200301784 玖、發明說明200301784 发明, description of the invention
(發明說明應钦明：路日日 H 之技術領域、先前技術、内容、實施方式及圖式簡單說明） 【發明所屬^技術領域】 本發明係關於-種财熱且具有高溫抗氧化性之合金， 以Ni、Cr、A卜Fe為其主要成分。 5 【先前技術】 特別在汽車一排氣觸媒轉換器的應用中，會裝上比 卿m更薄的金屬泊。對此，目前基本上係採用：：鉻— 鋁—合金，例如DE-A 39 08 526及EP-A 〇 516 〇97中所記载 者。此等合金雖因其形成氧化銘而具有相當優良的高溫抗 1〇氧化性之優點，卻同時有耐熱性受到限制的缺點。 另一方面，奥氏體的鎳底原料雖然耐熱，卻會在溫度 > 1000 C，可能在排氣觸媒轉換器中於極端狀態下出現， 劇烈氧化。在-般的情況下會合成氧化絡層。在許多應用 中，此一問題於具有高鎳含量的合金中，可以透過添加一 15定範圍的反應性元素而獲得解決，例如DE-A 44 11 228中 所述者。此等原料經常含有較高含量的碳及氮，因而受劇 烈硬化的影響而不適用於壓延羯。在所舉案例中為〇•⑻i 一 0.15質量的碳及〇·25—12質量_0/〇的氮。此外，其中通 常含有超過50質量_%的鎳，導致其價格昂貴。像De_a料 20 11 228中，鎳約為65質量-%。 在含有大約30%之低鎳含量的廉價原料族群之研究中 ，特別引人注意的是其中僅含有相當少量的鋁。在經常被 使用的原料L4876/合金800中，含量低於1質量-%。如果將 該等合金長時間置於100(rc或者更高的空氣溫度中，主要 200301784 玖、發明說明 會在其等的表面上形成氧化鉻。 在鎳含量介於20%與40%間之此種合金中，當以傳統 的製造方式經過鑄旋澆鑄及後續的熱加工一及冷加工成型 後，銘含量會提高，形成易脆裂的金屬間相，一方面對熱 5 加工成型，另一方面亦對壓延箔造成影響。因此文獻中已 有利用爐垢來檢驗加工方法，藉而得以防止此種易脆的相 。例如EP-A 0 497 992中記載的製造方式係藉一熔融液之 相當快速的凝結。然而此方法有無法製造均勻的，其組織 結構就像利用鑄錠澆鑄或連續澆鑄所製成之材料一樣均質 10的，寬帶材之缺點。因此並不適用於製造比40μιη更薄的 金屬箔，而且在壓延成品的過程中，其等之微孔和雜質會 引發生成孔隙。此外，有嘗試利用被覆較易成型之基礎材 料來提高鋁含量者，例如DE-A 199 57 646中所述者。雖然 這是一個通用的方法，但是經常發生該方法會導致額外的 15 ，成本密集的操作步驟之缺失。 依據 ΕΡ-Α 0801 140，一含有 30一35% Ni、14一 18%(Explanation of the invention should be clear: the technical field, prior art, content, implementation and drawings of Lu Riri H are briefly explained. [Technical field to which the invention belongs] The present invention relates to a kind of financial heat and high temperature oxidation resistance. The alloy contains Ni, Cr, and Fe as its main components. 5 [Previous technology] Especially in the application of automobile-exhaust catalyst converter, it will be fitted with a thinner metal moor than Qing m. In this regard, currently: chromium-aluminum-alloys, such as those described in DE-A 39 08 526 and EP-A 0 516 097. Although these alloys have the advantage of excellent oxidation resistance at high temperature due to the formation of oxidation inscriptions, they also have the disadvantage of limited heat resistance. On the other hand, although the austenitic nickel base material is heat-resistant, it may appear in extreme conditions in the exhaust catalyst converter at temperatures > 1000 C and undergo severe oxidation. Under normal conditions, an oxide complex will be synthesized. In many applications, this problem is solved in alloys with a high nickel content by adding a range of reactive elements, such as those described in DE-A 44 11 228. These materials often contain relatively high levels of carbon and nitrogen and are therefore not suitable for calendaring because of the effects of severe hardening. In the examples given, it is 0 • ⑻i—0.15 mass carbon and 0.25—12 mass_0 / 〇 nitrogen. In addition, it usually contains more than 50% by mass of nickel, making it expensive. Like De_a material 20 11 228, nickel is about 65 mass-%. In the study of a group of inexpensive raw materials with a low nickel content of about 30%, it was particularly noticeable that it contained only a relatively small amount of aluminum. In the frequently used raw material L4876 / Alloy 800, the content is less than 1 mass-%. If these alloys are exposed to air temperatures of 100 ° C or higher for a long period of time, the main 200301784 玖, the invention description will form chromium oxide on the surface of them. The nickel content is between 20% and 40%. Among these alloys, when the traditional manufacturing method is used for casting and subsequent hot working and cold working and forming, the content of the metal will increase to form a brittle intermetallic phase. On the one hand, it is processed by hot 5 forming; It also affects the rolled foil. Therefore, in the literature, furnace scale has been used to check the processing method, thereby preventing this fragile phase. For example, the manufacturing method described in EP-A 0 497 992 is equivalent to the use of a molten liquid. Fast setting. However, this method can not be made uniform. Its structure is as homogeneous as that of 10 made by ingot casting or continuous casting. The disadvantages of broadband materials. Therefore it is not suitable for making thinner than 40μιη Metal foil, and in the process of rolling the finished product, their micropores and impurities will cause the generation of pores. In addition, there are attempts to increase the aluminum content by using a base material that is easier to form. For example, as described in DE-A 199 57 646. Although this is a general method, it often occurs that this method results in an additional 15, cost-intensive operating steps missing. According to EP-A 0801 140, one contains 30 one 35% Ni, 14-18%
Cr ’ 0.5 - 1.5% Nb + Ta、0.8 - 1 ·5〇/〇 A1、〇 2 一 〇 5% Μη， 以及含Ni、Ca與Mg量的合金，係以鑄錠澆鑄—熱加工成 型一冷加工成型製作。惟該申請案中所記載之氧化試驗僅 20以850°C的溫度進行’而850°C雖然應用於柴油機是足夠的 ，卻顯著地低於鄂圖發動機中之排氣管道的最高溫度。此 點特別在適用於因基於觸媒轉換器的快速啟動性能，而必 需將其儘可能置放在靠近發動機處的情形。惟已知類似的 合金，其含有2%以下之紹添加量及少於2〇%之鉻，易於形 7 200301784 5久、發明說明 成鋁一及，當其含有鈦時，鈦氮化物，並基於此原因而無 法做為鄂圖一發動機之排氣觸媒轉換器的承載箔。 C發明内容;j 因此，本發明之課題在於提供一種便宜且均質的原料 ，其具有可與鐵一鉻一鋁一合金相比較之高溫抗氧化性， 但是在1000°c顯示出至少高出50%的熱拉強度，且可利用 傳、、'充的~技術及後續的熱—及冷加工成型加以製造。 此課題可以利用一種耐熱且具有高溫抗氧化性之合金 而獲得解決，其具有如后之組成（質量_%) ·· 30-40% Ni 15—23% Cr 〇·〇1-0.07% Y及/或Hf及/或心 < 0.15% Μη 其餘為Fe及因冶煉而生成之雜質。 依據本發明之合金的詳細優點將引用於後述之請求内 容。 一較佳合金之特徵在於具有下列組成（質量: 30- 40% Ni !5-23% Cr 〇·01 —0·ϋ7% Y及 / 或 Hf及 / 或 Zr <0.15% Μη 其餘為Fe及因冶煉而生成之雜質。 另一可能的合金之特徵在於具有下列組成（質量: 30.5 — 37% Ni 200301784 玖、發明說明 15-22% Cr 4.0-5.5% A1 0.04-0.1% Μη 至多0.04% Υ 5 至多 0.05% Hf 至多 0.03% Zr 其餘為Fe及因冶煉而生成之雜質。 另一較佳合金之特徵在於具有下列組成（質量-%): 30- < 33% Ni 10 19-22% Cr > 4.0- < 5.5% A1 0.01 — <0.05% Y及/或Hf及/或Zr 0.04- < 0.15% Μη 其餘為Fe及因冶煉而生成之雜質。 15 合適的總量為Cr + A1幺28%，且Y + Hf + Zr <0.15% 依據本發明之合金的製造方法，特徵在於，該合金在 經過冶煉後係透過鑄錠一或連續澆鑄，以及熱一及冷軋， 和必需的中間退火處理而產生。 如此所產生之合金在其最終的應用前，以在l〇〇〇°C至 20 1200°C的溫度範圍内進行溶體化退火為宜。 依據本發明之合金特別適合於應用至下列領域： -運輸工具之排氣系統的構件，特別是應用於汽車之 金屬觸媒轉換器及排氣管； -航空科技中之建構元件，特別是急速轉動的渦輪機； 200301784 玖、發明說明 -燃料電池的建構元件； -熱敏電阻或電阻材料； -閥門材料； •柴油機一熱線引火塞； 5 - λ一探針之建構元件； -溶爐結構之構件，特別是要承受高溫的構造元件； -金屬噴絲。 圖式簡單說明 第1圖為例示LB 878及LB 895在1100°c下於空氣中轉 10移後之單位質量的變化； 第2圖顯示例示lB 895和15 1007在1100°C下於空氣中 轉移後之單位質量的變化。 【貧施方式】 為防止Ni—Al—型之金屬間相的產生，鎳含量以低於 貝量/〇為且。同時令人驚訝地，其顯示易破裂的性質可 猎而降低，而就錳則規定0.15質量％之上限。類似之具有 曰遍超過2質量％錳含量的合金，在熱加工成型期間易於 產生邊緣fe/f裂及表面破裂。其鉻含量必需超過15質量 2〇猎此而可以在開始時的氧化過程中形成阻止氮滲入並從而 2〇阻錢化物之形成的覆蓋層。除此之外，為了使氧化链的 μ蒦作用發揮效應，基本上I呂含量至少要有4質量％。基 於生產性之故，鋁和鉻的總含量不能超過28質量。為了 =所需的高溫抗氧化性，必需添加反應性元素。然而其 含量過高時會在加工成型過程導致裂痕，故其總量限制在 10 200301784 玖、發明說明 至多0.15質量％。在依據本發明之合金中，不同的元素有 相當窄之公差限制實具有特殊意義。 組成例係如表1所不。 表1化學組成 含量/質量_% LB 878 LB 895 151007 Ni 30.7 32.0 30.5 Cr 15.5 20.8 19.85 A1 1 4.9 4.1 5.15 Μη 0.07 0.08 0.06 Υ 0.01 0.02 0.02 Hf 0.04 Zr 0.02 將例示的合金熔煉做為實驗室進料（LB)，澆鑄成錠塊 並熱軋成4.5 mm或5 mm。和適業上慣用的組成，即錳含 量介於0.5及1質量的類似合金相反，可以良好地進行熱 加工成型。當試圖以較高的錳含量進行時，反而會引發邊 1〇緣斷裂或表面破裂。同樣地，添加高溫下會產生氧化缺陷 的釔也必需在狹窄的範圍内進行，因為高釔含量也會妨礙 加工成型性。這點對於有效元素釔（γ)、铪（Hf)、锆（^)的 總合而言也是成立的。 除去表面的鱗皮後，將其製作成表面積約1〇 cm2的試 15品並施以溶體化退火。這些是在1UKTC下，於空氣中總共 轉移400小時。在每次100小時的循環之後，測量質量變化 並鑑定表面氧化物。質量變化示於第1圖，其處於和我們 從Fe—Cr—A1—合金所認知者相同的期望等級，而適於應 11 200301784 玖、發明說明 用做為供金屬的排氣觸媒轉換器用之載體。值得一提的是 ，沒有發現剝落的情形。例示的LB 895(第1圖）以其特別輕 微的質量變化而顯得突出，其可歸因於額外添加铪與結。 因此，只要透過預先規劃範圍較嚴緊的公差限度，其添加 5 依然是有利的，即便是可能發生的生產上之問題，依然可 以避開。 在400小時ll〇〇°C下的轉移後所進行之衍射儀測量證 貫在表面上形成銘一鉻一混合氧化物，其結果導致高抗氧 化性。 10 特別是和高溫氧化性有關的優點，在試品於轉移前經 過溶體化退火的處理中獲得證明。 依據本發明之合金的的屈服極限在1000°c下平均達到 50 MPa，代表其相對於習知的Fe—Cr—八丨合金提高了大約 60%，而在供應用做為汽車之金屬的觸媒轉換器載體上相 15 當的值得期待。 【圖式簡單說明】 第1圖為例示LB 878及LB 895在llOOt下於空氣中轉 移後之單位質量的變化； 第2圖顯示例示LB 895和15 1007在11〇〇。(：下於空氣中 20 轉移後之單位質量的變化。 【圖式之主要元件代表符號表】 Μ ή、 12Cr '0.5-1.5% Nb + Ta, 0.8-1.5 · 50 / 〇A1, 〇2, 105% Mn, and alloys containing Ni, Ca, and Mg contents are cast by ingot casting-hot working forming-cold working Molding. However, the oxidation test described in this application is only performed at a temperature of 850 ° C '. Although 850 ° C is sufficient for diesel engines, it is significantly lower than the maximum temperature of the exhaust pipe in the Etu engine. This is especially applicable when the catalyst-based converter is required to be placed as close to the engine as possible due to its fast start performance. However, it is known that similar alloys, which contain less than 2% of added amount and less than 20% of chromium, are easy to shape. 7 200301784 5 years, the invention description is aluminum, and when it contains titanium, titanium nitride, and For this reason, it cannot be used as the carrier foil of the exhaust catalyst converter of the Etu-1 engine. C Summary of the Invention; j Therefore, the problem of the present invention is to provide a cheap and homogeneous raw material which has high temperature oxidation resistance comparable to iron-chromium-aluminum-alloy, but shows at least 50% higher at 1000 ° c. % Hot tensile strength, and it can be manufactured by heat transfer, cold-filling, and subsequent hot- and cold-work forming. This problem can be solved by using a heat-resistant and high-temperature oxidation resistant alloy, which has the following composition (mass_%): 30-40% Ni 15-23% Cr 〇〇〇-0.07% Y and / Or Hf and / or heart < 0.15% Μη The balance is Fe and impurities generated by smelting. The detailed advantages of the alloy according to the present invention will be cited in the claims described below. A preferred alloy is characterized by having the following composition (mass: 30-40% Ni! 5-23% Cr 〇01--0 · ϋ7% Y and / or Hf and / or Zr < 0.15% Μη and the rest Fe and Impurities generated by smelting. Another possible alloy is characterized by the following composition (mass: 30.5 — 37% Ni 200301784 玖, description of the invention 15-22% Cr 4.0-5.5% A1 0.04-0.1% Μη up to 0.04% Υ 5 up to 0.05% Hf up to 0.03% Zr The rest are Fe and impurities generated by smelting. Another preferred alloy is characterized by having the following composition (mass-%): 30- < 33% Ni 10 19-22% Cr > 4.0- < 5.5% A1 0.01 — < 0.05% Y and / or Hf and / or Zr 0.04- < 0.15% Μη The rest is Fe and impurities generated by smelting. 15 A suitable total amount is Cr + A1 幺 28%, and Y + Hf + Zr < 0.15%, the method for manufacturing an alloy according to the present invention, characterized in that, after smelting, the alloy is cast through ingot one or continuous casting, and hot one and cold rolling, and It is produced by the necessary intermediate annealing treatment. The alloy thus produced is used at a temperature range of 1000 ° C to 20 1200 ° C before its final application. The solution annealing is suitable. The alloy according to the present invention is particularly suitable for application to the following fields:-components of exhaust systems of transportation vehicles, especially metal catalyst converters and exhaust pipes for automobiles;-aviation technology Construction elements, especially fast-rotating turbines; 200301784 发明, description of the invention-construction elements of fuel cells;-thermistors or resistance materials;-valve materials; • diesel engine hot-plugs; 5-λ-probe Construction elements;-Components of the melting furnace structure, especially those that must withstand high temperatures;-Metal spinneret. Brief description of the figure The first picture is an example of LB 878 and LB 895 after being moved in air at 1100 ° c for 10 movements. Unit mass change; Figure 2 shows an example of unit mass change after lB 895 and 15 1007 are transferred in the air at 1100 ° C. [Poor application method] To prevent the generation of Ni—Al—type intermetallic phases The nickel content is below the amount of shellfish / 0. At the same time, surprisingly, it shows that the easy-to-break property can be hunted and reduced, while the upper limit of 0.15% by mass is specified for manganese. The alloy with a manganese content of% is liable to produce edge fe / f cracks and surface cracks during hot forming. Its chromium content must exceed 15 masses. This can be formed during the initial oxidation process to prevent nitrogen infiltration and thus 2 〇The cover layer formed by the hindering compound. In addition, in order to make the μ 蒦 action of the oxidized chain work, the content of I is basically at least 4% by mass. For productivity reasons, the total content of aluminum and chromium cannot exceed 28 masses. In order to obtain the required high-temperature oxidation resistance, reactive elements must be added. However, when its content is too high, it will cause cracks during processing and molding, so the total amount is limited to 10 200301784 发明, the description of the invention is at most 0.15% by mass. In the alloys according to the invention, the relatively narrow tolerance limits of different elements are of special significance. Composition examples are shown in Table 1. Table 1 Chemical composition content / mass_% LB 878 LB 895 151007 Ni 30.7 32.0 30.5 Cr 15.5 20.8 19.85 A1 1 4.9 4.1 5.15 Mn 0.07 0.08 0.06 Υ 0.01 0.02 0.02 Hf 0.04 Zr 0.02 The exemplified alloy melting is used as the laboratory feed (LB), cast into ingots and hot rolled to 4.5 mm or 5 mm. Contrary to the commonly used composition in the industry, that is, similar alloys with manganese content between 0.5 and 1 mass, they can be hot-formed well. Attempts at higher manganese content will instead cause edge 10 edge breaks or surface cracking. Similarly, the addition of yttrium, which causes oxidation defects at high temperatures, must also be performed within a narrow range, because high yttrium content can also impede processability. This also holds true for the total of the effective elements yttrium (γ), hafnium (Hf), and zirconium (^). After removing the scale on the surface, it was made into a test sample having a surface area of about 10 cm2 and subjected to solution annealing. These are a total of 400 hours of air transfer at 1UKTC. After each 100-hour cycle, mass changes were measured and surface oxides were identified. The mass change is shown in Figure 1. It is at the same level of expectation as we know from Fe—Cr—A1—alloys, and it is suitable for use as an exhaust catalyst converter for metal in accordance with 11 200301784. Carrier. It is worth mentioning that no peeling was found. The exemplified LB 895 (Figure 1) stands out with its particularly slight mass change, which can be attributed to the additional addition of knots and knots. Therefore, as long as the tighter tolerance limits are planned in advance, its addition 5 is still beneficial, and even production problems that may occur can still be avoided. The diffractometer measurement performed after the transfer at 400 ° C for 400 hours consistently confirmed the formation of a chromium-mixed oxide on the surface, which resulted in high oxidation resistance. 10 In particular, the advantages related to high-temperature oxidizing properties have been demonstrated in samples that have been subjected to solution annealing before transfer. The yield limit of the alloy according to the present invention reaches an average of 50 MPa at 1000 ° C, which represents an increase of about 60% compared to the conventional Fe-Cr-VIII alloy, and the contact of the alloy used as a metal for automobiles The media converter carrier is worth looking forward to. [Brief description of the figure] Figure 1 illustrates the change in unit mass of LB 878 and LB 895 after being transferred in the air at 1100 t; Figure 2 illustrates the example of LB 895 and 15 1007 at 1100. (: The change in unit mass after the transfer in the air 20. [Representative symbol table of the main elements of the drawing] Ｍή, 12