TWI251518B - Method of brazing titanium alloy to stainless steel - Google Patents

Abstract

A brazing method for joining titanium alloy and stainless steel at low temperature was developed. By means of depositing a thin film of silver on the faying surface of stainless steel, and using the Al-Si alloy as filler metals, the strength could be significantly increased. The assembly is then placed in a vacuum furnace during a brazing operation. This brazing process can make a sound join for titanium alloy to stainless steel and the tensile strength after brazing is more than 70 kg/cm<2>.

Description

1251518 五、發明說明（1)1251518 V. Description of invention (1)

【發明所屬之技術領域】 本發明是一種低溫的鈦 法，接合溫度為6 0 0 °c左右 產生的尺寸變形與材質劣化 使用壽命。 合金與不鏽鋼真空硬銲接合方 ，接合件可避免因高溫硬銲所 等不良影響，並可延長模夾具 【先前技術】 已知相關的硬銲接合技術如us. Pat· Nq63 6 1 68069，採商用 Ag-Cu-pa (68.5wt%Ag，265討％(^， 5wt· %Pa )等合金填料，此類填料之硬銲溫度皆高達❺⑽ 以上。其缺點如下：〈1〉由於硬銲溫度甚高，因此接八 件谷易變形。〈2〉於此溫度操作，對不鏽鋼而 全退火狀態，接合件於硬銲完忐饴，备、生少μ 尺％ 訐凡成後，會造成機械強度下 降。甚至在硬銲完成後，若考膚各、入 .^ ^ ^ 右哼愿急冷，會造成變形，而採BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-temperature titanium method in which dimensional deformation and material deterioration life are caused by a joining temperature of about 60 °C. Alloy and stainless steel vacuum hard solder joint, joints can avoid adverse effects such as high temperature brazing, and can extend the mold fixture [Prior Art] Known related hard solder joint technology such as us. Pat·Nq63 6 1 68069 Commercial Ag-Cu-pa (68.5wt% Ag, 265%% (^, 5wt· %Pa) and other alloy fillers, such fillers have a brazing temperature of more than ❺ (10). The disadvantages are as follows: <1> due to brazing temperature Very high, so eight pieces of valleys are easy to deform. <2> This temperature is operated, the stainless steel is fully annealed, the joints are brazed, and the preparation is less than 5%. The strength is reduced. Even after the completion of the brazing, if the skin is tested, the ^^ ^ ^ right will be quenched, which will cause deformation.

用爐冷的方式’對一般的不鐘彻而丄 ^ X 口 j个罐綱而$，更會產生敏化現 象，如此將嚴重地降低不鏽鋼的耐蝕性。〈3古加 會造成模爽具變形與材質急速劣化，減少模’ 增加硬銲成本。 /、可p 【發明内容】 〈1〉發明背景 硬#疋一種局於4 5 0 C的接人姑供，y» A J丧 &gt; 技術，在硬銲時需要使In the way of furnace cooling, it is not punctual, and it is more likely to produce sensitization, which will seriously reduce the corrosion resistance of stainless steel. <3 Gujia will cause deformation of the mold and rapid deterioration of the material, reducing the mold' to increase the cost of brazing. /, can p [invention content] <1> invention background hard #疋 a bureau in the 4 5 0 C access to the guise, y» A J mourning &gt; technology, in the brazing needs to make

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用填料（fi 1 ler metal )，工件在硬銲時需尊 加熱，加熱方式可以是爐具（真空爐或氣氛、母材整體 應、感應加熱、火炬或紅外線等加熱方式。；，2學反 或非鐵合金填料，其熔點需高於45 〇。〇，而 I基合金 相線溫度（S〇lidus temperature )，使用的填料=固 低於45(TC，則稱之為軟銲（s〇ldering)。異枓/皿度若 硬銲同熔銲一樣，都是冶金鍵結，因此1 可能會大於母材。所選用的填料，必須考慮^與度有 金相容性（metallurgical compatibiliti〜es，y、、材之冶With the filler (fi 1 ler metal), the workpiece needs to be heated during brazing. The heating method can be the heating method of the furnace (vacuum furnace or atmosphere, base material, induction heating, torch or infrared). Or a non-ferrous alloy filler, the melting point needs to be higher than 45 〇. 〇, and the I-based alloy phase line temperature (S〇lidus temperature), the use of filler = solid below 45 (TC, then called soldering (s〇ldering If the brazing/difficulty is the same as the fusion welding, it is a metallurgical bond, so 1 may be larger than the base metal. The selected filler must be considered for metal compatibility (metallurgical compatibiliti~es, y, Metallurgical

因為如此，只要選對填料，硬銲可以完成傳統熔銲正是 (fusion processes )所無法辦到的異質材料接合。 接合時是填料溶母材不$，因此可應用於如銅與銘此炫 點差距大（銅熔點：1 083 t，鋁熔點：66〇)的異所 接。亦可用於金屬與非金屬（如陶瓷與金屬）的接合貝。、 當硬銲完成時，由於填料會與母材產生冶金反^， 形成介金屬化合物（intermetaUic c〇mp〇unds)，、因此 其機械強度有時會優於母材，且其再熔融溫度會提高。 於是整體加熱，因此操作時可藉著昇降溫速率的調整，Because of this, as long as the filler is selected, brazing can complete the joining of heterogeneous materials that traditional fusion welding cannot. When joining, the filler-soluble base material is not $, so it can be applied to the difference between copper and the bright point (copper melting point: 1 083 t, aluminum melting point: 66 〇). It can also be used for the joint of metal and non-metal (such as ceramic and metal). When the brazing is completed, the filler will form a metallurgical reaction with the base metal to form a metametal (intermetaUic c〇mp〇unds), so the mechanical strength is sometimes superior to the base metal, and the remelting temperature will be improve. Therefore, the whole is heated, so the operation can be adjusted by the temperature rise and fall rate.

少工件變形罝的發生，且因為是整體加熱，因此銲後工 可達到一均勻的應力分佈。 τ 在工程上，硬銲的品質 合間隙：一般而言，接合間 銲溫度與時間：較好的硬銲 的時間，以避免脆性相的生 由下列參數決定：即（1 )接 隙愈大，強度愈差。（2 )硬 條件應該是較低的溫度與較短 成而使機械強度變差。（3 )Less workpiece deformation occurs, and because of the overall heating, a uniform stress distribution can be achieved after welding. τ In engineering, the quality of brazing is combined with the gap: in general, the inter-bonding temperature and time: better brazing time to avoid the brittle phase is determined by the following parameters: (1) the larger the gap The worse the strength. (2) The hard condition should be lower temperature and shorter to make the mechanical strength worse. (3)

1251518 五、發明說明（3) 接合面的表面處理·不良的接合面會使溶融的填料難以潤 濕，此時填料與接合面的接觸角會變大，而無法完成接 合。表面處理的方式一般為脫脂、化學清洗或是機械處理 (如研磨），主要目的是除去接合面上的油脂與氧化層 (4 )填料的選擇：不同的填料會有不同的機械性能表曰 現。 真空硬銲是爐内硬銲的一種方法，所需之設備為直办 爐，真空度約為10-4t〇rr以下，大氣中氧含量約為21%、， 因此爐内氧分壓約為2.1\10-5^1^左右，如此之硬 境已是相#好的保言蔓Λ氛，優於其他如^氣氣衣 保護氣氛的氣氛爐，因此真空硬銲不需使用助 〃^為 )，銲後就不會有因flux殘留所造成的腐蝕 ux 問題，可以達到一品質優良的接合。 β洗的 由不需使用保護氣氛與後清洗這兩點 的成本在長期使用，會較傳統氣氛爐^ ^空硬銲 本發明所使用之母材鈦合金，因比^更、、二凊。 佳，因此被廣泛應用於航太與化工 又大，耐蝕性 結構上或者是經濟上的考量，此义=因特殊需求，如 而為工程上所使用：如 ς淼須與不鏽鋼接合’ :堯室，甚至是高爾夫球；储：岸=儲存筒、推進器 =H化學儲槽的内部，以鈦合金來制w將耐腐麵性的 覆，兩者以硬銲的方式作ί:作，而外部則以 接合件於硬銲時，忒作接合，以節省 夾具材質的高溫劣 里除接合強度外，。 为化與尺寸的變形亦「母材與模 點。本發明的主 1251518 五 發明說明（4) 要目的，Ρπϊ 3 一 _ Ρ疋開發一種低溫、高口曾 法，以避务丁从k &gt; 貝的真空碩锃4立人 光工件的咼溫變形金好祖 更if·接合方 加工件的可靠_ * “，與材料機械性質下P备、公 罪度，並延長模夾具的使用壽 I，進而增 本 ^，降低製造成 〈2〉詳細說明 如發明背景所述，高溫硬銲對接合 :良：影響。為避免高溫硬銲之變形二劣:j爽具會有 ^本發明採用低炼點之紹1合金作填才料化作問二產 h母材（10) (14)先作脫脂及表面化 成表面清洗後，於不鏽鋼（1〇)接合 二洗，在完 )或化學（銀鏡反…方式，被覆上一層d(滅鍍 度為 15-30 /zm。 ) ’ 厚 2.將鋁合金填料，片狀（12 )或膏狀（21 ) 份特性如表一’以預置法（第—圖）或毛細吸入、枓成 二圖）等方式，與接合件組裝，組裝完成後，置入/直★弟 中進行硬銲，硬銲溫度為582 °C至6 00 t：，真空爐之^ =二 必須維持$10_4torr，硬銲時間為卜5分鐘。 …工又 3 ·接合件可以用夹具（1 8 )或點銲（2 3 )的方式進^一 組裝固定’並藉以施加約l-5Psi的壓力。若是以毛=吸= 法作組裝時，則必須預留〇· 02-〇· 1 〇mm的間隙（25 )(如 第二圖）。 口 4·硬銲完成後’直接作氣冷，避免不鏽鋼產生敏化現1251518 V. INSTRUCTIONS (3) Surface treatment of the joint surface. A poor joint surface makes it difficult to wet the melted filler. At this time, the contact angle of the filler with the joint surface becomes large, and the joint cannot be completed. The surface treatment method is generally degreasing, chemical cleaning or mechanical treatment (such as grinding). The main purpose is to remove the grease and oxide layer on the joint surface. (4) The choice of filler: different fillers will have different mechanical properties. . Vacuum brazing is a method of brazing in the furnace. The equipment required is a direct furnace. The vacuum is about 10-4t〇rr, and the oxygen content in the atmosphere is about 21%. Therefore, the oxygen partial pressure in the furnace is about 2.1\10-5^1^ or so, such a hard environment is already a good #言保蔓Λ, which is superior to other atmosphere furnaces such as air-protective atmosphere, so vacuum brazing does not need to use 〃^ Therefore, there is no corrosion ux problem caused by flux residue after welding, and a good quality joint can be achieved. The cost of the β-washing is not required to use the protective atmosphere and the post-cleaning. The cost of the two points is longer than that of the conventional atmosphere furnace. The base metal alloy used in the present invention is more than two. Good, so it is widely used in aerospace and chemical industry, corrosion resistance structural or economic considerations, this meaning = for special needs, such as engineering use: if you do not need to be joined with stainless steel ' :尧Room, even golf ball; storage: shore = storage cylinder, propeller = H chemical storage tank inside, made of titanium alloy to make the surface of the anti-corrosion surface, both of which are hard-welded On the other hand, when the joint is brazed, the joint is joined to save the high temperature of the fixture material except the joint strength. For the deformation and size of the deformation also "base metal and modulus. The main 1251518 of the present invention five invention description (4) The purpose, Ρπϊ 3 a _ Ρ疋 develop a low temperature, high mouth method to avoid Ding from k &gt ; Bei's vacuum mastery 4 Liren's light workpiece's temperature deformation gold good ancestor more if · joint processing parts of the reliable _ * ", with the mechanical properties of the material P preparation, public sin, and extend the life of the mold fixture I, and then increase the manufacturing cost, reduce the manufacturing into <2> Detailed Description As described in the background of the invention, high temperature brazing is good for bonding: good: influence. In order to avoid the deformation of high-temperature brazing, the following two problems: j-slurry will have ^ the invention uses a low-refining point of the 1 alloy as a filling material for the second production of the parent material (10) (14) first for degreasing and surface formation After the surface is cleaned, the stainless steel (1〇) is joined to the second wash, at the end) or chemically (the silver mirror is reversed... the coating is coated with a layer d (the degree of de-plating is 15-30 /zm.) 'Thickness 2. The aluminum alloy filler, The characteristics of the sheet (12) or the paste (21) are as shown in Table 1 by the preset method (Fig.) or capillary suction, and the two parts are assembled with the joint. After assembly, insert/ Hard soldering is carried out in straight, the brazing temperature is 582 °C to 6 00 t:, the vacuum furnace must be maintained at $10_4torr, and the brazing time is 5 minutes. The work piece 3 can be assembled and fixed by means of a jig (18) or spot welding (2 3) and by applying a pressure of about 1-5 psi. If it is assembled by the wool = suction method, the clearance (25) of 〇·02-〇·1 〇mm must be reserved (as shown in the second figure). Port 4·After the brazing is completed, the air is directly cooled to avoid sensitization of stainless steel.

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表 銘-石夕合金填料成份與硬銲範圍表Table Ming-Shixi Alloy Filler Composition and Brazing Range Table

Si ΜηSi Μη

MgMg

Zn 硬銲範圍（ -10 〇. 10 1 · 0 - 2 · 588-604 〈3〉内容說明 無—石夕合金填料通常僅用在鋁合 ::能應用在鈦合金與不鏽鋼異質材硬？上 為在，接合面上，鑛上一層銀當作阻乃-因 此類目!上，可知Αΐ^會形成Mi或是AM ’ 填料中的=匕“目雖硬脆，但依然能為工程上所應用；而 介金屬4^、不鐵鋼中的^會形成^12 ΜΑ15及FeAl3等 裎上應用！ …、法於工 母材ii避免鲜道内不良介金屬化合相的產生’在不鏽鋼 μ a面上鍍上一層厚度約15至30//m之銀薄膜作阻障 止 此阻卩早層可有效地避免接合件中原子的相互擴散，防 膽* H相的形成，進而提高接合件的機械強度。 銀錢層的方法，有物理方式，如濺鍍Zn brazing range ( -10 〇. 10 1 · 0 - 2 · 588-604 <3> Description of content - Nothing - Shixi alloy filler is usually only used in aluminum alloy:: can be applied to titanium alloy and stainless steel heterogeneous material hard? In the joint surface, a layer of silver on the ore is used as a resistance - so the category! On the surface, it is known that Αΐ^ will form Mi or AM' filler = 匕 "The surface is hard and brittle, but it can still be used for engineering. Application; and the intermetallic 4^, non-ferrous steel ^ will form ^12 ΜΑ15 and FeAl3 and other applications on the crucible! ..., the method of the base metal ii to avoid the formation of poor intermetallic metallization in the fresh channel 'in the stainless steel μ a surface Plating a silver film with a thickness of about 15 to 30//m as a barrier to prevent the mutual diffusion of atoms in the joint member, preventing the formation of a bile*H phase, thereby improving the mechanical mechanism of the joint member. Strength. The method of silver layer, there are physical methods, such as sputtering

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1251518 I、發明說明（6) ' -- (sputtering )，有化學方式，如銀鏡反應，亦有電鍍 式等諸方法。 x 【實施方式】 一 二組鈦合金板材與不鏽鋼格網之異質硬銲試片，如 三圖所示，底板為2mm厚之鈦合金（Ti-6A1_4V合金 (31 ),以熱壓之方式彎成曲率半徑約為2〇〇mm之 材 網狀304不鏽鋼（32)之接點為5&gt;&lt;5龍2，每組試/ 個硬銲接合點。本工件接點之機械強度設計 、有 45kg/cm2。 。 相組5片為鈦合金與不鏽鋼未加銀鍍層；第二袓為 層=二Γ鋼Λ合面上，以化學銀的方式，鑛上士 兩母材的接合面Γ，皆:化障層；第三組為相同母材’在 度約30 _)作為阻障層。b予銀的方式’鍍上—層銀（厚 硬輝三=持組裝方式，於同-爐次作真空 為60(TC，硬銲時為.真空度5x 10_5torr，硬銲溫度 力作氣冷處理，採用4刀鐘’硬銲完後以5psig之氮氣壓 度測試。抗拉气矽合金硬銲填料，之後作抗拉強 tester 式驗所用之儀器為EleCometer，AdheSi0n 6點計算’Γ平^ UK. 1 1 791 49，US. 3527093，每組試片取 句值’所得數據如下；1251518 I, invention description (6) ' -- (sputtering), there are chemical methods, such as silver mirror reaction, there are also methods such as electroplating. x [Embodiment] One or two sets of heterogeneous brazing test pieces of titanium alloy sheet and stainless steel grid, as shown in the three figures, the bottom plate is 2mm thick titanium alloy (Ti-6A1_4V alloy (31), bent by hot pressing The joint of the mesh 304 stainless steel (32) with a radius of curvature of about 2 mm is 5&gt;&lt;5 dragon 2, each set of test / hard solder joint. The mechanical strength design of the workpiece joint, 45kg/cm2. The phase set of 5 pieces is titanium alloy and stainless steel without silver plating; the second layer is layer=2Γ steel joint surface, in the form of chemical silver, the joint surface of the two mineral materials of the mine sergeant, All: the barrier layer; the third group is the same base material 'at a temperature of about 30 _) as a barrier layer. b silver to the 'plated-layer silver (thick hard Hui three = holding assembly method, in the same - furnace vacuum for 60 (TC, hard welding, vacuum 5x 10_5torr, brazing temperature for air cooling treatment, After 4 hardenings, the test was carried out with a nitrogen pressure of 5 psig after brazing. The tensile strength of the gas-filled alloy was used for the test of the tensile strength tester. The instrument used for the tensile tester was EleCometer, and the AdheSi0n 6 point was calculated as 'Γ平^ UK. 1 1 791 49, US. 3527093, the value of each set of test pieces is obtained as follows;

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組別 ---— ----一 一 .—1 1 一 一—___ 抗拉強度（k g / c m2 ) -———. 鍍銀層 第一 組 40 —-———-_ 無 第二 組 70 鍍於不名 第三 組 71 兩邊皆4 由 拉強度 薄膜作 未加銀 層上較 膜，但 就成本 為不鏽 面顯微 度約30 且冶金 無空孔 劑，因 第 上表可知，未加阻障層處理之試片（第一组）直抗 計要求（45kg/cm2)，而母材在鍍上、銀 早層後，其抗拉強度可達到7〇kg/cm2以上與 曰目比，其抗拉強度增加γ 5 %。第三組試片在鍍 ，： 多-道次，即在鈦合金上亦鍍上一層銀薄 強度上只增加了丨kg/cm2，效益不大。因此 里可考慮只須在不鏽鋼上鍍銀即可。第四圖 :ϋ)00與鈦合金（44)真空硬銲試片之銲道橫截 、，且、我（100Χ )，由圖中可觀察出銀鍍層（42 )厚 n w鐸道（4 3) $約4 〇 #m，銲道中無空孔裂缝， 目令佳，可稱得上是相當好的異質接合。銲道中 =真空硬銲的特性，因硬鮮時不需使用助銲 此2免其銲後在銲道的殘留而形成空孔與裂縫。 五圖為以本發明技術製作之鈦合金外殼（51 )與不Group------一一.—1 1一一—___ Tensile strength (kg / c m2 ) -————. Silver plating first group 40 —-———-_ No The second group of 70 is plated in the third group 71. Both sides are made of tensile strength film as the film on the unsilvered layer, but the cost is about 30 microscopic microscopic surface and metallurgical no porosity agent, because the first table It can be seen that the test piece (the first group) without the barrier layer treatment has a direct resistance test requirement (45kg/cm2), and the tensile strength of the base material after plating and silver early layer can reach 7〇kg/cm2 or more. Compared with the eye, the tensile strength is increased by γ 5 %. The third set of test pieces is plated, multi-pass, that is, a thin layer of silver is also plated on the titanium alloy. The strength is only increased by 丨kg/cm2, and the benefit is not significant. Therefore, it is only necessary to plate silver on stainless steel. The fourth picture: ϋ) 00 and titanium alloy (44) vacuum brazed test piece of the weld cross section, and, I (100 Χ), from the figure can be observed silver plating (42) thick nw ( Road (4 3 ) About 4 〇#m, there are no holes in the weld bead, and the order is good. It can be called a fairly good heterojunction. In the weld bead = the characteristics of vacuum brazing, no need to use the flux when it is hard and fresh. This 2 avoids the formation of voids and cracks in the weld bead after welding. Figure 5 is a titanium alloy casing (51) made with the technique of the present invention and

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第13頁 1251518 圖式簡單說明 第一圖 預置型片狀填料組裝法 ίο —不鑛鋼母材。 1 2 --鋁合金填料。 14--鈦合金母材。 1 6 --母材接合面上的銀鍵層。 18 —接合件以爽具固定’並施以l_5psi的壓力。 第二圖 填料毛細吸入型組裝法 10 —不鐵鋼母材（含銀鑛層）。Page 13 1251518 Schematic description of the figure First figure Pre-formed sheet filler assembly method ίο — not mineral steel base material. 1 2 -- Aluminum alloy filler. 14--Titanium alloy base material. 1 6 -- Silver bond layer on the joint surface of the base metal. 18 - The joint is fixed with a squeegee and applied at a pressure of 1-5 psi. Figure 2 Packing capillary suction assembly method 10 - Non-ferrous steel base material (including silver ore layer).

14- -鈦合金母材（含銀鑛層）。 2 1 --膏狀鋁合金填料的位置。 2 3 --接合件以點銲固定。 25——0·02—0·10mm 間隙。 第三圖 欽合金板材與不鐘鋼格網之真空硬鲜抗拉試片 31--鈦合金外殼（厚2mm，曲率半徑200mm )。 3 2 —不鐘鋼格網。14- - Titanium alloy base material (including silver ore layer). 2 1 -- Location of the paste-like aluminum alloy filler. 2 3 -- The joint is fixed by spot welding. 25——0·02—0·10mm clearance. The third picture is the vacuum hard fresh tensile test piece of Qin alloy plate and non-clock steel grid. 31--Titanium alloy shell (thickness 2mm, radius of curvature 200mm). 3 2 — Not the steel grid.

第四圖 硬銲試片銲道橫截面顯微組織（1 0 0 X ) 41 —不鐵鋼。 42 —銀鍵層。 4 3 —鲜道。 t 44- -鈦合金。Figure 4: Brazed test piece weld cross-section microstructure (1 0 0 X) 41 - not iron. 42 — Silver bond layer. 4 3 — Fresh road. t 44- - titanium alloy.

第14頁 1251518 圖式簡單說明 第五圖 鈦合金外殼與不鏽鋼格網硬銲接合實體照片 51- -欽合金外殼。 5 2 —不鐘鋼格網。 ill 第15頁Page 14 1251518 Brief description of the diagram Fifth figure Titanium alloy casing and stainless steel grid hard welded joint photo 51--Chin alloy shell. 5 2 — Not the steel grid. Ill page 15

Claims (1)

1251518 p年β月％日修(更)正替換頁 i________ ___________ 六、申請專利範圍 1 . 一種鈦合金與不鏽鋼的真空硬銲接合方法，包括： a )在不鏽鋼接合面上的銀被覆； b )使用填料為鋁-矽合金填料； c )使用爐具為真空爐。 2 .如申請專利範圍第1項所述之真空硬銲接合方法，硬銲 接合母材為鈦合金與不鏽鋼。 3.如申請專利範圍第1項所述之真空硬銲接合方法，硬銲 接合前須在不鏽鋼接合面上作銀被覆，被覆方法可為化學 銀、丨賤鐘、電鍍。1251518 p year beta month% repair (more) replacement page i________ ___________ VI. Patent scope 1. A vacuum hard bonding method for titanium alloy and stainless steel, comprising: a) silver coating on stainless steel joint surface; b) The filler used is an aluminum-niobium alloy filler; c) the furnace is used as a vacuum furnace. 2. The vacuum hard bonding method according to claim 1, wherein the brazing joining base material is titanium alloy and stainless steel. 3. The vacuum hard soldering method according to claim 1, wherein the stainless steel joint surface is silver-coated before the brazing joint, and the coating method may be chemical silver, a cuckoo clock, or electroplating. 第16頁Page 16