M titanium tetrachloride (TiC14) alcohol solution to carry out 1. OmA, 1200S electrolytic deposition, the main reaction mechanism is as follows:

TiC14->Ti+4+4Cl- Ti+4+4 0H—Ti0(0H)2.H20TiC14->Ti+4+4Cl- Ti+4+4 0H—Ti0(0H)2.H20

Ti0(0H)2. H2O~>Ti0(0H)2+H20 t TiO(OH)2—TiO2+H20 个 反應完成後，氫氧化鈦Ti0(0H)2介面層係形成於純鈦金屬 基材上。 接者’將該純鈦金屬基材置入〇.〇42MCa(N03)2.4H20與 0· 025MNH4H2P04混合水溶液中進行1. 〇mA、2400S電解沉積， 其反應機制如下：Ti0(0H)2. H2O~>Ti0(0H)2+H20 t TiO(OH)2—TiO2+H20 After completion of the reaction, the titanium hydroxide Ti0(0H)2 interface layer is formed on the pure titanium metal substrate. on. The pure titanium metal substrate was placed in a mixed aqueous solution of 〇.〇42MCa(N03)2.4H20 and 0·025MNH4H2P04 to carry out 1. 〇mA, 2400S electrolytic deposition, and the reaction mechanism is as follows:

Ca(N03)2—Ca+2+2N03-2HP04 2-+2e-—2P04 3-+H2 2H20+2e-~>H2+20H-10Ca+2+6PO4 3-+20H-—CalO(P〇4)6(OH)2 在反應完成後，一 CalO(P04)6(OH)2層係形成於該氫氧化 鈦介面層上。然後，將披覆CalO(P04)6(OH)2和TiO(〇H)2的純 鈦金屬基材進行緩慢乾燥與l〇〇°C恆溫30分鐘，再升至2〇〇t： 恆溫30分鐘，再升至400°C恆溫30分鐘進行低溫燒結，以形 成HA/Ti02複合塗層。其中，低溫燒結製程係以不高於5〇〇<t 的溫度完成。 電解沉積製程參數眾多，本發明人發現影響本發明沉積薄 膜的主要因素在於_電流密度、_時間和電驗濃度三個 參數。茲將此三個影響因素分別說明如下： 不同的沉積電流會影響ΗΑ在Ti02上的附著性。在製備Ti〇2 的步驟裡’電流範圍為〇. 8〜5mA/cm2，較佳為卜3mA/cm2。在形 成Μ的步驟裡，電流範圍為〇 3〜5mA/cm2，較佳為〇· 9〜3mA/cm2。 利用上述範圍的電流密度進行沉積所得之鍍層的附著力較 佳’無剝落現象產生。當電流紐大於上述範圍之上限時，基 材表面容奸氣泡喊，導致其表®的μ鍍層不夠敏密。當電 流密度小於上述範圍之下限時，基材表面之臥鍍層尚未均勻。 適當的沉積時間不但可以提昇各鍍層的均勻性、致密性， 也可以增加沉積的效率《氫氧化鈦鍍層的表面型態會影響ΗΑ的 /儿積情況。若沉積時間太短，則無法使ΗΑ鍍層均勻披覆。若沉 積時間過長，則會造成ΗΑ鍍層剝落。在形成Ti02的步驟裡， 沉積時間為300〜1500秒，較佳為6〇〇〜800秒。在形成HA的步 驟裡，沉積時間為1〇〇〇〜4000秒，較佳為1500〜2500秒。 在相同的沉積時間内，濃度越低所沉積的鍍層越均勻，裂 缝亦較J/，相對地欲得到相同厚度的鍍層，則沉積時間亦相對 的^加絲成Τι〇2的步驟裡，電解液四氯化欽的濃度範圍為 〇. 0001 0· 5Μ ’較佳為〇⑽卜請Μ。在形成μ的步驟裡電 解液中Ca⑽3)2· 4Η20與腿4Η2Ρ04的濃度分別為0隱〜〇. 15Μ 及〇. 005M 0.5M ’較佳的濃度範圍分別為〇 〇4m im及 〇. 02M 0· 25M。上述之電解液濃麟根據沉積時間決定。 在電解"L積完成之後，乾燥及燒結過程是影響鍵層曰後品 質的重要因素。右鍍層未經紐乾燥，例如陰乾，就直接燒結 的話會紅易因為騎表面的水分已經蒸發轉層底層的水 分來不及擴朗表面，使得表·收縮應力產生縣。這種情 況會使得TiG2與基材之間紐與⑽之間_著性不良造 成鍵層剝落而無法達到保護基材的效果。因此，為了避免鐘層 因未陰乾MU成燒結後的附著性不佳，通常將沉積後的基材進 行陰乾的動作是必要的1且為避免乾燥過程蒸發速度過快而 產生裂縫’係將沉積後之基材放置於怪溫怪濕的環境中緩慢乾 燥。較佳的乾燥條件為溫度15-4(TC及相對澄度75%以上。 乾燥後的基材仍含有少量的水分，需要經過燒結步驟方能 將水分完全去除並進一步進行縮合反應以形成M/Ti〇2雙層塗 層。 根據TGA/DTA分析’ HA在25〜15(rc溫度間會有大量的吸附 水跑掉’在之間產生劇烈的放熱反應，所以為了 避免燒結過程中發生激烈體積變化，因此在燒結過程中每次經 1361230 過溫度變化後，均需做一段時間的停留。且升溫降溫速率均不 月t*太决’以避免因膨脹係數的差異而使鑛層附著力變差。 第二圖係_本發财法中燒結程序的操作過程。燒結程 序包括至少數個階段的溫度變化以符合上述之需求，在本具體 實施例裡，燒結程序包括J )〜YJJ)段。 請參閱第二圖’在1 )階段裡，以Mc/min的速率升溫到 φ 80〜150°C。在Π)階段裡’以別〜150°C持溫5~120分鐘。在瓜） 階段裡’以S2C/min的速率升溫到18〇〜22〇。〇在iv)階段裡， 以180〜22(TC持溫5〜120分鐘。在V)階段裡，以$2〇c/min的 速率升溫到300〜50(TC。在VI)階段裡，以3〇〇〜5〇〇〇»c持溫512〇 - 分鐘。在珊)階段裡，以g2〇C/min的速率降溫到室溫。 本發明之方法在進行電解沉積，可先進行前處理。前處理 包括拋光及表面潔淨等步驟。 # 本發明的方法是以中濃度的電解液及適當的電流密度來進 行HA/Ti02的沉積。首先在純鈦金屬基材上沉積二氧化鈦鍍# 層，再進行第二次電解沉積HA，以二氧化鈦作為介面，提昇鍍 層與基材間之鍵結，並增加HA之機械強度。鍍層均勻性決定於 電場分佈，只要電場分佈均勻，所得之鍍層厚度亦為均勻。 完成沉積二氧化鈦與HA鍍層之純鈦金屬基材，發現剛沉積 後的鐘層（即未加以熱處理之塗層）即已出現HA的結晶相，經過 熱處理後的HA結晶象的繞射強度更高，且與金屬基材附著度更 12 1361230 佳。因此本發明方法在純鈦金屬基材上形成私/以〇2雙層鍍層 來保護金屬基材避免腐蝕，並且增加基材的生物活性及鍍層附 著強度。 將純鈦金屬基材剪裁成直徑14mm，厚度0 2腿之圓形試片 後，分別以#240、#400、#600、#800、#1200 及#1500 號水砂紙 研磨。接著再以〇· 3微米之氧化鋁粉末拋光至亮面，置入含有 清潔劑之去離子水中以超音波震盪器震盪1〇分鐘，再置入丙酮 中以超音波洗淨，以達到去潰的效果。最後以去離子水洗淨，馨 並自然陰乾。 然後以白金為陽極，試片為陰極，先在（濃度〇 〇1M)四氣 化鈦(TiC14)酒精溶液中進行Ti〇(〇H)2之沉積，再浸入（濃度 〇. 〇42M)Ca(N03)2.4H20 與濃度（〇. 〇25M)NH4H2P〇4 混合水溶液 ~ 使氫氧基磷灰石（HA)沉積於試片上。 然後將試片放置於30°C ’ 80%相對濕度的怪溫怪濕爐中進 行乾燥。將試片分別經過以室溫升至1〇(rc保持3〇分鐘，再升 Φ 溫至200°C保持30分鐘’再升溫至棚。c保持3〇分鐘，且升溫 及降溫速率均不得快於2口_，並進行電化學極化試驗及TGA 試驗將試片於人工模擬體液(Hank，s s〇luti〇n)且溫度控制在 37°C之環境下進行動態猶環極化，實驗結果係列於表一。 13Ca(N03)2—Ca+2+2N03-2HP04 2-+2e-—2P04 3-+H2 2H20+2e-~>H2+20H-10Ca+2+6PO4 3-+20H-—CalO(P〇 4) 6(OH)2 After the reaction is completed, a layer of CalO(P04)6(OH)2 is formed on the titanium hydroxide interface layer. Then, the pure titanium metal substrate coated with CalO(P04)6(OH)2 and TiO(〇H)2 was slowly dried and kept at 1 °C for 30 minutes, and then raised to 2 〇〇t: constant temperature 30 After a minute, it was further heated to 400 ° C for 30 minutes for low temperature sintering to form a HA/TiO 2 composite coating. Among them, the low-temperature sintering process is completed at a temperature not higher than 5 〇〇 < t. There are numerous parameters for the electrolytic deposition process, and the inventors have found that the main factors affecting the deposited film of the present invention are three parameters: current density, _ time, and plasma concentration. These three influencing factors are described as follows: Different deposition currents affect the adhesion of niobium to Ti02. In the step of preparing Ti〇2, the current range is 〇8~5 mA/cm2, preferably 3 mA/cm2. In the step of forming the crucible, the current range is 〇 3 to 5 mA/cm 2 , preferably 〇· 9 to 3 mA/cm 2 . The adhesion of the plating layer deposited by the current density in the above range is better than that without peeling off. When the current is greater than the upper limit of the above range, the surface of the substrate is bubbled, causing the μ plating of the watch® to be less sensitive. When the current density is less than the lower limit of the above range, the plating of the surface of the substrate is not uniform. Appropriate deposition time can not only improve the uniformity and compactness of each coating, but also increase the deposition efficiency. The surface morphology of titanium hydroxide coating will affect the enthalpy/child accumulation. If the deposition time is too short, the ruthenium plating cannot be uniformly coated. If the deposition time is too long, it will cause the enamel coating to peel off. In the step of forming TiO 2 , the deposition time is 300 to 1500 seconds, preferably 6 Å to 800 seconds. In the step of forming HA, the deposition time is from 1 〇〇〇 to 4000 seconds, preferably from 1,500 to 2,500 seconds. In the same deposition time, the lower the concentration, the more uniform the deposited layer, and the crack is better than J/, and the opposite thickness is required to obtain the same thickness of the coating, and the deposition time is also relative to the step of adding silk to Τι〇2, electrolysis The concentration of liquid tetrachlorinated chin is 〇. 0001 0· 5 Μ 'It is better to 〇 (10) Μ please. In the step of forming μ, the concentrations of Ca(10)3)2·4Η20 and the legs 4Η2Ρ04 in the electrolyte are 0 隐. Μ. 15 Μ and 〇. 005M 0.5M 'The preferred concentration ranges are 〇〇4m im and 〇. 02M 0 · 25M. The above electrolyte is determined according to the deposition time. After the electrolysis "L product is completed, the drying and sintering process is an important factor affecting the quality of the bond layer. If the right coating is not dry, such as dry, it will be red if it is directly sintered. Because the moisture on the surface of the surface has evaporated, the water at the bottom of the layer has not reached the surface, which makes the table shrinkage stress. In this case, the bond between the TiG2 and the substrate and the bond between the substrates (10) causes the bond layer to peel off and the effect of protecting the substrate cannot be achieved. Therefore, in order to avoid the poor adhesion of the bell layer to the sintered MU after sintering, it is usually necessary to perform the dry operation of the deposited substrate 1 and to prevent the evaporation process from being too fast to cause cracks in the drying process. The back substrate is placed in a strangely weird environment and slowly dried. The preferred drying conditions are temperature 15-4 (TC and relative resolution of 75% or more. The dried substrate still contains a small amount of water, and the sintering step is required to completely remove the moisture and further carry out a condensation reaction to form M/. Ti〇2 double-layer coating. According to TGA/DTA analysis, 'HA in 25~15 (there will be a large amount of adsorbed water running away between rc temperatures) produces a strong exothermic reaction between them, so in order to avoid the intense volume during sintering Change, so each time after the temperature change of 1361230 in the sintering process, it is necessary to stay for a period of time. And the temperature rise and decrease rate are not too long* to avoid the adhesion of the ore layer due to the difference of the expansion coefficient. The second figure is the operation process of the sintering process in the present financing method. The sintering process includes at least several stages of temperature changes to meet the above requirements. In the present embodiment, the sintering process includes J)~YJJ) segments. . Please refer to the second figure 'in 1' stage to raise the temperature to φ 80~150 °C at the rate of Mc/min. In the Π) stage, hold the temperature at a temperature of ~150 °C for 5 to 120 minutes. In the melon) stage, the temperature is raised to 18〇22〇 at the rate of S2C/min. 〇In the iv) stage, in the stage of 180~22 (TC holding temperature 5~120 minutes. In V), increase the temperature to 300~50 (TC. in VI) at the rate of $2〇c/min, to 3 〇〇~5〇〇〇»c Hold the temperature 512〇-minute. In the stage, the temperature was lowered to room temperature at a rate of g2 〇 C/min. The method of the present invention can be pre-treated prior to electrolytic deposition. Pretreatment includes steps such as polishing and surface cleaning. # The method of the present invention performs the deposition of HA/Ti02 with a medium concentration of electrolyte and a suitable current density. First, a titanium dioxide plating layer is deposited on a pure titanium metal substrate, and a second electrolytic deposition of HA is performed, and titanium dioxide is used as an interface to enhance the bonding between the plating layer and the substrate, and to increase the mechanical strength of the HA. The uniformity of the coating is determined by the electric field distribution. As long as the electric field is evenly distributed, the resulting coating thickness is also uniform. The pure titanium metal substrate on which the titanium dioxide and the HA coating are deposited is completed, and it is found that the crystal layer of HA has appeared in the layer immediately after deposition (ie, the coating which has not been heat treated), and the diffraction intensity of the HA crystal image after heat treatment is higher. And the adhesion to the metal substrate is better than 12 1361230. Therefore, the method of the present invention forms a private/bis 2 double layer coating on a pure titanium metal substrate to protect the metal substrate from corrosion and increase the biological activity of the substrate and the adhesion strength of the coating. The pure titanium metal substrate was cut into circular test pieces having a diameter of 14 mm and a thickness of 0 2 legs, and then ground with #240, #400, #600, #800, #1200, and #1500 water sandpaper, respectively. Then polish it to a bright surface with 〇·3 micron alumina powder, place it in deionized water containing detergent and shake it for 1 minute in an ultrasonic oscillator, then place it in acetone and wash it with ultrasonic wave to achieve the collapse. Effect. Finally, wash with deionized water, scent and dry naturally. Then, using platinum as the anode and the test piece as the cathode, the deposition of Ti〇(〇H)2 was first carried out in a titanium tetrahydrate (TiC14) alcohol solution (concentration 〇〇1M), and then immersed (concentration 〇. 〇42M) Ca. (N03) 2.4H20 and concentration (〇. 〇25M) NH4H2P〇4 mixed aqueous solution ~ Hydroxyapatite (HA) was deposited on the test piece. The test piece was then placed in a strange oven at 30 ° C '80% relative humidity for drying. The test piece was separately raised to 1 室温 at room temperature (rc was kept for 3 〇 minutes, then increased by Φ temperature to 200 ° C for 30 minutes) and then warmed to the shed. c was kept for 3 minutes, and the temperature and temperature were not fast. Electrochemical polarization test and TGA test were carried out in a 2-port _, and the test piece was subjected to dynamic helium circular polarization in an artificial simulated body fluid (Hank, ss〇luti〇n) and the temperature was controlled at 37 ° C. The series is in Table 1. 13

表一 I試片種_ J 一，ww i未經披復 UA/Ti02 雙 !層塗層 卜 ^ " ·* *— *.丨1經彼a i »A/Ti〇2 ft 丨層塗層之 I試月 » -I腐飪電流密度（nA/cn2) I腐任電位（ay) ’ ____ __ _ _ 」 rr·· - ·_· · _ " _ "· ·，* 擊·ΜΜ Μβ» —♦_ 'll |lM rn^m _ I ·__·Table I I test piece _ J one, ww i uncovered UA/Ti02 double! layer coating b ^ " · * *- *. 丨 1 by AI » A / Ti 〇 2 ft 丨 layer coating I test month » -I rot current density (nA/cn2) I rot potential (ay) ' ____ __ _ _ ” rr·· - ·_· · _ " _ "· ·,* 击·ΜΜ Μβ» —♦_ 'll |lM rn^m _ I ·__·

—I 231 -406, + Η—I 231 -406, + Η

K89S 53. 45K89S 53. 45

由上列表一可知，經彼覆HA/Ti02雙層塗層之試片的腐钱 電流密度相較於未經披覆ΗΑ/Ή02雙層塗層之試片顯著下降。 然後’分別針對具單層HA鍵層之試片及具ΗΑ/ΤΪ02雙層塗層之 試片進行拉伸試驗，實驗結果係示於下列表二。 表二As can be seen from the above list 1, the current density of the rotted money of the test piece coated with the HA/Ti02 double layer was significantly lower than that of the test piece without the 披/Ή02 double layer coating. Then, tensile tests were carried out on test pieces having a single layer of HA bond layer and test pieces having a double layer of ΗΑ/ΤΪ02, respectively, and the results of the experiment are shown in Table 2 below. Table II

試片毪類Test strip

— ___ Λ l· 具單廣丨丨A效層之试片I _ * .......__!，— 具8Α/Ή02雙層塗Jf I 拉伸试驗所承受之拉力（UPa )— ___ Λ l· Test piece I _ * .......__!, with 8 Α / Ή 02 double coating Jf I Tensile test (UPa)

—ν··,_ -Μ—ν··,_ -Μ

L Π. 3 4δ. 7 Η 由表二可知’ HA/Ti〇2雙層塗層之試片可承受之最大拉伸 強度遠大於HA·。顯示HA/Ti02雙層錢層之^的附著強 度遠較單層HA鍍層提昇。 14 從上述實驗發現，經電解沉機雙層鍍層之試片 在抗钱性與附著力方面均有明顯提昇。 综上所述，本發明之方法利用電解沉積及階段溫度變化之 燒結程序所形成之HA/Ti02雙層鋪具紐佳的瞒力及抗钱 性。本發明的燒結製程係以400〇c的溫度完成。MXR〇發現， 所得鍍層沒有包含其他相摻雜於其中。上述之電解沉積與燒結 程序乃屬於減本之餘’因此本發明可錄餘成本獲得附 著力與抗钱性佳的HA/Ti〇2雙層鑛層。 此外，可藉由電化學參數之控制，來決定^丁幻]雙層鍍 層的厚度及型態，再辅以燒結參數之控制，即可獲得理想之生 醫陶瓷鍍層。本發明除了應用於將_1^〇2沉積在平滑金屬合 金表面上，亦可應用於多孔或複雜形狀之基材上。 雖然本發明之較佳具體實施例揭露如上所述，然其並非用 以限定本發明，任何熟悉相關技藝者在不脫離本發明之精神和 範圍内，當可做些許之更動與潤飾，因此本發明之專利保護範 圍需視本發明說明書所附之申請專利範圍所界定者為準。 【圖式簡單說明】 為進一步了解本發明之目的、特徵及其功能，茲配合圖示 詳細說明如下： 第圖係為本發明在純欽金屬基材表面上形成pj/\/Ti02雙 1361230 層塗層之方法的製程流程圖。 第二圖係為本發明在純鈦金屬基材表面上形成HA/Ti02雙 層塗層之方法的燒結溫度變化及升溫降溫速率示意圖。 【主要元件符號說明】L Π. 3 4δ. 7 Η It can be seen from Table 2 that the maximum tensile strength of the test piece of the HA/Ti〇2 double-layer coating is much greater than that of HA·. The adhesion strength of the HA/Ti02 double-layered money layer is much higher than that of the single-layer HA coating. 14 From the above experiments, it was found that the test pieces of the double-layer coating by the electrolytic deposition machine were significantly improved in terms of resistance to money and adhesion. In summary, the method of the present invention utilizes the HA/Ti02 double-layered fabric formed by the electrolytic deposition and the temperature change sintering process to achieve the strength and resistance of the utility. The sintering process of the present invention is completed at a temperature of 400 〇c. MXR〇 found that the resulting coating did not contain other phases doped therein. The above-described electrolytic deposition and sintering process is a reduction of the present invention. Therefore, the present invention can obtain a HA/Ti〇2 double-layered ore layer with good adhesion and good resistance. In addition, the thickness and shape of the double-layer coating can be determined by the control of electrochemical parameters, and the control of the sintering parameters can be used to obtain the ideal ceramic coating. The present invention can be applied to a porous or complex shaped substrate in addition to the deposition of _1^2 on a smooth metal alloy surface. While the preferred embodiment of the present invention has been described above, it is not intended to limit the present invention, and it is intended that those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The patent protection scope of the invention is subject to the definition of the scope of the patent application attached to the specification of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS In order to further understand the object, features and functions of the present invention, the following is a detailed description of the following: The first figure is a pj/\/Ti02 double 1361230 layer formed on the surface of a pure metal substrate. Process flow chart for the coating method. The second figure is a schematic diagram of the sintering temperature change and the temperature rising and cooling rate of the method for forming a HA/Ti02 double layer coating on the surface of a pure titanium metal substrate. [Main component symbol description]

Claims (1)

1361220 公告專利齋窗1361220 Announcement of patents 正本, 1.一種在純鈦金屬基材表面上形成HA/jiO】雙層鍍層的方 法，其中將純鈦金屬基材置入於四氯化鈦(TiC14)酒精溶液中進 行電解沉積，再置入Ca(N03)2.4H20與NH4H2P04混合\溶 液中進行電解沉積，恆溫恆濕乾燥，然後經過燒結後形成 HA/Ti02雙層鍍層於純鈦金屬基材表面上， a. 其中將純鈦金屬基材置入於四氯化鈦(Ticl4)酒精溶液中進 行電解沉積後，形成氫氧化鈦介面層於純鈦金屬基材， b. 其中將純鈦金屬基材置入於4H2〇與顺犯处…Original, 1. A method for forming a HA/jiO double-layer coating on a surface of a pure titanium metal substrate, wherein a pure titanium metal substrate is placed in a titanium tetrachloride (TiC14) alcohol solution for electrolytic deposition, and then placed Into Ca(N03)2.4H20 and NH4H2P04 mixed\solution for electrolytic deposition, constant temperature and humidity drying, and then sintered to form HA/Ti02 double-layer coating on the surface of pure titanium metal substrate, a. which will be pure titanium metal base The material is placed in a titanium tetrachloride (TiCl4) alcohol solution for electrolytic deposition to form a titanium hydroxide interface layer on a pure titanium metal substrate, b. wherein the pure titanium metal substrate is placed in the 4H2 〇 and the punctuality ... 混合水溶液中進行電解沉積後，形成Cal〇(p〇4)6(〇H^層於 該氫氧化鈦介面層上， ' c·其中將CalO(P〇4)6(〇H)2和Ti0(0H)2.H20進行乾燥與燒 結’以形成ΗΑ/ΤΪ02雙層塗層， d·其中四氯化鈦的濃度範圍為〇〇〇〇1]VM)5]VI， 其中將純鈦金屬基材置入於四氯化鈦(Ticl4)酒精溶液中進 行電解沉積的時間為15〇秒〜2〇〇〇秒， 其中Ca(N03)2.4H20與NH4H2P04的濃度分別為 0.02M-0.15M 及 0.005M-0.5M，After electrolytic deposition in a mixed aqueous solution, Cal〇(p〇4)6 is formed (the 〇H^ layer is on the titanium hydroxide interface layer, 'c· where CalO(P〇4)6(〇H)2 and Ti0 are (0H) 2.H20 is dried and sintered 'to form a bismuth/ΤΪ02 double layer coating, d· wherein the concentration of titanium tetrachloride is in the range 〇〇〇〇1]VM)5]VI, wherein the pure titanium metal base The time for electrolytic deposition of the material in titanium tetrachloride (TiCl4) alcohol solution is 15 〜 2 to 2 〇〇〇 seconds, wherein the concentrations of Ca(N03) 2.4H20 and NH4H2P04 are 0.02M-0.15M and 0.005, respectively. M-0.5M, g·其中將純鈦金屬基材置入於Ca(N03)2.4H20與NH4H2P04 處合水溶液中進行電解沉積的時間為100秒〜3600秒， h三其中將純鈦金屬基材置入於四氣化鈦(Ticl4)酒精溶液中進 行電解沉積的電流密度範圍為〇 8mA〜5mA， 其中將純鈦金屬基材置入於C9^03)2.4112。與NH4H2P04 屍合水溶液中進行電解沉積的電流密度範圍為0.3mA〜5mA， j. 其中在燒結前先將經電解沉積之純鈦金屬基材放置於恆溫恆 濕的環境中緩慢乾燥’其中恆溫為15_4(rc，恆濕^75%的相 對濕度， k. 中燒結過。程係以室溫升至8〇_15(rc保持5 3〇分鐘，再升溫 至180-220¾保持5-30分鐘，再升溫至300-500。(：保持5-120 分鐘，且升溫及降溫速率S2°C/min。 17g· wherein the pure titanium metal substrate is placed in an aqueous solution of Ca(N03) 2.4H20 and NH4H2P04 for electrolytic deposition for 100 seconds to 3600 seconds, wherein the pure titanium metal substrate is placed in the four gas The current density of electrolytic deposition in a titanium oxide (TiCl4) alcohol solution ranges from 〇8 mA to 5 mA, wherein a pure titanium metal substrate is placed in C9^03) 2.4112. The current density in the electrolytic deposition with NH4H2P04 cadaver aqueous solution ranges from 0.3 mA to 5 mA, j. wherein the electrodeposited pure titanium metal substrate is placed in a constant temperature and humidity environment and slowly dried before sintering. 15_4 (rc, constant humidity ^75% relative humidity, k. Sintered. The system is raised to 8 〇 _15 at room temperature (rc is maintained for 5 3 〇 minutes, then heated to 180-2203⁄4 for 5-30 minutes, Increase the temperature to 300-500. (: Maintain 5-120 minutes, and increase the temperature and cooling rate S2 °C / min. 17