TWI227741B - The use of rapid brazing in joining Ti-Ni shape memory alloys - Google Patents

Abstract

A method of fast brazing Ti-Ni shape memory alloys are featured with firstly rapid heating and melting the braze filler, and the molten braze can subsequently wet and bonding Ti-Ni shape memory alloys. Experimental results demonstrate that excellent shape memory property is preserved in the bonded specimen after fast brazing Ti-Ni shape memory alloy, and the brazed specimen has fairly good toughness. Therefore, this patent has the value of pragmatic engineering applications.

Description

12277411227741

所謂硬銲是指需在接合件工件之間使用填充合金， 並升溫到填充合金的熔點以上約1 〇 °c〜1 〇 〇 °c後，使填充人 金充份溶化並和接合件的表面產生鍵結（13〇]1(1丨118)的~種 接合方式。在硬銲製程中母材並未發生熔化，僅填料發生 全溶，故此製程常被用來接合一些傳統銲接製程所無法接 合的異種材料。此製程與另一種軟銲製程非常類似，區分 軟銲和硬銲最簡單的方法，就是由填充合金的熔點來區刀 分。通常製程溫度低於4 50 °c的稱為軟銲，高於45〇t的 為硬銲。故在軟銲製程中所使用的填充合金大多是溶點乾 低的元素如：鉛（Pb)、錫（Sn)…等，其所組成填充合金= 熔點較低，大多是低於4 5 0 °C。反觀，在硬銲製程中使用 的填充合金大多由熔點較高的元素所組成，如銀（A (Cu)、鎳（Ni )、鈦（Ti)…等。這些銀基、鋼基、鎳美 鈦基填充合金的熔點大多高於45 〇。〇，甚至於達、土^疋 以上（鎳基硬銲填充合金）。 门達1 00 0 C 由於硬銲在比較高的製程溫度，所以在硬 =比較廣泛的冶金現象發生，使得部分硬銲合中 中，或是基材中的元素由於在高溫的環境下，葬二材 :進入填充合金中，因而改變了合金的成分，纟而旦H ^合金的流動性、潤濕性，並使接合強度〜β真 =金化作用。此外，…高温的製程也會：：銲= :$對於周圍的氣氛（特別是氧氣）軟銲人今、充 :感。所以在保護氣氛或是真空下硬銲，將預期：ί f加 的效果。在硬鮮接合製程步驟中可以m較佳 々芍·（ 1 )將The so-called brazing refers to the need to use a filler alloy between the workpieces of the joint and raise the temperature to about 10 ° c ~ 100 ° c above the melting point of the filler alloy, and then fully dissolve the filler gold and the surface of the joint. A variety of bonding methods that produce bond (13〇) 1 (1 丨 118). In the brazing process, the base material does not melt, only the filler is completely dissolved, so this process is often used to join some traditional welding processes that cannot Jointed dissimilar materials. This process is very similar to another soldering process. The easiest way to distinguish between soldering and brazing is to divide by the melting point of the filler alloy. Usually the process temperature is lower than 4 50 ° c is called Soft soldering, those above 45 ° t are hard soldering. Therefore, the filler alloys used in the soldering process are mostly elements with low melting points such as lead (Pb), tin (Sn), etc., and their composition is filled. Alloy = low melting point, mostly below 450 ° C. In contrast, the filler alloys used in the brazing process are mostly composed of elements with higher melting points, such as silver (A (Cu), nickel (Ni), Titanium (Ti) ... etc. These silver-based, steel-based, nickel-nickel-titanium-based filler alloys have large melting points Much higher than 45 〇, even more than, and more than ^ 镍 (nickel-based brazing filler alloy). Menda 1 0 0 0 C due to brazing at a relatively high process temperature, so hard = a more extensive metallurgical phenomenon Occurred, so that some of the elements in the brazing joint or the base material were buried in the high temperature environment, entering the filler alloy, thus changing the composition of the alloy, and then the fluidity of the H ^ alloy, Wettability, and make the joint strength ~ β true = aluminization. In addition, the high temperature process will also :: Weld =: $ For the surrounding atmosphere (especially oxygen) soft soldering people, charge: feel. So in Protective atmosphere or brazing under vacuum will be expected: the effect of f plus. In the hard and fresh joining process steps, m can be better. (1)

第5頁 1227741 五、發明說明（2) 工件升溫到填充合金熔點以上，使填充合金完全液化（不 可超過基材的熔點）。（2 )完全液化的填充合金和基材間發 生冶金反應並潤濕母材。（3 )利用對接基材間的間隙產生 毛細流（C a p i 1 1 a r y F 1 〇 w )現象，將溶化的填充合金充滿 於接合面間隙之中。（4 )冷卻後即可形成硬銲接點。 鈦錄形狀記憶合金（Ti-Ni Shape Memory Alloys)之 化學組成依原子比約為T i 5 0 N i 5 0，因其具有優良的形狀記 憶性、良好的常溫機械性質（包含強度及韋刃性）、優良的抗 腐蝕能力...等優點，故為一深具潛力之工程材料。所謂 形狀記憶性為材料於低溫下之變形，可以利用加熱的方式 使此已變形之材料升溫至某特定溫度以上時，材料即可回 復原狀之特性。本發明中鈦鎳形狀記憶合金即擁有此性 質。而因鈦鎳形狀記憶合金，可藉由其他元素（如：金、 I巴...等）之添加而改變其形狀記憶性質，故本專利内所涵 蓋之鈦鎳形狀記憶合金，係泛指所有以鈦鎳成份為主體之 形狀記憶合金。 傳統硬銲接合作業因加熱速率低（約5- 2 0 °C / m i η )，為了減少基材暴露於高溫環境下可能產生之 不良影響，工作溫度往往設定在硬銲填料熔點溫度以上約 3 0〜5 0 °C的範圍内，再持溫1 0〜1 5分鐘，藉由輕微過熱之 液相填料與基材間的潤溼作用，來結合兩端之基材。然而 在鈦鎳形狀記憶合金之硬銲接合製程中，由於熔融的硬銲 填充合金，可能會對於鈦鎳形狀記憶合金造成合金化的效 果，因而改變鈦鎳形狀記憶合金之化學組成。此外，由於Page 5 1227741 V. Description of the invention (2) The workpiece is heated above the melting point of the filler alloy to completely liquefy the filler alloy (not to exceed the melting point of the substrate). (2) Metallurgical reaction occurs between the fully liquefied filler alloy and the substrate and wetting the base material. (3) Capillary flow (C api 1 1 a r y F 1 0 w) phenomenon is generated by using the gap between the butt base materials, and the molten filler alloy is filled in the gap between the joint surfaces. (4) A hard solder joint can be formed after cooling. The chemical composition of Ti-Ni Shape Memory Alloys is about T i 5 0 N i 5 0 in terms of atomic ratio, because of its excellent shape memory, good mechanical properties at room temperature (including strength and Wei blade) Properties), excellent corrosion resistance, etc., so it is a potential engineering material. The so-called shape memory is the deformation of a material at a low temperature. When the deformed material is heated to a certain temperature or higher by heating, the material can return to its original shape. The titanium-nickel shape memory alloy in the present invention possesses this property. And because the shape of titanium nickel nickel shape memory alloy can be changed by the addition of other elements (such as: gold, I bar, etc.), the shape of titanium nickel nickel shape memory alloy is covered by this patent. All shape memory alloys based on titanium nickel. Due to the low heating rate (about 5- 2 0 ° C / mi η) of the traditional brazing welding industry, in order to reduce the possible adverse effects of the substrate exposed to high temperature environment, the working temperature is often set to about 3 above the melting point of the brazing filler. In the range of 0 ~ 50 ° C, hold the temperature for another 10 ~ 15 minutes, and use the wetting effect between the slightly overheated liquid-phase filler and the substrate to combine the substrates at both ends. However, in the welding process of the titanium-nickel shape memory alloy, due to the molten brazing filler alloy, the alloying effect of the titanium-nickel shape memory alloy may be caused, thereby changing the chemical composition of the titanium-nickel shape memory alloy. In addition, because

1227741 五、發明說明（3)1227741 V. Description of the invention (3)

母材内含有大量的鈦元素，而鈦元素本身又具有相當高的 活性，故於傳統之硬銲製程中，可能會形成鈦元素與硬銲 填料内部份元素發生反應，而形成具有脆性的介金屬化合 物。如此一來，不僅形狀記憶合金本身的記憶性質將喪 失，其接合部份亦因變脆而易發生斷裂無法使用。這造成 了目前大部份的接合製程，均無法應用於鈦鎳形狀記憶合 金之中。就目前所知，鈦鎳形狀記憶合金内可以固溶一定 程度的銅、鎳或鈦元素，而不會造成其形狀記憶性質的喪 失。此三種元素中，又以銅元素的溶點最低（攝氏1085 度），故銅元素應為理想的填充合金之一。 如前所述，若能使用快速硬銲接合製程，將造成基 材（鈦鎳形狀記憶合金）暴露於高溫中的時間大幅減少，故 而減低因高溫造成材料的不良影響，如：介金屬化合物之 生成或母材發生合金化的可能性。故使用快速硬銲接合製 程，於接合後將能夠保有原鈦鎳形狀記憶合金之性質。此 點為傳統硬銲接合製程所不及。而發明中所述快速硬銲接 合製程包含：紅外線硬銲、雷射硬銲及電子束硬銲等三種 主要方法。The base material contains a large amount of titanium, and titanium itself has a relatively high activity. Therefore, in the traditional brazing process, the titanium element may react with the internal elements of the brazing filler material to form a brittle Mediation metal compounds. As a result, not only the memory properties of the shape memory alloy itself will be lost, but the joints will become brittle and easily break, making it unusable. As a result, most of the current joining processes cannot be applied to titanium nickel shape memory alloys. As far as is known, a certain degree of copper, nickel or titanium can be dissolved in the titanium-nickel shape memory alloy without losing its shape memory properties. Of these three elements, the melting point of copper is the lowest (1085 degrees Celsius), so copper should be one of the ideal filler alloys. As mentioned earlier, if the rapid brazing process can be used, the time for which the substrate (titanium-nickel shape memory alloy) is exposed to high temperatures will be greatly reduced, so the adverse effects of materials caused by high temperatures will be reduced, such as: The possibility of formation or alloying of the base material. Therefore, using the rapid brazing process, the properties of the original titanium nickel shape memory alloy can be maintained after joining. This is beyond the reach of traditional brazing processes. The rapid brazing process described in the invention includes three main methods: infrared brazing, laser brazing and electron beam brazing.

玆以下列示實例，詳細說明本創作之具體工藝。發 明中所使用的紅外線硬銲接合裝置，係採用日本製ULVAC SINKO-RIKO RHL-P610C型之紅外線加熱爐體，具有六組石 英燈管（内有鎢電熱絲）與六個拋物線形之黃金聚光反射 曲面，最高工作溫度可達約1300 °C，輸入功率（Rating) 為12.0 KW。整體接合系統乃是於國内自行組裝而成。配The following examples are given to explain the specific process of this creation in detail. The infrared hard-welding device used in the invention is an infrared heating furnace made of Japanese ULVAC SINKO-RIKO RHL-P610C type. It has six groups of quartz lamps (with tungsten electric heating wires) and six parabolic gold gathers. Light reflective surface, the highest working temperature can reach about 1300 ° C, and the input power (Rating) is 12.0 KW. The integrated joint system is self-assembled in China. Match

第7頁 1227741 五、發明說明（4) --- 備有一端封口之石英保護管與其他附屬之進排氣設備。而 2紅外線快速加熱裝置可在流動氬氣保護氣氛（或高真 空，&lt; 5x 10-5 mbar )下進行紅外線硬銲製程。紅外線硬 銲溫度為1150 C，持溫時間分別為6〇及3〇〇秒。實驗中使 用2 5 m i c r 〇 m e t e r厚之純銅片為硬輝填料。紅外線硬銲接 合鈦鎳形狀記憶合金後，以鑽石切割機將試片切成大小為 20mm(長）、5mm(寬）及〇· 5mm(厚）的尺寸，再進行彎曲測試 如第一圖所示。第一圖内（1)為試片中央部份“填料於接 合後所形成硬銲接點的位置，（2)代表上、下兩片材料均 為欽鎳形狀記憶合金。於彎曲測試中，先將上述試片於低 溫下進行彎曲至㊀i，再將試片升溫至室溫以量測其回復 角度（Θ f)。此時可以依下列公式計算出回復率（Rec〇very R a t i 〇 ) - ( Θ i - Θ f ) /㊀i。結果顯示經紅外線硬銲接合持溫 60秒及3 0 0秒之試片，其回復率分別為86%及92%。而未經 紅外線硬銲之純鈦鎳形狀記憶合金母材，其回復率約為 9 7%。相較之下，於紅外線硬銲接合後之鈦鎳形狀記憶合 金，仍然保有相當優良之形狀記憶性質。另外，硬鲜接合 試片於測試後以立體顯微鏡下觀察，並未發現任何裂紋， 故可$正實此鲜點具有相當之勃性’而具有工程上應用的價 值。雖然紅外線硬銲技術已發展多年，但是應用紅外線硬 銲技術接合鈥鎳形狀記憶合金則為首創。使用本技術接合 後之鈦鎳形狀記憶合金，仍然保有相當優良之形狀記憶性 質，將使此製程深具未來發展潛力。 上述之具體實施例是用來詳細說明本發明之目的、Page 7 1227741 V. Description of the invention (4) --- Equipped with one end sealed quartz protection tube and other attached intake and exhaust equipment. The 2 infrared fast heating device can perform the infrared brazing process in a flowing argon protective atmosphere (or high vacuum, <5x 10-5 mbar). Infrared brazing temperature is 1150 C, holding time is 60 and 300 seconds, respectively. In the experiment, a pure copper sheet with a thickness of 25 m i c r 0 m e t e r was used as the hard glow filler. After infrared brazing with titanium nickel shape memory alloy, the test piece was cut into a size of 20mm (length), 5mm (width), and 0.5mm (thickness) with a diamond cutting machine, and then the bending test was performed as shown in the first figure Show. In the first figure (1) is the position of the "hard filler joint formed by the filler after joining in the central part of the test piece, and (2) represents the upper and lower pieces of material are both nickel nickel shape memory alloy. In the bending test, first Bend the test piece to ㊀i at low temperature, and then warm the test piece to room temperature to measure its recovery angle (Θ f). At this time, the recovery rate (Rec〇very R ati 〇) can be calculated according to the following formula- (Θ i-Θ f) / ㊀i. The results show that the test pieces with infrared holding temperature of 60 seconds and 300 seconds have a recovery rate of 86% and 92% respectively. Pure titanium without infrared brazing The nickel shape memory alloy base material has a recovery rate of about 9 7%. In comparison, the titanium-nickel shape memory alloy after infrared brazing still retains very good shape memory properties. In addition, hard and fresh joint test pieces Observed under a stereo microscope after the test, no cracks were found. Therefore, this fresh spot can be quite robust and has engineering value. Although infrared brazing technology has been developed for many years, infrared brazing is applied. Technology Joint — Nickel Shape Memory Alloy It is the first. The titanium-nickel shape memory alloy joined by using this technology still retains very good shape memory properties, which will make this process have great potential for future development. The above specific embodiments are used to explain the purpose of the present invention in detail

1227741 五、發明說明（5) 特徵及功效，對於熟悉該項技藝人士而言，根據上述說明 對該具體實施例作部分變更或修改，均不脫離本發明之精 神範疇。以任何更動與潤飾在不脫離本創作之基本精神 下，均應屬於本創作之適用範圍。1227741 V. Description of the invention (5) For those skilled in the art, some changes or modifications to the specific embodiment according to the above description will not depart from the spirit of the present invention. Any modification and retouching shall be within the scope of this creation without departing from the basic spirit of this creation.

第9頁 1227741 圖式簡單說明 第一圖為T i N i形狀記憶合金經快速硬銲接合後試片進行彎 曲測試之示意圖 圖式中元件符號之簡單說明： 1 -硬銲接點 2 -鈦鎳形狀記憶合金Page 91227741 Brief description of the diagram The first diagram is a schematic diagram of the bending test of the test piece of T i N i shape memory alloy after rapid hard welding. Brief description of the component symbols in the diagram: 1 -Hard solder joint 2 -Titanium nickel Shape Memory Alloys

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Claims (1)

.1227741 、申請專利範圍 六 種使用快速硬銲接合鈦鎳 徵在於快速加熱並熔化硬銲 /憶金之方法，其特 形狀記憶合金。 、科後’犯夠潤濕並接合鈦鎳 硬輝、雷射硬辉及電…之方法包含：紅外線 圍ί1:所述使用快速硬銲接合鈦銻形狀 成分為主體ίί金中鈦鎳形狀記憶合金包含所有以鈦錄 t ^ =申清範圍第1項所述使用快速硬銲接合鈦鎳开《狀 二二〇金之方法，其中硬鋅填料為用以接合鈑鎳开，、二 口、，其化學組成包含任選自銅、鎳及鈦基硬銲 /己隐 的群體之至少一種。 知填枓而成 第11頁.1227741, patent application scope Six kinds of rapid brazing with titanium nickel are characterized by rapid heating and melting of brazing / memory gold, its special shape memory alloy. The method of “Kouhou” is enough to wet and join titanium nickel hard glow, laser hard glow, and electricity. The method includes: infrared ray 1: the use of fast hard soldering of titanium and antimony shape components as the main body of gold and titanium nickel shape memory The alloy contains all the methods described in item 1 of the scope of the application of titanium t ^ = application of rapid hard welding of titanium and nickel to form titanium and nickel, where the hard zinc filler is used to join sheet nickel, Its chemical composition includes at least one of a group selected from copper, nickel, and titanium-based brazing / capping. Knowledge Filled Page 11