TWI463020B - Acier inoxydable duplex - Google Patents
Acier inoxydable duplex Download PDFInfo
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- TWI463020B TWI463020B TW096121708A TW96121708A TWI463020B TW I463020 B TWI463020 B TW I463020B TW 096121708 A TW096121708 A TW 096121708A TW 96121708 A TW96121708 A TW 96121708A TW I463020 B TWI463020 B TW I463020B
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Description
本發明係關於雙重不銹鋼,更特別是以不對其造成任何限制之方式,用以製造供材料製造裝置(化學、石油化學、造紙和近海工業)或能量製造裝置用之結構組件,及亦係關於自此鋼製造板、條、棒、棍、線或塊件之方法。The present invention relates to double stainless steel, and more particularly to structural components for use in material manufacturing equipment (chemical, petrochemical, paper and offshore industries) or energy manufacturing equipment in a manner that does not impose any limitation thereto, and also relates to A method of making plates, strips, rods, sticks, wires or blocks from this steel.
一般而言,在許多應用上,如在前述工業或在農食品工業上,包括自成形的棍或線(焊接的格網..等)、塊件(應力施加器..等)、軸幹..等製得之零件,此鋼可以作為304L型不銹鋼的替代品。其亦可製造鑄件和鍛件。In general, in many applications, such as in the aforementioned industries or in the agro-food industry, including self-forming sticks or wires (welded grids, etc.), blocks (stress applicators, etc.), shafts .. and other parts, this steel can be used as a substitute for 304L stainless steel. It can also make castings and forgings.
用於此目的,已經知道304型和304L型的不銹鋼等級品,其於經退火的狀態中,基本上具有沃斯田鐵微結構。在經冷加工的狀態下,它們可以進一步含有可變比例的麻田散鐵。但是,這些鋼包括大量添加的鎳,其成本通常非常高。此外,就技術觀點,這些等級品因為在經退火的狀態下之抗張性質欠佳(特別是屈服強度)及耐應力腐蝕性相當低,所以在某些應用上引發一些問題。For this purpose, stainless steel grades of type 304 and 304L are known which, in the annealed state, have substantially a Wolster iron microstructure. In the cold worked state, they may further contain a variable proportion of 麻田散铁. However, these steels include a large amount of added nickel, which is usually very expensive. In addition, from a technical point of view, these grades cause problems in some applications because of the poor tensile properties (especially yield strength) and stress corrosion resistance in the annealed state.
也已經知道沃斯田-肥粒鐵型不銹鋼,其主要由肥粒鐵和沃斯田鐵之混合物所構成,如,根據EP10088標準的鋼1.4362、1.4655、1.4477、1.4462、1.4507、1.4410、1.4501和1.4424,其皆含有超過3.5%鎳。這些鋼特別耐得住腐蝕和應力腐蝕。It is also known that the Worthfield-fertilizer iron type stainless steel is mainly composed of a mixture of ferrite iron and Worthite iron, for example, steels 1.4362, 1.4655, 1.4477, 1.4462, 1.4507, 1.4410, 1.4501 and according to the EP10088 standard. 1.4424, which all contain more than 3.5% nickel. These steels are particularly resistant to corrosion and stress corrosion.
也已經知道肥粒鐵型或肥粒-麻田散鐵不銹鋼等級品,用於明確的熱處理範圍,其微結構由兩個構份(肥粒鐵和麻田散鐵,以50/50比例為佳,如根據EN10088標準的1.4017等級品)所構成。這些等級品(鉻含量通常低於20%)具有高抗張機械性質,但耐蝕性無法令人滿足。It is also known that the ferrite iron type or the fat grain-Mita loose iron stainless steel grade is used for a clear heat treatment range, and its microstructure consists of two components (fertilizer iron and 麻田散铁, preferably 50/50 ratio, It is composed of 1.4017 grade according to EN10088 standard. These grades (typically less than 20% chromium) have high tensile mechanical properties, but corrosion resistance is not satisfactory.
此外,也希望簡化製造不銹鋼板、條、棒、棍、線或塊件之方法。In addition, it would be desirable to simplify the method of making stainless steel sheets, strips, rods, sticks, wires or blocks.
本發明的目的是要藉由提供具有良好機械性質(特別是在經退火或經溶解處理的狀態中之抗張強度高於400或甚至450MPa)、高耐蝕性(特別是與304L相同或優於304L)、在焊接區之良好微結構安定性和良好韌性、且未添加昂貴外加元素之不銹鋼及提供以較容易實施的方法,自此鋼製造板、條、棒、棍、線或塊件,以補救以前技術的鋼和製法之缺點。The object of the present invention is to provide high mechanical properties (especially tensile strength in the state of annealed or dissolved treatment of more than 400 or even 450 MPa), high corrosion resistance (especially the same or better than 304L) 304L), stainless steel with good microstructure stability and good toughness in the weld zone, and without the addition of expensive additional elements, and providing a method that is easier to implement, since the steel is used to make plates, strips, rods, sticks, wires or blocks, To remedy the shortcomings of the prior art steel and manufacturing methods.
就此目的,本發明的第一個標的是一種雙重不銹鋼,其組成,以重量%計,由以下各者所組成:C0.05%、21%Cr25%、1%Ni2.95%、0.16%N0.28%、Mn2.0%、Mo+W/20.50%、Mo0.45%、W0.15%、 Si1.4%、Al0.05%、0.11%Cu0.50%、S0.010%、P0.040%、Co0.5%、稀土金屬(REM)0.1%、V0.5%、Ti0.1%、Nb0.3%、Mg0.1%、餘者是鐵和源自冶煉之雜質,且其微結構由沃斯田鐵和35至65體積%肥粒鐵所組成,該組成另滿足下列關係:40IF 70,以40IF 60為佳其中IF =6x(%Cr+1.32x%Mo+1.27x%Si)-10x(%Ni+24x%C+16.15x%N+0.5x%Cu+0.4x%Mn)-6.17且ILCR 30.5,以ILCR 32為佳其中ILCR =%Cr+3.3x%Mo+16x%N+2.6x%Ni-0.7x%Mn。For this purpose, the first object of the invention is a double stainless steel whose composition, in weight %, consists of: C 0.05%, 21% Cr 25%, 1% Ni 2.95%, 0.16% N 0.28%, Mn 2.0%, Mo+W/2 0.50%, Mo 0.45%, W 0.15%, Si 1.4%, Al 0.05%, 0.11% Cu 0.50%, S 0.010%, P 0.040%, Co 0.5%, rare earth metal (REM) 0.1%, V 0.5%, Ti 0.1%, Nb 0.3%, Mg 0.1%, the remainder is iron and impurities derived from smelting, and its microstructure consists of Worthite iron and 35 to 65 vol% ferrite iron, which further satisfies the following relationship: 40 I F 70 to 40 I F 60 is preferably wherein I F = 6x (% Cr + 1.32 x % Mo + 1.27 x % Si) - 10 x (% Ni + 24 x % C + 16.15 x % N + 0.5 x % Cu + 0.4 x % Mn) - 6.17 and I LCR 30.5 to I LCR 32 is preferred wherein I LCR = % Cr + 3.3 x % Mo + 16 x % N + 2.6 x % Ni - 0.7 x % Mn.
根據本發明之鋼亦可包括下列單獨或合併的選用特徵:- 肥粒鐵的比例介於35和55體積%之間; - 鉻含量介於22和24重量%之間;- 錳含量低於1.5重量%;- 鈣含量低於0.03重量%;和- 鉬含量高於0.1重量%。The steel according to the invention may also comprise the following individual or combined optional features: - the ratio of ferrite iron is between 35 and 55 vol%; - a chromium content of between 22 and 24% by weight; - a manganese content of less than 1.5% by weight; - a calcium content of less than 0.03% by weight; and - a molybdenum content of more than 0.1% by weight.
本發明的第二個標的由自根據本發明之鋼製造熱軋板、條或線圈之方法所組成,其中:- 提供本發明之組成之鋼之鑄錠或厚片;和- 該鑄錠或厚片於介於1150和1280℃之間的溫度熱軋,以得到板、條或線圈。A second subject of the invention consists of a method for producing a hot rolled sheet, strip or coil from a steel according to the invention, wherein: - an ingot or slab of steel providing the composition of the invention; and - the ingot or The slab is hot rolled at a temperature between 1150 and 1280 ° C to obtain a plate, strip or coil.
一個特別的實施法中,該鑄錠或厚片於介於1150和1280℃之間的溫度熱軋,以得到所謂的四開尺寸(quarto)板;之後,於介於900和1100℃之間的溫度進行熱處理;和該板藉空氣淬火而冷卻。In a particular embodiment, the ingot or slab is hot rolled at a temperature between 1150 and 1280 ° C to obtain a so-called quarto plate; thereafter, between 900 and 1100 ° C The temperature is heat treated; and the plate is cooled by air quenching.
本發明的第三個標的由自根據本發明之鋼製造熱軋棒或棍之方法所組成,其中:- 提供根據本發明之組成之鋼的連續鑄錠或塊料;- 該鑄錠或塊料於介於1150和1280℃之間的溫度熱軋,以得到棒狀物(其經空氣冷卻)或線料之線圈(其經水冷卻);及之後,選擇性地:- 於介於900和1100℃之間的溫度進行熱處理;和- 該棒狀物或線料經淬火冷卻。A third object of the invention consists of a method for producing a hot rolled rod or stick from steel according to the invention, wherein: - a continuous ingot or block of steel providing a composition according to the invention; - the ingot or block Hot rolling at a temperature between 1150 and 1280 ° C to obtain a rod (which is cooled by air) or a coil of wire (which is cooled by water); and thereafter, selectively: - between 900 Heat treatment at a temperature between 1100 ° C; and - the rod or strand is quenched and cooled.
一個特別的實施法中,在冷卻之後,在該棒上進行冷拉伸操作或在該桿上進行模具拉伸操作。In a particular embodiment, after cooling, a cold drawing operation is performed on the rod or a mold stretching operation is performed on the rod.
本發明亦含括一種製造鋼塊件之方法,其中冷成型操作在根據本發明而得到的熱軋棒上進行;及亦含括一種製造鋼鍛件之方法,其中根據本發明得到的熱軋棒被切成金屬塊並於之後在該金屬塊上介於1100℃和1280℃之間時進行鍛造操作。The present invention also encompasses a method of making a steel block, wherein the cold forming operation is performed on a hot rolled bar obtained in accordance with the present invention; and also includes a method of making a steel forging, wherein the hot rolled bar obtained in accordance with the present invention The forging operation is performed when it is cut into metal pieces and then between 1100 ° C and 1280 ° C on the metal block.
本發明另含括可藉根據本發明之方法得到之多種產物及其用途,如:-熱軋鋼四開尺寸板,其厚度介於5和100毫米之間,及條和線圈,其可用以製造供材料製造或能量製造裝置用之結構組件,特別是供在介於-100和300℃之間操作(以在介於-50和300℃之間操作為佳)的材料和能量製造裝置用之結構組件;-冷軋鋼條,其可藉熱軋線圈之冷軋處理而得;-直徑為18毫米至250毫米的熱軋棒和直徑為4毫米至60毫米的冷拉伸棒,此產物可用以製造機械零件(如幫浦、閥軸、馬達和引擎軸)及在腐蝕性介質中操作之接合器;-直徑為4毫米至30毫米的熱軋桿和直徑為0.010毫米至20毫米的模具拉伸桿或線,此產物可用以製造冷成型的套組、農食品工業、油和礦萃取、或製造供化學品、礦物或食品過濾用之梭織或針織金屬織品;-塊件;-鍛件,其可用以製造托架或接合器;和-鑄件,其可藉由鑄造根據本發明之鋼而得。The invention further comprises a plurality of products obtainable by the process according to the invention and uses thereof, such as: - hot rolled steel four-open size plates having a thickness between 5 and 100 mm, and strips and coils, which can be used for manufacturing Structural components for the manufacture of materials or energy-generating devices, in particular for materials and energy manufacturing devices operating between -100 and 300 ° C (for operation between -50 and 300 ° C) Structural components; - cold rolled steel bars, which can be obtained by cold rolling of hot rolled coils; - hot rolled bars of 18 mm to 250 mm in diameter and cold drawn bars of 4 mm to 60 mm in diameter, this product is available For the manufacture of mechanical parts (such as pumps, valve shafts, motors and engine shafts) and adapters operating in corrosive media; - hot rolled rods from 4 mm to 30 mm in diameter and moulds from 0.010 mm to 20 mm in diameter Stretching rods or threads, this product can be used to make cold formed kits, agro-food industry, oil and mineral extraction, or to fabricate woven or knitted metal fabrics for chemical, mineral or food filtration; - block; - a forging that can be used to make a bracket or adapter; And castings which can be obtained by casting steel according to the invention.
讀完僅作為例子的下列描述,會瞭解本發明的其他特徵和優點。Other features and advantages of the present invention will be apparent from the following description, taken as example.
根據本發明之雙重不銹鋼包含以下定義之含量。The double stainless steel according to the present invention contains the content defined below.
此等級品的碳含量等於或低於0.05重量%,以低於0.03重量%為佳。這是因為此元素的含量過高會因為提高碳化鉻在焊接之受熱影響區域中析出的風險而降低局部耐蝕性。The grade has a carbon content of 0.05% by weight or less, preferably less than 0.03% by weight. This is because the excessive content of this element reduces the local corrosion resistance by increasing the risk of precipitation of chromium carbide in the heat affected zone of the weld.
此等級品的鉻含量介於21和25重量%之間,以介於22和24重量%之間為佳,以得到良好的耐蝕性,此耐蝕性至少與類型304或304L等級品所得者相當。This grade has a chromium content between 21 and 25% by weight, preferably between 22 and 24% by weight, for good corrosion resistance, which is at least comparable to that of the type 304 or 304L grade. .
此等級品的鎳含量介於1和2.95%之間,以等於或低於2.7%,或甚至低於2.5重量%為佳。添加此形成沃斯田鐵的元素以得到良好的裂縫耐蝕性。含量大於1%且以大於1.2重量%為佳時,其於抵抗引發凹洞(pitting)腐蝕方面具有有利的效果。但限制其含量,此因高於2.95重量%時,觀察到耐凹洞傳播性降低之故。添加鎳也使其能夠得到良好的韌度/延展性妥協,此因其具有韌性轉變曲線朝向低溫轉變的優點之故,此於製造厚的四開尺寸板(其韌度性質相當重要)時特別有利。The nickel content of this grade is between 1 and 2.95%, preferably equal to or lower than 2.7%, or even less than 2.5% by weight. This element forming the Vostian iron is added to obtain good crack corrosion resistance. When the content is more than 1% and more preferably more than 1.2% by weight, it has an advantageous effect against the initiation of pitting corrosion. However, the content was limited, and when it was more than 2.95 wt%, the pit-resistant property was observed to be lowered. The addition of nickel also makes it possible to obtain a good toughness/ductility compromise due to its advantage of having a toughness transition curve towards a low temperature transition, which is especially true when manufacturing thick four-size plates, where the toughness properties are important. advantageous.
因為限制根據本發明之鋼之鎳含量,已經發現到,為了要在介於900℃和1100℃之間的熱處理之後得到適當的沃斯田鐵含量,所以必須添加不尋常的大量的其他形成沃斯田鐵的元素及限制形成肥粒鐵之元素的含量。Since the nickel content of the steel according to the invention is limited, it has been found that in order to obtain a suitable Worth iron content after heat treatment between 900 ° C and 1100 ° C, it is necessary to add an unusually large amount of other formations. The elements and limits of the iron form the content of the element of the ferrite.
此等級品的氮含量介於0.16和0.28重量%之間,此通常意謂氮於冶煉期間內加至鋼中。此形成沃斯田鐵的元素先使其能夠得到肥粒鐵-沃斯田鐵兩相雙重鋼(含有適當比例的沃斯田鐵,具有良好的應力耐蝕性),及亦得到具有高機械強度的金屬。其亦使其在焊接處之受熱影響區域能夠具有良好的微結構安定性。限制其最大含量,這是因為,高於0.28%時,會觀察到溶解度問題;在厚片、塊料、鑄錠、鑄件或焊接處的固化期間內,會形成氣泡之故。The nitrogen content of this grade is between 0.16 and 0.28% by weight, which generally means that nitrogen is added to the steel during the smelting period. This element of the formation of the Worthite iron first enables it to obtain the ferrite-iron-Worstian iron two-phase double steel (containing a proper proportion of Worthite iron, which has good stress and corrosion resistance), and also has high mechanical strength. Metal. It also enables it to have good microstructure stability in the heat affected zone of the weld. The maximum content is limited because, above 0.28%, solubility problems are observed; during solidification of slabs, blocks, ingots, castings or welds, bubbles are formed.
錳(其亦為在低於1150℃形成沃斯田鐵的元素)的含量維持低於2.0重量%,且以低於1.5重量%為佳,此因此元素不利於許多方面之故。因此,此等級品於冶煉和精煉的期間內會發生問題,此因其攻擊長柄勺所用的一些耐火物之故。因此,必須更頻繁地替換這些昂貴的元素,因此使得製程更常被中斷。The content of manganese, which is also an element which forms Worth iron at less than 1150 ° C, is maintained below 2.0% by weight, and preferably less than 1.5% by weight, so that the element is disadvantageous in many respects. Therefore, this grade will have problems during the smelting and refining period due to some of the refractory used to attack the ladle. Therefore, these expensive elements must be replaced more frequently, thus making the process more interrupted.
鐵-錳之添加(常用以使得此等級品加至組成物中)亦含有可觀量的磷和硒,不希望將這些元素引至鋼中,且在精煉此等級品時,難以移除這些元素。錳也會藉由限制去碳作用之可能性而干擾此精煉。其於方法的進一步下游處亦有問題,其因為硫化錳(MnS)和經氧化的夾雜物形成而損及等級品的耐蝕性。此元素常被加至希望富含氮的等級品中,以提高元素於等級品中之溶解度。錳含量不足時,鋼中無法達到此氮含量。但是,本發明者發現,可以限制錳於根據本發明之鋼中之添加,並同時添加足量的氮,以在基礎材料的肥粒鐵-沃斯田鐵平衡上得到所欲的效果及安定焊接處之受熱影響區域。The addition of iron-manganese (usually such that this grade is added to the composition) also contains appreciable amounts of phosphorus and selenium. It is undesirable to introduce these elements into the steel and it is difficult to remove these elements when refining this grade. . Manganese also interferes with this refining by limiting the possibility of decarburization. It is also problematic further downstream of the process, which suffers from the corrosion resistance of grades due to the formation of manganese sulfide (MnS) and oxidized inclusions. This element is often added to grades that are expected to be rich in nitrogen to increase the solubility of the element in the grade. When the manganese content is insufficient, this nitrogen content cannot be reached in the steel. However, the inventors have found that it is possible to limit the addition of manganese to the steel according to the invention, and at the same time add a sufficient amount of nitrogen to achieve the desired effect and stability on the ferrite-Worthian iron balance of the base material. Heat affected area of the weld.
鉬(一種形成肥粒鐵的元素)維持於含量低於0.45重量%,鎢則維持於含量低於0.15重量%。但這兩種元素的含量使得Mo+W/2的和低於0.50重量%,以低於0.4重量%為佳,低於0.3重量%更佳。這是因為本發明者已發現,藉由維持這兩種元素及它們的含量和低於所示的值,不會觀察到脆化的介金屬之析出,藉此,藉由使得在熱處理之後或熱加工之後的板或條以空氣冷卻,特別能夠緩和此製造鋼板或條之方法。此外,已觀察到,藉由控制在聲明的限制內的這些元素,等級品的可焊性獲改良。但是,較佳地,最低鉬含量維持於0.1%,以改良此等級品的熱鍛造性。此外,冶煉鉬含量低於0.1%的等級品,會對此等級品的回收廢料之使用造成很大的限制,因此引起了加工問題,特別是必須使用由100%純鐵合金構成之進料。Molybdenum (an element forming ferrite iron) is maintained at a content of less than 0.45 wt%, and tungsten is maintained at a content of less than 0.15 wt%. However, the content of these two elements is such that the sum of Mo+W/2 is less than 0.50% by weight, preferably less than 0.4% by weight, more preferably less than 0.3% by weight. This is because the inventors have found that by maintaining the two elements and their contents and below the values shown, no precipitation of intercalated intermetallics is observed, whereby by heat treatment or The sheet or strip after hot working is cooled by air, and in particular, the method of manufacturing the steel sheet or strip can be alleviated. Furthermore, it has been observed that by controlling these elements within the stated limits, the solderability of the grades is improved. Preferably, however, the minimum molybdenum content is maintained at 0.1% to improve the hot forgeability of this grade. In addition, the smelting of grades with a molybdenum content of less than 0.1% imposes significant restrictions on the use of recycled waste for this grade, thus causing processing problems, in particular the use of a feed consisting of 100% pure iron alloy.
銅(一種形成沃斯田鐵的元素)存在的量介於0.11和0.50重量%之間,且以介於0.15和0.40重量%之間為佳。此元素改良在具有還原力的酸介質中之耐蝕性。但是,其含量限於0.50重量%,以防止形成ξ相(希望防止此相,這是因為這些導致肥粒鐵相之硬化和雙重合金變脆)。Copper (an element forming Vostian iron) is present in an amount between 0.11 and 0.50% by weight, and preferably between 0.15 and 0.40% by weight. This element improves the corrosion resistance in an acid medium having a reducing power. However, its content is limited to 0.50% by weight to prevent the formation of a ruthenium phase (it is desirable to prevent this phase because these cause hardening of the ferrite grain iron phase and double alloy embrittlement).
氧含量以限制於0.010重量%為佳,以改良其可鍛造性。The oxygen content is preferably limited to 0.010% by weight to improve its forgeability.
硼是選用的元素,其可以介於0.0005重量%和0.01重量%之間(以介於0.0005重量%和0.005重量%之間為佳,介於0.0005重量%和0.003重量%之間更佳)的量加至根據本發明之等級品中,以改良其熱轉化性。但在另一具體實例中,較佳地,將硼含量限制低於0.0005重量%,以限制在焊接和連續鑄造期間內破裂的風險。Boron is an optional element which may be between 0.0005 wt% and 0.01 wt% (preferably between 0.0005 wt% and 0.005 wt%, more preferably between 0.0005 wt% and 0.003 wt%). Amount is added to the grade according to the invention to improve its thermal conversion. In yet another embodiment, however, the boron content is preferably limited to less than 0.0005 weight percent to limit the risk of cracking during welding and continuous casting.
矽(一種形成肥粒鐵的元素)之存在含量低於1.4重量%。鋁(一種形成肥粒鐵的元素)之存在含量低於0.05重量%,並以介於0.005重量%和0.040重量%之間為佳,以得到低熔點的鋁酸鈣夾雜物。亦限制最高鋁含量,以防止氮化鋁之過度形成。這兩種元素(矽和鋁)的作用基本上是確保在冶煉期間內鋼浴之去氧化作用。The content of cerium (an element forming ferrite iron) is less than 1.4% by weight. Aluminum (an element forming ferrite iron) is present in an amount of less than 0.05% by weight, preferably between 0.005% by weight and 0.040% by weight, to obtain a low-melting calcium aluminate inclusion. The maximum aluminum content is also limited to prevent excessive formation of aluminum nitride. The role of these two elements (矽 and aluminum) is essentially to ensure deoxidation of the steel bath during smelting.
鈷(一種形成沃斯田鐵的元素)維持於含量低於0.5重量%,以低於0.3重量%為佳。此元素是源自於原料的殘留元素。特別地,其可能因為處理方面的問題(照射核能發電設備之組件之後,具有處理方面的問題)而受限。Cobalt, an element forming the Vostian iron, is maintained at a level of less than 0.5% by weight, preferably less than 0.3% by weight. This element is a residual element derived from the raw material. In particular, it may be limited due to processing problems (having processing problems after illuminating components of nuclear power generation equipment).
稀土金屬(以REM表示)可以0.1重量%的量(以低於0.06重量%為佳)加至組成物中。特別可提及的是鈰和鑭。限制這兩種元素的含量,此因它們易形成所不欲的介金屬之故。The rare earth metal (expressed as REM) may be added to the composition in an amount of 0.1% by weight (preferably less than 0.06% by weight). Mention may be made in particular of bismuth and strontium. The content of these two elements is limited because they tend to form unwanted intermetallics.
釩(一種形成肥粒鐵的元素)可以0.5重量%的量(以低於0.2重量%為佳)加至此等級品中,以改良鋼的耐裂縫腐蝕性。Vanadium (an element forming ferrite iron) may be added to this grade in an amount of 0.5% by weight (preferably less than 0.2% by weight) to improve the crack corrosion resistance of the steel.
鈮(一種形成肥粒鐵的元素)可以0.3重量%的量(以低於0.050重量%為佳)加至此等級品中。其憑藉氮化鈮之形成而有助於改良此等級品的抗張強度。限制其含量,以限制粗粒氮化鈮之形成。Niobium (an element forming ferrite iron) may be added to this grade in an amount of 0.3% by weight (preferably less than 0.050% by weight). It helps to improve the tensile strength of this grade by virtue of the formation of tantalum nitride. Limit its content to limit the formation of coarse-grained tantalum nitride.
鈦(一種形成肥粒鐵的元素)可以0.1重量%的量(以低於0.02重量%為佳)加至此等級品中,以限制氮化鈦之形成(特別是在液態鋼中之氮化鈦之形成)。Titanium (an element forming ferrite iron) can be added to this grade in an amount of 0.1% by weight (preferably less than 0.02% by weight) to limit the formation of titanium nitride (especially titanium nitride in liquid steel) Formation).
也可以將鈣加至根據本發明之等級品中,以使得鈣含量低於0.03重量%,以高於0.0002重量%為佳,高於0.0005重量%更佳,以控制氧化物夾雜物之本質及改良機械加工性。限制此元素的含量,此因其易於與硫形成硫化鈣(其減低耐蝕性)之故。在一個較佳的具體實例中,鈣含量限制於低於0.0005重量%,以低於0.0002重量%為佳。Calcium may also be added to the grade according to the invention such that the calcium content is less than 0.03% by weight, preferably more than 0.0002% by weight, more preferably more than 0.0005% by weight, to control the nature of the oxide inclusions and Improve machinability. The content of this element is limited because it is easy to form calcium sulfide with sulfur (which reduces corrosion resistance). In a preferred embodiment, the calcium content is limited to less than 0.0005 wt%, preferably less than 0.0002 wt%.
硫含量維持低於0.010重量%並以含量低於0.003重量%為佳。如前述者,此元素與錳或鈣形成硫化物,硫化物之存在將損及耐蝕性。硫被視為雜質。The sulfur content is maintained below 0.010% by weight and is preferably less than 0.003% by weight. As mentioned above, this element forms a sulfide with manganese or calcium, and the presence of sulfide will impair corrosion resistance. Sulfur is considered an impurity.
鎂的添加量可以使得其最終含量為0.1%,以修飾硫化物和氧化物的本質。Magnesium may be added in an amount such that the final content is 0.1% to modify the nature of the sulfides and oxides.
硒以維持低於0.005重量%為佳,此因其損及耐蝕性之故。此元素通常以肥粒鐵和錳鑄錠的雜質形式引至此等級品中。Selenium is preferably maintained at less than 0.005% by weight because of its damage to corrosion resistance. This element is usually introduced into this grade in the form of impurities in fermented iron and manganese ingots.
磷維持於含量低於0.040重量%,且其被視為雜質。Phosphorus is maintained at a level of less than 0.040% by weight and is considered an impurity.
組成物的餘者由鐵和雜質所組成。前述者以外,這些雜質亦可為鋯、錫、砷、鉛或鉍。錫可以低於0.100重量%的含量存在並以低於0.030重量%為佳,以防止焊接問題。砷可以低於0.030重量%的含量存在並以低於0.020重量%為佳。鉛可以低於0.002重量%的含量存在且以低於0.0010重量%為佳。鉍可以低於00002重量%的含量存在且以低於0.00005重量%為佳。鋯可以0.02%的量存在。The remainder of the composition consists of iron and impurities. In addition to the foregoing, these impurities may be zirconium, tin, arsenic, lead or antimony. Tin may be present in an amount of less than 0.100% by weight and preferably less than 0.030% by weight to prevent soldering problems. Arsenic may be present in an amount of less than 0.030% by weight and preferably less than 0.020% by weight. Lead may be present in an amount of less than 0.002% by weight and preferably less than 0.0010% by weight. The cerium may be present in an amount of less than 0.0002% by weight and preferably less than 0.00005% by weight. Zirconium can be present in an amount of 0.02%.
此外,本發明者發現,當鉻、鉬、氮、鎳和錳的重量百分比滿足以下關係式時,該等級品具有良好的局部耐蝕性,亦即,耐形成凹洞或裂縫的耐受性:
於經退火的狀態,根據本發明之鋼之微結構由沃斯田鐵和肥粒鐵所構成,較佳地,於1000℃處理1小時之後,其相以35至65體積%(35至55體積%特別佳)比例的肥粒體存在。In the annealed state, the microstructure of the steel according to the present invention is composed of Worthite iron and ferrite iron. Preferably, after treatment at 1000 ° C for 1 hour, the phase is 35 to 65 vol% (35 to 55). A particularly good volume % is present in the proportion of fat granules.
本發明者亦發現下列式適當地描述於1100℃的肥粒鐵含量:IF =6x(%Cr+1.32x%Mo+1.27x%Si)-10x(%Ni+24x%C+16.15x%N+0.5x%Cu+0.4x%Mn)-6.17。The inventors have also found that the following formula suitably describes the ferrite iron content at 1100 ° C: I F = 6 x (% Cr + 1.32 x % Mo + 1.27 x % Si) - 10 x (% Ni + 24 x % C + 16.15 x % N + 0.5 x % Cu + 0 .4x%Mn) - 6.17.
因此,欲使得於1100℃之肥粒鐵的比例介於35和65%之間,肥粒鐵指數IF 必須介於40和70之間。Therefore, in order to make the ratio of ferrite iron at 1100 °C between 35 and 65%, the ferrite iron index I F must be between 40 and 70.
在經退火的狀態中,微結構不含有會損及其機械性質之其他相,特別是,如σ相和其他介金屬相。在經冷加工的狀態中,一部分的沃斯田鐵可以被轉化成麻田散鐵,此視變形的實際溫度和施用的冷變形量而定。In the annealed state, the microstructure does not contain other phases that can damage its mechanical properties, particularly, such as the sigma phase and other intermetallic phases. In the cold worked state, a portion of the Worthite iron can be converted to a granulated iron, depending on the actual temperature of the deformation and the amount of cold deformation applied.
通常,根據本發明之鋼可經冶煉並可自厚片或鑄錠製成熱軋板形式(所謂的四開尺寸板),但亦可為熱軋條形式,亦可為熱軋條製成的冷軋條形式。其亦可以棒或棍或塊件或鍛件型式熱軋。這些產物可於之後藉鍛造而熱轉變或冷轉變成棒或經拉伸的塊件或模具拉伸的線。根據本發明之鋼亦可藉澆鑄而處理,此澆鑄之後進行或未進行熱處理。In general, the steel according to the invention can be smelted and can be made into a hot rolled sheet form (so-called four-open size sheet) from a slab or an ingot, but can also be in the form of a hot rolled strip or a hot rolled strip. Cold rolled strip form. It can also be hot rolled in the form of rods or sticks or blocks or forgings. These products can then be converted by hot forging or cold to a bar or a stretched block or die drawn line. The steel according to the invention may also be treated by casting, with or without heat treatment after casting.
欲得到可能的最佳效能,較佳地,使用根據本發明之方法,其中,首先包括提供具有根據本發明之組成之鋼錠、厚片或塊材。In order to obtain the best possible performance, it is preferred to use the method according to the invention, which first comprises providing a steel ingot, slab or block having the composition according to the invention.
此鑄錠、厚片或塊材通常係藉由使得原料在電爐中冶煉,及之後進行具有脫碳作用的AOD或VOD型真空熔解而得。可於之後在無底鑄模中連續鑄造,而將此等級品鑄造成鑄錠形式、厚片形式或塊料形式。也可以直接將此等級品鑄造成薄板形式,特別是藉由在相對旋轉的滾筒之間連續鑄造。The ingot, slab or block is usually obtained by smelting the raw material in an electric furnace and then performing vacuum melting of AOD or VOD type having decarburization. This grade can then be cast continuously in a bottomless mold, and this grade can be cast into ingot form, slab form or block form. It is also possible to cast this grade directly into a sheet form, in particular by continuous casting between relatively rotating drums.
提供鑄錠、厚片或塊料之後,此可以選擇性地再加熱,以達到介於1150和1280℃之間的溫度,但也可以在其仍熱時,立即以連續鑄造的方式,直接在厚片上加工。After the ingot, slab or block is provided, this can be selectively reheated to reach a temperature between 1150 and 1280 ° C, but it can also be directly cast in a continuous casting mode while it is still hot. Processing on thick sheets.
製板的情況中,厚片或鑄錠然後經熱軋以得到厚度通常介於5和100毫米之間的四開尺寸板。用於此階段的降低比例變化通常介於3和30%之間。之後,此板經熱處理,藉由再加熱至介於900和1100℃之間的溫度,以使得在此階段形成的析出物回到溶液中,並於之後冷卻。In the case of a panel, the slab or ingot is then hot rolled to obtain a four-open slab having a thickness typically between 5 and 100 mm. The reduction in the ratio used for this stage is usually between 3 and 30%. Thereafter, the plate is heat treated by reheating to a temperature between 900 and 1100 ° C so that the precipitate formed at this stage is returned to the solution and then cooled.
根據本發明之方法提供空氣淬冷,其比用於此類型的等級品之慣用的水冷卻法容易實行,後者更迅速地冷卻。但有需要時,其仍可進行水冷操作。Air quenching is provided in accordance with the method of the present invention, which is easier to perform than conventional water cooling methods for grades of this type, which cool more rapidly. However, it can still be water cooled when needed.
此緩慢的空氣冷卻特別獲益於根據本發明組成物之有限的鎳和鉬含量,其沒有會損及其使用性質之介金屬相析出的情況發生。此冷卻特別可以0.1至2.7℃/秒範圍內的速率進行。This slow air cooling benefits in particular from the limited nickel and molybdenum content of the composition according to the invention, which does not occur in the case of precipitation of the intermetallic phase which would detract from its use properties. This cooling can be carried out in particular at a rate in the range from 0.1 to 2.7 ° C / sec.
熱軋之後,若其欲以此狀態輸送,則四開尺寸板可經平坦化、切割和酸洗。After hot rolling, if it is intended to be transported in this state, the four-open size plate can be planarized, cut and pickled.
也可以在條滾模機中滾軋此條鋼至厚度介於3和10毫米之間。It is also possible to roll the strip in a strip rolling machine to a thickness between 3 and 10 mm.
在自鑄錠或塊料製造長產物的例子中,可以在單一熱軋機中,在多股滾軋機上,於介於1150和1280℃之間的溫度熱壓通過有凹槽的滾筒之間,以得到線料的棒或線圈,或成捲。初塊料和最終產物之間的截面積比例以大於3為佳,以確保成捲產物的內部健全。In the case of the manufacture of long products from ingots or blocks, it can be hot pressed between the grooved rolls at a temperature between 1150 and 1280 ° C in a single hot rolling mill in a single hot rolling mill. To get the rod or coil of the strand, or to roll. The ratio of the cross-sectional area between the primary block and the final product is preferably greater than 3 to ensure the internal integrity of the rolled product.
當製得棒時,其於離開滾軋機之後,藉簡單的噴空氣而冷卻。When the rod is made, it is cooled by a simple air spray after leaving the rolling mill.
製造直徑大於13毫米的滾軋棒時,其可以在離開滾軋機時,藉由使其以線圈形式在水槽中淬火而冷卻。When a rolled bar having a diameter of more than 13 mm is produced, it can be cooled by quenching it in a water tank in the form of a coil when leaving the rolling mill.
製造直徑為13毫米或以下的棒時,其可以散佈在運輸機上的匝形式,在該匝延著運輸機通過溶解處理爐(溫度介於850℃和1100℃之間)2至5分鐘之後,藉水淬而冷卻。When a rod having a diameter of 13 mm or less is produced, it can be spread on the conveyor in the form of a crucible, after the conveyor is passed through a dissolution treatment furnace (temperature between 850 ° C and 1100 ° C) for 2 to 5 minutes, Water quenched and cooled.
如果希望完成結構之再結晶作用及略為降低抗張性質,後續之介於900℃和1100℃之間的爐熱處理可以選擇性地施於此棒或線圈(其已經過熱軋處理)上。If it is desired to complete the recrystallization of the structure and to slightly reduce the tensile properties, a subsequent furnace heat treatment between 900 ° C and 1100 ° C can be selectively applied to the rod or coil (which has been subjected to hot rolling treatment).
在此棒或桿的線圈冷卻之後,可以進行多種熱成型或冷成型處理,此視產物的最終用途而定。在被冷卻之後,此條可經過冷拉伸操作或者桿可進行模具拉伸操作。After the rod or rod coil is cooled, various thermoforming or cold forming treatments can be performed depending on the end use of the product. After being cooled, the strip can be subjected to a cold drawing operation or a rod can be subjected to a mold stretching operation.
熱軋棒亦可經冷成型,或者,在棒被切成金屬小塊及於之後鍛造之後,可製得零件。The hot rolled rod may also be cold formed, or the part may be produced after the rod is cut into small pieces of metal and then forged.
欲說明本發明,製得受熱物且特別參考圖1至5描述這些。To illustrate the invention, a heated object is made and these are described with particular reference to Figures 1 to 5.
藉真空感應熔解純鐵合金原料,之後藉由在氮分壓下氮化以添加鐵合金的方式引入氮,及在外在氮氣壓力為0.8巴時鑄造成金屬模製物而製得25公斤實驗室鑄錠。這些受熱物中,僅受熱物14441和14604係根據本發明。The pure iron alloy raw material is melted by vacuum induction, and then nitrogen is introduced by nitriding under a nitrogen partial pressure to add nitrogen, and a metal molded product is cast at an external nitrogen pressure of 0.8 bar to prepare a 25 kg laboratory ingot. . Of these heats, only the heat-receiving materials 14441 and 14604 are in accordance with the present invention.
根據本發明之工業加熱,製得150噸參考物8768。此等級品藉由在電爐中熔化而冶煉,之後進行真空精煉而脫碳,以達到所欲碳含量。其於之後連續地鑄成厚片(截面積為220x1700毫米),之後,再加熱至1200℃之後,熱軋成厚度為7、12和20毫米的四開尺寸板。之後,藉此而得到的板於約1000℃進行熱處理,使得此階段存在的許多析出物回到溶液中。熱處理之後,此板以水加以冷卻,之後平坦化、切割和酸洗。According to the industrial heating of the present invention, 150 tons of reference material 8768 were obtained. This grade is smelted by melting in an electric furnace, followed by vacuum refining to decarburize to achieve the desired carbon content. It was then continuously cast into slabs (having a cross-sectional area of 220 x 1700 mm), and then, after heating to 1200 ° C, hot rolled into four-thickness plates having thicknesses of 7, 12 and 20 mm. Thereafter, the thus obtained sheet is heat-treated at about 1000 ° C so that many precipitates present at this stage are returned to the solution. After the heat treatment, the plate was cooled with water, followed by planarization, cutting and pickling.
以實驗室規模或工業規模精煉的多種等級品之重量百分比組成示於表1;在電爐中精煉,之後藉AOD精煉並鑄造成錠或連續鑄造之多種工業產品或半成品之組成亦示於表1以資比較。The composition of the weight percentages of various grades refined on a laboratory scale or an industrial scale is shown in Table 1; the composition of various industrial products or semi-finished products refined in an electric furnace and then refined by AOD and cast into ingots or continuously cast is also shown in Table 1. For comparison.
1.1剛處理之產物的肥粒鐵含量 自這些實驗室受熱物(於剛鑄造的狀態)或自工業產物(於剛鑄造的狀態)切下體積為1至8立方公分的樣品,這些樣品在鹽浴中,於許多不同溫度熱處理30分鐘,之後進行處理後之水淬,以測定於高溫時的肥粒鐵比例。由於肥粒鐵具磁性(此與沃斯田鐵、可能存在的碳化物和氮化物不同),所以使用測定飽和磁化作用之分析法。藉此而測得的肥粒鐵含量示於表2並繪於圖1。 1.1 Fertilizer iron content of the product just processed from these laboratory heats (in the state of just casting) or from the industrial product (in the state of just casting) cut samples of 1 to 8 cubic centimeters, these samples are in the salt In the bath, heat treatment was carried out for 30 minutes at various temperatures, followed by water quenching after treatment to determine the ratio of ferrite to iron at high temperatures. Since the ferrite is magnetic (this is different from the Worth iron, possibly carbides and nitrides), an analytical method for determining the saturation magnetization is used. The ferrite iron content thus measured is shown in Table 2 and plotted in Figure 1.
圖1顯示指數IF 和肥粒鐵含量(以於1100℃處理之後之基礎金屬測得)之間具有良好的關聯性。Figure 1 shows a good correlation between the index I F and the ferrite iron content (measured as the base metal after treatment at 1100 ° C).
也已經顯示根據本發明受熱物14441於低於1300℃所具有的肥粒鐵含量適合熱轉變成雙重結構。此外,於950℃至1100℃範圍中熱處理之後,其肥粒鐵含量適用於耐應力腐蝕性。It has also been shown that the ferrite iron content of the heat-receiving material 14441 according to the present invention at less than 1300 ° C is suitable for thermal conversion into a dual structure. Further, after heat treatment in the range of 950 ° C to 1100 ° C, the ferrite iron content is suitable for stress corrosion resistance.
1.2終產物之肥粒鐵含量 亦藉方格法(根據ASTM E 562標準)測定鍛造的棒(其經1030℃熱處理)和焊接珠(其藉塗覆的電極以穩定的能量,源自於700℃以冷卻速率20℃/秒冷卻)所沉積)之受熱影響區域的肥粒鐵含量。其結果(基礎金屬和受熱影響區域的肥粒鐵含量)示於表3。此顯示根據本發明之受熱物14441和14604在基礎金屬中和在受熱影響區域中之肥粒鐵含量有利於局部耐應力腐蝕性,且亦有利於韌性(參考表5來比較)。 1.2 The iron content of the final product is also determined by the grid method (according to ASTM E 562 standard) for the forged rod (which is heat treated at 1030 ° C) and the welded beads (which are stabilized by the coated electrode), derived from 700 The ferrite iron content of the heat affected zone deposited by °C at a cooling rate of 20 ° C / sec. The results (fertilizer iron content of the base metal and the heat affected zone) are shown in Table 3. This shows that the ferrite iron content in the base metal and in the heat affected zone in accordance with the present invention contributes to local stress corrosion resistance and also contributes to toughness (compared with reference to Table 5).
鑄錠14439具有氣泡且無法使用。為防止在空氣中於大氣壓下鑄造的期間內的此現象,證實必須將根據本發明之受熱物的氮含量限制於低於0.28重量%。The ingot 14439 has air bubbles and cannot be used. In order to prevent this phenomenon during the casting at atmospheric pressure in the air, it was confirmed that the nitrogen content of the heat-receiving material according to the present invention must be limited to less than 0.28% by weight.
使用在試樣上進行的熱抗張試驗評估此熱轉變能力,試樣的校正部分(直徑8毫米,長5毫米)藉焦耳加熱而於1280℃加熱80秒鐘,並於之後以2℃/秒的速率冷卻至試驗溫度(其變化於900和1280℃之間)。到達此溫度時,立即以速率為73毫米/秒進行快速抗張試驗;破裂之後,測定破裂處的頸縮直徑。The thermal transition capability was evaluated using a thermal tensile test conducted on the sample. The corrected portion of the sample (8 mm in diameter and 5 mm in length) was heated by Joule heating at 1280 ° C for 80 seconds and then at 2 ° C / The rate of seconds is cooled to the test temperature (which varies between 900 and 1280 °C). Upon reaching this temperature, a rapid tensile test was performed at a rate of 73 mm/sec; after the rupture, the neck diameter of the rupture was measured.
以下所定義之相對直徑變化(表4)反映熱可變形性:△ψ=100 x(1-(最終直徑/初直徑))。The relative diameter variation (Table 4) defined below reflects the thermal deformability: Δψ = 100 x (1-(final diameter / initial diameter)).
表4和圖2(其以曲線形式代表數據)中,可以看出根據本發明之受熱物14441所具有的熱可變形性與比較用的參考受熱物14382相仿。In Table 4 and Figure 2, which represent the data in the form of a curve, it can be seen that the heat-reducible material 14441 according to the present invention has a thermal deformability similar to that of the comparative reference heat-receiving material 14382.
抗張性質Re0.2 和Rm 係根據NF EN 10002-1標準測定。韌度Kv 係根據NF EN 10045標準於許多溫度測定。The tensile properties R e0.2 and R m are determined according to the NF EN 10002-1 standard. Toughness K v is determined at a number of temperatures according to the NF EN 10045 standard.
實驗室受熱品14441和14604及工業受熱品8768(此三者皆根據本發明)之結果顯示屈服強度可大於450MPa,即,兩倍於AISI 304L型的沃斯田鐵型鋼所得者。The results of laboratory heat products 14441 and 14604 and industrial heat products 8768 (all of which are in accordance with the present invention) indicate that the yield strength can be greater than 450 MPa, i.e., twice the yield of the Worthfield iron profile steel of the AISI 304L type.
實驗室受熱品14441和14604和工業受熱品8768(此三者皆根據本發明)於20℃測得之韌度值皆大於200焦耳,將這些等級品的屈服強度列入考慮後此令人滿意。至於非根據本發明之受熱品14383,具有低氮含量和高肥粒鐵含量,其於退火狀態中,於20℃的韌度值低於100焦耳。此證實須添加足量的氮以得到令人滿意的韌度。The laboratory heat samples 14441 and 14604 and the industrial heat products 8768 (all of which are according to the invention) have a toughness value greater than 200 joules at 20 ° C. It is satisfactory after considering the yield strength of these grades. . As for the heat-receiving product 14383 not according to the present invention, it has a low nitrogen content and a high fat iron content, and in the annealed state, the toughness value at 20 ° C is less than 100 joules. This confirms that a sufficient amount of nitrogen must be added to obtain a satisfactory toughness.
在源自實驗室受熱品之經鍛造的棒和在源自於工業受熱品之自熱軋板移除的試樣胚上進行耐蝕性試驗。Corrosion resistance tests were carried out on forged bars derived from laboratory heat and on sample embryos removed from hot rolled sheets derived from industrial heat.
5.1局部耐蝕性 藉由繪出電流-電位曲線並測定i=100微安培/平方公分的凹洞電位來評估耐凹洞腐蝕性。在高氯化物濃度([Cl- ]=30克/升)的中性介質(pH=6.4)中、於50℃(E1 )(以此模擬在海水去鹽設備中遇到海水的情況)及在低氯化物濃度([Cl- ]=250 ppm)之略酸的介質(pH=5.5)中、於室溫(E2 )(以此模擬飲用水)測定此參數。在氯化鐵介質(6% FeCl3 )中之臨界凹洞溫度係根據ASTM G48-00標準的方法C測定。 5.1 Local Corrosion Resistance The pit corrosion resistance was evaluated by plotting the current-potential curve and measuring the cavity potential of i = 100 microamperes per square centimeter. In a neutral medium (pH = 6.4) with a high chloride concentration ([Cl - ] = 30 g / liter) at 50 ° C (E 1 ) (this simulates the case of seawater encountered in seawater desalination equipment) This parameter was determined in a slightly acidic medium (pH = 5.5) at a low chloride concentration ([Cl - ] = 250 ppm) at room temperature (E 2 ) (to simulate drinking water). The critical cavity temperature in the ferric chloride medium (6% FeCl 3 ) is determined according to Method C of the ASTM G48-00 standard.
另一系列的試驗中,在含有0.86莫耳/升NaCl(相當於5重量%NaCl)之經脫氣的中性介質中,於35℃測定耐凹洞腐蝕性。進行900秒鐘的浮動電位測定。之後,於100毫伏特/分鐘速率的浮動電位繪出電動勢曲線直到到達凹洞電位。於i=100微安培/平方公分測定此凹洞電位(E3 )。在這些條件下,測試根據本發明之試樣和參考試樣304L等級品和1.4362型的沃斯田鐵-肥粒鐵雙重等級品和其他者。In another series of tests, the pit corrosion resistance was measured at 35 ° C in a degassed neutral medium containing 0.86 mol/liter NaCl (corresponding to 5% by weight NaCl). A 900 second floating potential measurement was performed. Thereafter, the electromotive force curve is plotted at a floating potential at a rate of 100 millivolts per minute until the cavity potential is reached. The cavity potential (E 3 ) was measured at i = 100 μA / cm ^ 2 . Under these conditions, the sample according to the present invention and the reference sample 304L grade and the type 1.4362 of the Worthite iron-fertilizer iron grade and others were tested.
以在高氯化物濃度([Cl- ]=30克/升)的中性介質(pH=6.4)中測定臨界裂縫溫度的方式來研究耐裂縫腐蝕性。有助於浮動的裂縫腐蝕之排列係根據ASTM G78-99標準中所列之建議。臨界裂縫溫度是觀察到裂縫深度大於25微米的最低溫度。The crack corrosion resistance was investigated by measuring the critical crack temperature in a neutral medium (pH = 6.4) having a high chloride concentration ([Cl - ] = 30 g / liter). Arrangements that contribute to floating crack corrosion are based on the recommendations listed in the ASTM G78-99 standard. The critical crack temperature is the lowest temperature at which the crack depth is observed to be greater than 25 microns.
表6中列出所得的值。比較UNS S32304製的板及自受熱物14382得到的棒(此二者的化學組成類似)所得之結果,指出棒的耐蝕性低於具有相同組成之熱軋板的耐蝕性。The values obtained are listed in Table 6. Comparing the results of the panels made of UNS S32304 and the rods obtained from the heat-receiving material 14382 (the chemical compositions of the two are similar), it is pointed out that the corrosion resistance of the rods is lower than that of the hot-rolled sheets having the same composition.
本發明者發現局部耐蝕指數(即,耐得住腐蝕凹洞或裂縫之形成)縮寫為ILCR 且定義為:ILCR =Cr+3.3xMo+16xN+2.6xNi-0.7xMn(Cr、Mo、N、Ni和Mn的含量以重量%表示)The inventors have found that the local corrosion index (i.e., resistance to formation of corrosion pits or cracks) is abbreviated as I LCR and is defined as: I LCR = Cr + 3.3 x Mo + 16 x N + 2.6 x Ni - 0.7 x Mn (Cr, Mo, N, Ni, and Mn) Content is expressed in % by weight)
說明考慮局部耐蝕性時所有組份之分類的鎳含量皆低於6%(請參考圖3、4和5)。Note that the nickel content of all components is considered to be less than 6% when considering local corrosion resistance (please refer to Figures 3, 4 and 5).
非根據本發明之受熱物14383和14660(具有ILCR 的指數等於28.7和29.8)所具有的腐蝕行為不及AISI 304L型的鋼。根據本發明之受熱物14604和14441(具有的ILCR 指數為30.9和33)之行為至少與304L型鋼相仿。已經發現,欲得到耐蝕性至少等於AISI 304L等級品,較佳地,根據本發明之鋼所具有的ILCR 必須大於30.5,並以大於32為佳。The heat-receiving materials 14383 and 14660 (having an index of I LCR equal to 28.7 and 29.8) according to the present invention have less corrosion behavior than the steel of the AISI 304L type. The heat-receiving materials 14604 and 14441 (having an I LCR index of 30.9 and 33) according to the present invention behave at least as similar as the 304L steel. It has been found that to obtain corrosion resistance at least equal to the AISI 304L grade, preferably, the steel according to the present invention must have an I LCR greater than 30.5 and preferably greater than 32.
5.2均勻耐蝕性 藉由評估浸泡在已加熱至40℃的2%稀硫酸溶液中72小時之後之腐蝕速率而定出均勻腐蝕之特性。 5.2 Uniform Corrosion Resistance The characteristics of uniform corrosion were determined by evaluating the corrosion rate after soaking in a 2% dilute sulfuric acid solution heated to 40 ° C for 72 hours.
比較含有2.5%Ni和0.2%N的實驗用受熱物(根據本發明之14441和非根據本發明之14660),清楚顯示高Mn含量對於在硫酸介質中之均勻耐蝕性之負面影響。Comparing the experimental heat containing 2.5% Ni and 0.2% N (14441 according to the invention and 14660 not according to the invention) clearly shows the negative effect of the high Mn content on the uniform corrosion resistance in the sulfuric acid medium.
5.3再鈍化電位 鋼試樣於水中使用SiC紙拋光至1200,之後於空氣中老化24小時。 5.3 Repassivation potential The steel sample was polished to 1200 in water using SiC paper and then aged in air for 24 hours.
測定浮動電位15分鐘,之後自浮動電位以100毫安培/分鐘循環動態極化至電流強度為300微安培/平方公分之電位,之後回到電流為0的電位,藉此進行在氯化物介質中之循環極化試驗。The floating potential was measured for 15 minutes, and then the self-floating potential was dynamically polarized at a current of 300 mA/cm 2 at a current of 100 mA/min, and then returned to a potential of 0, thereby performing in a chloride medium. Cyclic polarization test.
藉此,測定凹洞電位(P凹洞 )和之前形成的凹洞之再鈍化電位(V再鈍化作用 )。所得結果示於表7。Thereby, the pit potential (P- cavity ) and the re-passivation potential of the previously formed pit (V re-passivation ) were measured. The results obtained are shown in Table 7.
由在NaCl介質中之再鈍化電位試驗,鎳含量越高,凹洞電位與再鈍化電位之間的差異越大。此顯示鎳不利於之前已凹洞腐蝕之根據本發明之等級品的再鈍化作用。From the repassivation potential test in NaCl medium, the higher the nickel content, the greater the difference between the pit potential and the repassivation potential. This shows that nickel is detrimental to the repassivation of grades according to the invention which have previously been corroded.
圖1:於1100℃處理之後的肥粒鐵%和以此方式加工的產物IF 之關係圖;圖2:相對直徑變化△ψ與變形溫度之關係圖;圖3:凹洞電位E1和E2(在經鍛造的棒上測得)與指數ILCR 之關係圖;圖4:均勻腐蝕速率V(在經鍛造的棒上測得)與指數ILCR 之關係圖;和圖5:臨界溫度TCC 和TCP (在經鍛造的棒上測得)與指數ILCR 之關係圖。Figure 1: Relationship between % ferrite iron after treatment at 1100 °C and product I F processed in this way; Figure 2: plot of relative diameter change Δψ versus deformation temperature; Figure 3: pit potential E1 and E2 (measured on a forged rod) versus index I LCR ; Figure 4: graph of uniform corrosion rate V (measured on a forged rod) versus index I LCR ; and Figure 5: critical temperature T Diagram of CC and T CP (measured on forged rods) versus index I LCR .
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- 2007-06-15 PL PL07803755T patent/PL2038445T3/en unknown
- 2007-06-15 KR KR1020087030667A patent/KR101169627B1/en active IP Right Grant
- 2007-06-15 EP EP07803755A patent/EP2038445B1/en active Active
- 2007-06-15 AU AU2007259069A patent/AU2007259069B2/en active Active
- 2007-06-15 CA CA2656946A patent/CA2656946C/en active Active
- 2007-06-15 DK DK07803755.3T patent/DK2038445T3/en active
- 2007-06-15 TW TW096121708A patent/TWI463020B/en active
- 2007-06-15 SI SI200731163T patent/SI2038445T1/en unknown
- 2007-06-15 ES ES07803755T patent/ES2401601T3/en active Active
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2008
- 2008-12-15 ZA ZA200810587A patent/ZA200810587B/en unknown
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2015
- 2015-02-13 US US14/622,402 patent/US20150167135A1/en not_active Abandoned
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2019
- 2019-04-01 US US16/371,563 patent/US20190226068A1/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4331474A (en) * | 1980-09-24 | 1982-05-25 | Armco Inc. | Ferritic stainless steel having toughness and weldability |
US4798635A (en) * | 1984-03-30 | 1989-01-17 | Santrade Limited | Ferritic-austenitic stainless steel |
WO2005073422A1 (en) * | 2004-01-29 | 2005-08-11 | Jfe Steel Corporation | Austenitic-ferritic stainless steel |
Also Published As
Publication number | Publication date |
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ES2401601T3 (en) | 2013-04-23 |
EP2038445A2 (en) | 2009-03-25 |
KR101169627B1 (en) | 2012-07-30 |
PL2038445T3 (en) | 2013-09-30 |
BRPI0713673B1 (en) | 2014-11-25 |
KR20090031864A (en) | 2009-03-30 |
CN101501234A (en) | 2009-08-05 |
WO2007144516A2 (en) | 2007-12-21 |
BRPI0713673A2 (en) | 2012-10-23 |
CA2656946C (en) | 2012-01-24 |
AU2007259069A1 (en) | 2007-12-21 |
US20100000636A1 (en) | 2010-01-07 |
SI2038445T1 (en) | 2013-06-28 |
MX2008016172A (en) | 2009-03-26 |
TW200815613A (en) | 2008-04-01 |
EP2038445B1 (en) | 2012-12-26 |
AU2007259069B2 (en) | 2011-04-28 |
CA2656946A1 (en) | 2007-12-21 |
WO2007144516A3 (en) | 2008-04-10 |
DK2038445T3 (en) | 2013-04-08 |
WO2007144516A9 (en) | 2009-01-29 |
RU2009101139A (en) | 2010-07-27 |
EP1867748A1 (en) | 2007-12-19 |
RU2406780C2 (en) | 2010-12-20 |
ZA200810587B (en) | 2009-11-25 |
US20190226068A1 (en) | 2019-07-25 |
CN101501234B (en) | 2012-01-04 |
US20150167135A1 (en) | 2015-06-18 |
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