200813238 九、發明說明： 【發明所屬之技術領域】 鈦鎳系功能性材料視其變態溫度及使用溫度可分別有高制震 能(阻尼）、超彈性或形狀記憶等效應。利用這些特性可應用 在致動為、管接頭、連接器、減震板(環）、耐折曲超彈性天 線、人造衛星用天線、齒列矯正線、骨隨内釘與内銷、骨接 合甩扣釘、骨接合用超彈性線、脊柱彎症Harringtor矯正、棒、 微機電微小引擎與儲氫合金等產品上。 【先前技術】 ^鎳系功，性材料之麻田散體變態溫度深受主成份比例及雜 ^兀素含量，特別是氧，之影響。通常改變〇· 1%之鎳原子人 量，其麻田散體變態溫度將會有1(rc左右之魏。傳統直二 感應爐之金屬氧化物或石墨掛糊在高溫下極易與鈦錄系： =材料巾之鈦反應，例如在金魏錄_中，鈦會將 物屬（Mg、A1 〇r Si)還原而與游離之氧反i形成 Γ方面造成欽錄系功能性材料中Ni含量的增加使成 f 一方面也會使材質變脆不利於機械加工，在石累、 卿中也有類似問題，只是反應形成Tic而非氧化物= 亚不適合鈦鎳系功能性材料之熔煉驗常 ^人200813238 IX. Description of the invention: [Technical field to which the invention pertains] Titanium-nickel functional materials may have high seismic energy (damping), superelasticity or shape memory depending on their metamorphic temperature and service temperature. These characteristics can be applied to actuation, pipe joints, connectors, shock absorbing plates (rings), flexure-resistant superelastic antennas, satellite antennas, orthodontic lines, bone-to-nails and internal pins, and bone joints.甩 Studs, superelastic lines for bone joints, Harringtor correction for spine curvature, rods, micro-electromechanical micro-engines and hydrogen storage alloys. [Prior Art] ^Nickel work, the metamorphic temperature of the granules of the material is deeply affected by the proportion of the main component and the content of the halogen, especially oxygen. Usually changing the amount of nickel atoms in 〇·1%, the metamorphic temperature of the Matian bulk will have 1 (the RC or so. The metal oxide or graphite paste of the traditional straight induction furnace is very easy to be associated with the titanium at high temperatures: = Titanium reaction of the material towel, for example, in Jin Weilu _, the titanium will reduce the genus (Mg, A1 〇r Si) and form a ruthenium with the free oxygen, resulting in an increase in the Ni content in the functional material of the nucleus system. On the one hand, it will make the material brittle and unfavorable for mechanical processing. There are similar problems in Shi Li and Qing, but the reaction forms Tic instead of oxide = sub-suitable for the melting of titanium-nickel functional materials.
電弧、電子束或電“= 二S 授拌功此與太耗錢，也不適合大量 、夕 J^CInduction scull Melt.ng) ^式㈣’且有零污染及攪拌作用 彳 j 冷鋼坩鍋壁上有一層凝因夕厶屬斜 里杈2仁因其水 :外仍然有與上述採用水冷銅坩S之電弧’ 統真空感應爐價格之數倍以上，“ 格叩貝，是傳 5 200813238 中了上田斤雖冒針對此問題於中華民國« 13醒號發明專利 儀卜用ίΐϊϊΐ所調配之漿體並塗佈燒結於傳統氧化鎮 之及廡’ ^功^*減緩鈦鎳系功能性材料中之高活性鈦與掛網 果：ίί業上所需要的連續生產應用上卻發現這種 射’除了高活性元 H繼對於氧化 2決上述_ ’本發日肢要目的係提供—種具有合 之；d ί:低且加工性能優異之鈦鎳系功能性材料熔製 柄加_使轉命餅生賴本魏行方式更為H也口為 【發明内容】 第-圖為習知之氧化缝層獅在連續五爐次的等原子比職 功能性材料炫煉後之SEM剖面金相。從第—圖中可發現經過五 爐次之轉’補絲之減錄層遭沖料㈣失殆盡，同 時從EM定性分析可清楚證實因失去氧化紀塗層保護之氧化鎮 底材更受到総性元雜融鈦之嚴重侵贼應。第一圖亦 顯，到了連續五爐次輯後，富鈦之合金_液對失去保護層 之氧化鎂不健健表層’更沿魏蝴齡與顆粒之^ 界或間隙滲透翁釐米深處。此金屬穿透現象不僅有工安的危 險’所影響範圍尚包括所溶製之NiTi功能性材料材料有劣化 與加工時易脆斷的問題。 6 200813238 驗發贴以氧尬粉末巾添加二氧切粉末共 同调蚊諸_錄絲傳統減卿虹啊得到完全不 同t先前技術之塗層形態(如第二圖所示）。從金相顯微组織中 可發現此塗由先前之粉«合物結構轉魏塊片狀結構 此=狀有«之抗賴能力。由於二氧切相對於溶融欽 亚非女疋’耻其舰^宜過高，經#驗發現只縣加量相對 於氧化鍾量百分比不超過ι_不致有嚴重之反應。另外二 氧化石夕之劑量太辦職法形錢片狀結制時也沒有足夠強 =，’嶋獅磁_騎氧购百 雖然純鎳與純鈦_點分別高達14阶與丨⑽。c，但是随 功能性材料的_卻只有丨靴。這個特點，在本發明 中么現”要在第-爐次之轉上將補與純鈦原料分離，在氧 化紀塗層蛛置人純鎳’並加熱至鎳的魅後將感應線圈 之加熱功率㈣在最小’使树蘭近特約三十分鐘後再緩 缓添加純鈦，賴氧祕錢_之賴抗錢麟禍壽命之 延續有意想列的好處。因為—來是二氧化㈣會與與溶融鎳 反應，再則於炫點附近之鎳金屬液紅黏滞狀態，因此不會受 到磁力線之攪拌個帶來沖_問題。而在氧化錄層初形成 日守’利用1453Ϊ之高溫更可強化其與购之結合強度。當以 二次加料方式加人純鈦後，由於合金熔點與掛翻之金屬溶融 液溫度均迅速下降，金屬熔融液中之鈦與塗層中之二氧化矽反 200813238 應也因此得以減缓，實驗結果齡#二氧切之量控制在相對 於氧化_量百分比之7個綱_乎沒雜何反應。 ^過以下之實施舰比較罐能更妓朗本㈣之特色與優 【實施方式】 【比較例】 、在一直# 1mm料原子比NiTi功能性材料超彈性線材製 造中，百先將氧化紀重量百分比為45%及其餘包含有溶劑、 1 雜劑、可塑劑與分散劑之氧化紀漿财接塗佈在氧化麟 堝上。_在1G5(rc燒結，燒結完畢後再將此塗層職與耐 火爐於真空感應爐之感應、，並將成份為犯― 49.6 at/Ji具有室溫超彈性合金之純鎳與純鈦原料置入坩 堝，先抽真空至4x10-2 torr以下再通氮氣至3〇〇 t〇rr，並 以感應式加熱少谷煉，待原料全熔並攪拌均勻後洗注至内徑 20πιηιφ長度150咖之石墨模冷卻而成鑄棒。 I 此鎊棒隨後在8’反覆進行熱型鍛⑽—sw_g)與退火 處理’ §直從減縮至3mm左右開始進行冷抽線直爿lmm為止。 ♦抽加工過私中NiTi合金線材均浸泡在液態氮中以確保線材 时不超過As變態溫度。在量產的試製中，此塗層除溶 、東人外又以相同方式再連續溶煉四爐次，總計有得到五 支超彈性鑄棒並進行相同之抽線製程。由於溶煉製程中溶融 Μ功能性材料與關反應造魏、碳雜f等元素的增加常 會導致材料的劣化與抽線加工過程的脆斷並增加生產製造成 8 200813238 本’因此除了氧含量以外特將冷抽_程隨_之斷裂次. 數作為一量化評估數據並詳列於表1中。 表1 數 鑄錠含氧量 (ppm) 2 yArc, electron beam or electricity "= two S-spinning work is too costly, not suitable for a large number, eve J^CInduction scull Melt.ng) ^式(四)' and has zero pollution and agitation 彳j cold steel crucible wall There is a layer of condensed yin 厶 厶 斜 斜 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因Although Ueda has taken the initiative to solve the problem in the Republic of China, the slurry of the invention has been applied to the traditional oxidized town and the smelting of titanium-nickel functional materials. Highly active titanium and hanging net fruit: ίίThe continuous production application required in the industry has found that this kind of shot 'except for the high activity element H, followed by the oxidation 2, the above-mentioned ;d ί: Low-temperature and excellent processing performance of titanium-nickel functional material melting handle _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ SEM section of lion after smelting of equi-atomic functional materials in five consecutive furnaces Kim Sang. From the figure, it can be seen that after five cycles of the 'replacement of the silk, the subtraction layer has been lost (4), and from the qualitative analysis of EM, it can be clearly confirmed that the oxidized town substrate which is protected by the oxidation of the oxide layer is more affected. Severe elementary miscellaneous titanium is a serious intrusion of thieves. The first picture also shows that after the continuous five-furnace series, the titanium-rich alloy _ liquid on the magnesium oxide unhealthy surface layer of the loss of protective layer is further penetrated into the depth of the Weng cm and the gap between the Wei and the granules. This metal penetration phenomenon not only has the danger of safety and safety, but also affects the problem that the dissolved NiTi functional material has deterioration and is brittle during processing. 6 200813238 The hair-testing paste is added with oxy-powder powder towel to add dioxin-cut powder to the same mosquito. The traditional _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ From the metallographic microstructure, it can be found that the coating is resistant to the flaky structure of the previous powder. Since the dioxotomy is relatively high compared to the melting of the Qinya non-female 疋 耻 其 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In addition, the dose of sulphur dioxide is not strong enough when it is too ruthless. =, 嶋 磁 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ c, but with the functional material _ but only ankle boots. This feature, in the present invention, "is to be separated from the pure titanium raw material on the first-furnace turn, and the induction coil is heated after the oxidized coating is placed on the pure nickel' and heated to the charm of nickel. Power (4) at the minimum 'Let the tree orchid nearly 30 minutes later, then slowly add pure titanium, Lai oxygen secret money _ depends on the continuation of the life of the loss of money to the benefits of the intention. Because - is the dioxide (four) will It reacts with molten nickel, and then the nickel metal liquid near the bright point is red-viscous, so it will not be affected by the stirring of magnetic lines of force. However, at the beginning of the oxidation recording layer, it is formed by using the high temperature of 1453. Strengthening the strength of the combination with the purchase. When the pure titanium is added by the secondary feeding method, the titanium in the molten metal is opposite to the cerium oxide in the coating due to the rapid decrease of the melting point of the alloy and the temperature of the metal melt of the hanging metal. 200813238 should also be able to slow down, the experimental results age #2 oxygen cut amount is controlled in relation to the percentage of oxidation _ amount of 7 _ _ no mixed reaction. ^ The following implementation of the ship comparison can be more ambiguous (four) Features and advantages [Embodiment] [Comparative example In the manufacture of #1mm material atomic ratio NiTi functional material superelastic wire, Baixie will have an oxidation percentage of 45% and the rest of the oxidized particles containing solvent, 1 impurity, plasticizer and dispersant. The cloth is on the oxidized linden. _ In 1G5 (rc sintering, after the sintering is completed, the coating is applied to the refractory furnace in the induction furnace, and the composition is made - 49.6 at/Ji has a room temperature superelastic alloy The pure nickel and pure titanium raw materials are placed in the crucible, first vacuuming to 4x10-2 torr and then passing nitrogen to 3〇〇t〇rr, and inductive heating is less, and the raw materials are fully melted and stirred evenly after washing. The graphite mold with an inner diameter of 20πιηιφ and a length of 150 coffee is cooled to form a cast rod. I this pound rod is then subjected to hot forging (10)-sw_g and annealing treatment at 8' repeatedly. § Straight reduction from about 3 mm to cold drawing爿lmm. ♦The NiTi alloy wire is drawn in liquid nitrogen to ensure that the wire does not exceed the As temperature. In the trial production of the mass production, the coating is dissolved in the same way as the East. Continuously smelting four heats, totaling five super Casting rods and carrying out the same drawing process. Due to the increase of elements such as ferrite and functional materials in the smelting process, the deterioration of the materials and the process of the wire drawing process will increase the production and increase the production. Made into 8 200813238 this 'so in addition to the oxygen content will be cold pumping _ Cheng with _ break times. The number as a quantitative evaluation data and detailed in Table 1. Table 1 number of ingots oxygen (ppm) 2 y
> 20 ^20~ 1670 炫煉爐次 從表1中魏以f知之氧她塗層_及辑方法做為生 產N1Ti功能性材料之溶製方式僅對第-爐次結果有功效。缺 而從第二爐次起，抽線斷裂次敦即迅速上升，例如，僅僅抽 至2麵就已斷裂超過2〇次以上並因材質太脆而無法續抽。經 脚_6氮氧儀分析發現所_之Nm功能性材料中之 • 乳含置則從原本第一爐次之450 Μ上升到第五爐次之1670 ppm’ -個與_完全未塗佈_相#的水準，顯示此塗層掛 ㈣失去基本的抗氧化還原能力。對此_本案發明人特從 連續五爐魏煉後的·缝層_進行SEM剖面金相分 析’如第-圖所不。結果發現經過五爐次之絲，表面之氧 化纪塗層不僅遭賴作㈣失殆盡，同時因失去氧化妃塗層 保護之氧傾_紐更受到高活性元素縣鈦之嚴重侵儀 反應彳<第-圖的簡金相再加上針對不同區域的丽半定 9 200813238 量分析可清楚證實這侵趙象;顯示到 Μ·τ· 硬、、、貝五爐次熔煉後， 备鈦之NlTl功靖料溶融液對失去 僅錢其絲，更沿著氧傾齡與 2崎禍不 與氧化還;f反岸到數料〜、Α &界或間隙渗透 、乳八原反綱數屋“處，導致賴之 鑄錠氧含量之上升與材質之劣化。 力此〖生材科 【實施例一】. . 在同樣直徑為1mm的等原子比NiTl· ·于匕NlTl功忐性材料超彈性線材製 U中，先將相對於氧化纪重量百分比為 挽〜 里曰刀比马12· 5%之二氧化石夕粉末 攙入乳化⑽末中，其中氧尬佔漿體總重為仙重量百分比， 並與其餘包含有溶劑、黏結劑、可塑劑與分散劑等所共同調合 之水體直接塗佈在氧化鎂掛禍上。隨後在1〇5代燒結，燒结 後再將此塗層卿與耐火泥共同築爐於真空感應爐之感應、= 内。之後將成份為Mi-49· 6 at%Ti具有室溫超彈性之Nm功 能性材料原料分成兩部分，切純鎳原料置人塗層賴掛塌 中^屯鈦原料則放置在加料斗中，再抽真空至4前2切订以 下入氬氣至_ torr，並以感應式力口熱熔煉至純鎳的溶 ’、、、占附近立即將感應線圈之加熱功率調降，控制在剛好能 λ使溫度_在熔點，㉟14肌贼的程度，而在熔點附近之 純鎳i屬;^貞彳王黏滞狀態，因此不會受到磁力線之攪拌作用帶 來沖勉的_ ’氧化_層則得以再被強化。當維持約三十分 鐘後再從加料斗巾魏添加人純鈦原料。由於Nm功能性材 料的$谷”、、1、有1240 c ’因此雖然塗層掛禍内之金屬液溫度下 200813238 牛i屬液抓動性部增加，待純鎳與純鈦原料全部溶解並擾拌 句勻後此主至内徑20ιηπιφ長度150mm之石墨模冷卻而成NiTi 功能性材料鑄棒。> 20 ^ 20 ~ 1670 炫炼炉次 From Table 1 in the Wei to know the oxygen her coating _ and the method of production as a production method for the production of N1Ti functional materials only for the first - heat results. Shortly after the second heat, the wire breaks quickly and rises. For example, it has been broken more than 2 times only after being drawn to 2 sides and cannot be continuously pumped because the material is too brittle. According to the analysis of the foot _6 nitroxeter, the emulsification of the Nm functional material increased from 450 原 of the first heat to 1670 ppm of the fifth heat - and _ completely uncoated The level of _phase# shows that this coating hangs (4) loses its basic antioxidant reduction ability. In this regard, the inventor of the present invention specially performed the SEM profile metallographic analysis from the seam layer after the continuous five furnaces, as shown in the first figure. It was found that after five times of wire, the surface of the oxidized coating was not only lost (4), but also due to the loss of yttrium oxide coating protection. <The first figure of the simple metal phase plus the different regions of Li Banding 9 200813238 quantitative analysis can clearly confirm this invading Zhao Xiang; shows that after the Μ·τ· hard,,, Beibei smelting, Titanium The NlTl Gongjing melt solution loses only its money, and it is not along with the oxygen dumping age and 2 the ruggedness is not oxidized; f reverse shore to the number of materials ~, Α & boundary or gap penetration, milk eight original anti-class The number of houses “causes the rise of the oxygen content of the ingots and the deterioration of the material. The force of this is [1] in the case of the same diameter of 1mm, the atomic ratio of NiTl··匕NlTl In the material super-elastic wire U, the weight percentage relative to the oxidation volume is firstly plucked into the emulsified (10) end of the bismuth dioxide powder, wherein the total weight of the slurry is Percentage of weight, and blended with the rest of the solvent, binder, plasticizer and dispersant The water body is directly coated on the magnesia, and then sintered in the 1st and 5th generations. After sintering, the coating and the refractory mud are co-fired in the induction of the vacuum induction furnace, and then the composition is Mi- 49· 6 at%Ti Nm functional material with room temperature superelasticity is divided into two parts. The pure nickel raw material is placed on the coating. The titanium material is placed in the hopper and then vacuumed to 4 2 Cut the following argon gas into _ torr, and heat-smelting to the pure nickel solution by inductive force, immediately reduce the heating power of the induction coil, and control the temperature to λ at the melting point. The degree of 3514 muscle thief, and the pure nickel i near the melting point; ^ 贞彳 king viscous state, so it will not be affected by the stirring of the magnetic field line _ 'oxidation _ layer can be strengthened again. After about 30 minutes, add pure titanium raw materials from the feeding towel. Since the Nm functional material is $谷, 1, and has 1240 c', although the temperature of the molten metal in the coating is under the temperature of 200813238 The liquid gripping part is increased, and the pure nickel and pure titanium raw materials are all dissolved and disturbed. This master to an inner diameter of 150mm length 20ιηπιφ cooled graphite mold from the cast rods NiTi functional material.
在量產的試製巾’此塗層綱除依上述方式進行第—爐次溶煉 外，隨後則以習知方式再連續溶煉五爐次，總計有得到六支超 彈性鑄棒。此鱗並在默反覆進行_鍛齡_加) 與退火處理，當直徑減縮至3mm左右開始進行冷抽線直到_ 為止。冷抽加工過程中㈣合金線材均浸泡在祕氮中以確 保線材溫度不超過As變態溫度。這些Nm功能性材料轉棒之 乳含量以及冷抽線過程之斷裂次數則詳列於表2中。 =2中發現與比較例（習知方式)之最大不同乃是氧含量及斷 衣二人數並衫熔賴讀的辟，齡之本翻咖功能性 材料之鰣方法聽-爐讀麵麵效，耻雜 表2 熔煉爐次In the mass-produced test towel, the coating was subjected to the first-stage solubilization in the above manner, and then the furnace was continuously lysed in five times in a conventional manner, and a total of six superelastic cast rods were obtained. This scale is repeated in the same way as the aging process, and the annealing process is performed. When the diameter is reduced to about 3 mm, the cold drawing is started until _. During the cold drawing process, (4) the alloy wire is immersed in the secret nitrogen to ensure that the wire temperature does not exceed the As metamorphic temperature. The milk content of these Nm functional materials and the number of breaks in the cold drawing process are detailed in Table 2. The biggest difference between the founder and the comparative example (the conventional method) is that the oxygen content and the number of broken clothes are the same as the number of people who wear the functional materials. , shame table 2 smelting furnace
抽線過程斷裂次數 可利用性。細成果亦從連續福切煉後喊她塗層掛禍 200813238 進行SEM刳面金相分析及釔元素之線性掃瞄，如第三圖所示 絲發__過六爐奴麟，表蚊氧化峰層依舊完好 成功抵檔熔煉過程之沖蝕作用，因此可保護氧化鎂坩堝底二不 受到高活性元素'熔融鈦之侵餘反應。 【實施例二】 在同樣直徑為1腿的等原子比NlTi功能性材料超彈性線材製 造^先將相對於氧化紀重量百分比為16%之二氧化石夕粉末^ _ 人氧化紀粉末中，其中氧化紀佔漿體總重為40重量百分比， 並與其餘包含有溶劑、黏結劑、可塑劑與分散劑等所共同調人 之漿體直接塗佈在氧化鎂_上。隨後在1〇5〇。^纽，燒^ 後再將此塗層_與耐火泥制㈣於真空感應爐之感應ς圈 .内。之後將成份為Ni-49. 6 aUTi具有室溫超彈性之随功 能性材料原料分成兩部分，切純鎳原料置人塗層掛網掛禍 ^純鈦原料則放置在加料斗中，再抽真空m咖以 φ 了時通入氬氣至3GG torr ’並以感應式加熱炼煉至純鎳的炫 點附近。此日守立即將感應線圈之加熱功率調降，控制在剛好能 使/皿度維#在溶點’❸14肌附近的程度，而在炫點附近之 純鎳金屬液則呈黏滯狀態，因此不會受到磁力線之難作用帶 來沖钱的問題，氧化纪塗層則得以再被強化。當維持約三十分 叙後再彳<加料斗巾緩緩添加人純鈦原料。由於㈣功能性材 料的熔點只有·。C ’雖缝層職狀金屬液溫度下 降但金屬液流動性卻增加，待純鎳與純鈦原.料全雜解並授摔 12 200813238 句勻後％庄至内控20πκηφ長度150mm之石墨模冷卻而成㈣ 功能性材料禱棒。 . 在量產的試製中，此塗層_除依上述方式進行第-爐次猶 外’隨後則以習知方式再連續溶煉五爐次，總計有得到六支超 雜鑄棒。此鑄棒並在咖它反覆進行熱型鍛(H〇t_swaging) 與退火處理，當直徑減縮至3·左右開始進行冷減直到_ 為々抽加工過程中NiTi合金線材均浸泡在液態氮中以確 • 保線材溫度不超過As變態溫度。這些NiTi功能性材料鑄棒之 氧含畺以及冷抽線過程之斷裂次數則詳列於表3中。 從表3中發現與比較例（習知方式）之最大不同乃是氧含量及斷 裂次數並不受熔煉爐次數的影響，換言之本發明NiTi功能性 材料之熔製方法對每一爐次結果均有功效，因此明顯具備產業 可利用性。從連續六爐次熔煉後的氧化釔塗層坩堝進行SEM剖 面金相分析則得到與第三圖相似的結果，顯示經過六爐次之、熔 表3 溶煉爐次 抽線過程斷裂次數 ——______ 鑄錠含氧量 (ppm) 1 —— 12 560 — 2 13 —------ — — 3 10 --—-- —. — 4 13 —-------- — 5 12 — L 6 11 --—— 530 — 13 200813238 煉’表面之氧倾塗層依舊完好成功抵觀煉過程之沖飯作 用’因此可保護氧化鎮掛禍底材未受到高活性元素溶融欽之侵 =應。惟與表2之實施例—她，無論是㈣功能性材料 鑄杯之氧含量或是抽線斷裂次數均有略為上升之趨勢，因此二 氧化石夕之添加量不宜超過相對於氧化纪重量百分比之繼。 【實施例三】 在同樣直#為1_崎軒比NiTi功能性材料超雜線材製 參 _，先將相對於氧化紀重量百分比為7%之二氧化石夕粉末攙 、氧化I乙粕末中，其中氧化紀佔漿體總重為4〇重量百分比， p其餘包含有溶劑、黏結劑、可關與分散麟所共同調 ^之襞體直接塗佈在氧化騎耻。隨後在1G5(TC燒結，燒 結後再將職層_與耐火泥制㈣於該絲爐之感應 線圈内。之後將成份為49. 6 at%Ti具有室溫超彈性之桁巧 功祕材料補分成兩部分，先將純鎳補置人塗層掛獅 φ 堝中，純鈦原料則放置在加料斗中，再抽真空至4xl(T2 torr 以下時通入氬氣至3〇〇 torr，並以感應式加熱熔煉至純鎳的 溶”沾附近。此時立即將感應線圈之加熱功率調降，控制在剛 好能使溫度維持在熔點，約1453°C附近的程度，而在熔點附 近之純鎳金屬液則呈黏滯狀態，因此不會受到磁力線之攪拌 作用帶來沖蝕的問題，氧化釔塗層則得以再被強化。當維持 約二十分鐘後再從加料斗中緩緩添加入純鈦原料。由於NiTi 功能性材料的熔點只有1240°C，因此雖然塗層坩堝内之金屬 14 200813238 液/皿度下降但金液流紐卻增加’待純鎳與純鈦原料全部 k解並攪拌均勻n主至内徑施_長度⑽刪之石墨模冷 卻而成NiTi功能性材料鑄棒。 在量產的試製巾’此塗糾嫩依上述該進行帛—爐次溶 煉外，Ik制以習知方式再連續絲五爐次，總計有得到六 支超彈性鑄棒。此鑄棒並在⑼代反覆進行触鍛㈣— sw_g)與退火處理，#直徑減縮至_左右開始進行冷抽 * ，直到lmm為止。冷抽加工過程中NiTi合金線材均浸泡在液 悲氮中以確保線材溫度不超過As變態溫度。這些师功能 性材料禱棒之氧含量以及冷抽線過程之斷裂次數則詳列於: 4中。 從表4中發現與比較例（習知方式）之最大不同乃是氧含量及 斷裂次數幾乎不受溶煉爐次數的影響，換言之本發明咖功 紐材狀賴紐對每―爐次結果财魏，耻顯然具備 • 錢可利祕。對此成果亦從連續六爐次罐後的氧化紀塗層 掛禍進行SEM剖面金相分析，發現經過連續六爐次之溶煉，表 面之乳化纪塗層在熔煉過程雖已受沖餘作用幾乎消失户全，但 尚未失去保護氧化紐禍底材受到高活性元素炫融欽2反應 之功能。從EDX的半定量分析亦證實不僅氧化鎮掛禍之内部^ 也就是氧化鎂顆粒無粒之邊界間隙，尚未遭到渗透盘氧化還 原倾反應，其表層亦未受到嚴重之侵觀象。然而金=分= 結果亦顯示此關已使用到了臨界點，再下去的炫練將導致失 15 200813238 去保護層之_ ’如第1般，麵富鈦之Nm功能性材料 熔融液之财錢絲，紐敏氧含量之上賴材質之劣 化。因此二氧化石夕之添加量不宜超低於相對於氧化紀重 比之7%。The number of breaks in the drawing process is available. The fine results also shouted her coating hazard from the continuous blessing after the 200813238 SEM surface metallographic analysis and linear scanning of the yttrium element, as shown in the third figure __ over six furnace slaves, mosquitoes The peak layer is still intact and successfully resists the erosion of the smelting process, so it can protect the magnesia base and not be subjected to the reversion reaction of the high-activity element 'molten titanium. [Embodiment 2] In the same diameter of 1 leg of the equal-area ratio NlTi functional material superelastic wire material, the first part will be 16% by weight relative to the oxidation volume of the dioxide dioxide powder _ human oxidized powder, wherein The oxidized particles accounted for 40% by weight of the total weight of the slurry, and were directly coated on the magnesium oxide with the remaining slurry containing the solvent, the binder, the plasticizer and the dispersing agent. Then at 1〇5〇. ^纽, after burning ^ then this coating _ and refractory mud (four) in the induction coil of the vacuum induction furnace. After that, the composition is Ni-49. 6 aUTi has a room temperature superelastic with the functional material raw material divided into two parts, cut pure nickel raw materials placed on the coating hanging net hazard ^ pure titanium raw materials placed in the hopper, and then vacuum When m is φ, argon gas is introduced into 3GG torr ' and heated inductively to the vicinity of the bright point of pure nickel. This day, the control immediately reduces the heating power of the induction coil, and controls it to the extent that it can be near the melting point '❸14 muscle, and the pure nickel metal liquid near the bright point is sticky. The oxidized coating can be strengthened without being affected by the difficulty of magnetic lines. When you maintain about 30 minutes, you can add a pure titanium material slowly by adding a towel. Because (4) the melting point of the functional material is only ·. C 'Although the temperature of the molten metal in the seam layer is decreased, but the fluidity of the molten metal is increased, and the pure nickel and pure titanium are all miscible and thrown 12 200813238 After the sentence is evenly mixed, the internal mold is 20πκηφ and the length of the graphite mold is 150mm. Made (four) functional material prayer rod. In the trial production of mass production, this coating_except for the first-furnace in the above manner is followed by continuous liquefaction of five furnaces in a conventional manner, and a total of six super-hybrid cast rods are obtained. The cast rod is further subjected to hot forging (H〇t_swaging) and annealing treatment, and the diameter is reduced to about 3·, and the reduction is continued until the _ is immersed in the liquid nitrogen during the 々 pumping process. Ensure that the wire temperature does not exceed the As metamorphic temperature. The oxygen enthalpy of these NiTi functional material cast rods and the number of breaks in the cold draw line process are detailed in Table 3. It is found from Table 3 that the biggest difference from the comparative example (conventional method) is that the oxygen content and the number of fractures are not affected by the number of melting furnaces, in other words, the melting method of the NiTi functional material of the present invention has a result for each heat treatment. It is effective, so it is clearly available for industry. The SEM profile metallographic analysis of the yttria-coated ruthenium after six consecutive furnace smelting results in similar results to the third figure, showing the number of breaks in the secondary drawdown process after six furnaces and the melting table 3 ______ Ingot Oxygen Content (ppm) 1 - 12 560 — 2 13 —------ — — 3 10 ----- — — — 4 13 —-------- — 5 12 — L 6 11 --—— 530 — 13 200813238 The surface of the oxygen-deposited coating is still intact and can be used to protect the oxidized town. The substrate is not attacked by highly active elements. = should. However, with the embodiment of Table 2, she, whether it is (iv) the oxygen content of the casting cup of the functional material or the number of times of the wire breakage, has a slight upward trend, so the addition amount of the dioxide should not exceed the weight percentage relative to the oxidation volume. Succession. [Embodiment 3] In the same straight #为1_崎轩 ratio NiTi functional material super-hybrid material preparation _, first with respect to the oxidation percentage of 7% of the weight of the dioxide dioxide powder, oxidized I Among them, the oxidation group accounts for 4% by weight of the total weight of the slurry, and the remaining p-containing scorpion containing solvent, binder, and can be separated and dispersed is directly coated on the oxidation shame. Then, after 1G5 (TC sintering, sintering, and then refractory layer _ and refractory mud (4) in the induction coil of the wire furnace. After that, the composition is 49.6 at% Ti with room temperature super elastic and skillful materials to make up Divided into two parts, the pure nickel is added to the human coat and the lion is placed in the φ 埚, the pure titanium material is placed in the hopper, and then vacuumed to 4xl (under T2 torr, argon is introduced to 3 〇〇torr, and Inductive heating smelting to the vicinity of the solution of pure nickel. At this time, the heating power of the induction coil is immediately lowered, controlled to just maintain the temperature at the melting point, around 1453 ° C, and pure nickel near the melting point. The molten metal is in a viscous state, so it is not subject to the erosion caused by the agitation of the magnetic lines. The cerium oxide coating can be strengthened again. After about 20 minutes, it is slowly added to the hopper. Titanium raw material. Since the melting point of NiTi functional material is only 1240 ° C, although the liquid 14 grade of 200813238 in the coating crucible decreases, the gold liquid flow increases. Uniform n main to inner diameter application _ length (10) deleted graphite Cooling into a NiTi functional material cast rod. In the production of the trial towel, this coating is based on the above-mentioned sputum-furnace smelting, Ik is made in a conventional manner and then five times in total, for a total of six Super-strength cast rod. This cast rod is subjected to contact forging (4)-sw_g and annealing treatment in (9) generation, #小直径缩缩缩__Start to cold-extraction* until lmm. NiTi alloy wire during cold drawing process Soak in liquid sad nitrogen to ensure that the temperature of the wire does not exceed the temperature of As. The oxygen content of the functional material of these divisions and the number of fractures during the cold drawing process are listed in 4. 4. From Table 4, the comparison and comparison examples are found. The biggest difference (the conventional method) is that the oxygen content and the number of fractures are hardly affected by the number of melting furnaces. In other words, the invention of the present invention is a good result for each of the furnaces. The result is also the metallographic analysis of the SEM profile from the oxidized coating of the six consecutive furnaces. It is found that after six consecutive furnaces of liquefaction, the surface of the emulsified coating has been affected by the smelting process. The residual effect almost disappeared However, it has not yet lost the function of protecting the oxidized substrate. The semi-quantitative analysis from EDX also confirms that not only the internal oxidation of the oxidized town is the boundary gap of the magnesium oxide particles, but also has not been affected. The surface of the osmotic disk is not subject to serious intrusion. However, the result of gold = minute = the result also shows that the critical point has been used, and the further training will lead to the loss of 15 200813238 'As in the first place, the richness of titanium-rich Nm functional material melts the money, the neo-sensitive oxygen content depends on the deterioration of the material. Therefore, the addition amount of the dioxide should not be lower than the relative oxidation to weight ratio 7%.
【圖式簡單說明】 ιίτ· 以叾知之氧化紀塗層渺尚在連續五爐次的等原子比 一 1功能性材料熔煉後之SEM剖面金相； 、’、 中具有優異之抗沖蝕及侵蝕反應能力之典型 塗層表面形悲金相顯微組織結構； iiKff种經過連續六爐次之等原子比贈丨功能性材 之線性倾塗層卿舶金相，以及針對記元素 之綠性知瞄（line scan)。 【主要元件符號說明】 16[Simple description of the diagram] ιίτ· The SEM profile metallographic layer of the oxidized coating of 叾 叾 在 在 在 在 在 在 在 在 连续 连续 连续 连续 连续 连续 SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM The typical coating surface of the erosive reaction is characterized by a sinister metallographic structure; iiKff is a linear tilt coating of the six-cylinder equivalent atomic ratio of the functional material, and a green target for the element (line scan). [Main component symbol description] 16