EP0657556B1 - Austenitische Legierungen und deren Verwendung - Google Patents

Austenitische Legierungen und deren Verwendung Download PDF

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Publication number
EP0657556B1
EP0657556B1 EP94118682A EP94118682A EP0657556B1 EP 0657556 B1 EP0657556 B1 EP 0657556B1 EP 94118682 A EP94118682 A EP 94118682A EP 94118682 A EP94118682 A EP 94118682A EP 0657556 B1 EP0657556 B1 EP 0657556B1
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EP
European Patent Office
Prior art keywords
max
alloys according
weight
resistant
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94118682A
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German (de)
English (en)
French (fr)
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EP0657556A1 (de
Inventor
Michael Dr. Köhler
Ulrich Dr. Heubner
Kurt-Wilhelm Dr. Eichenhofer
Michael Dr. Renner
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Bayer AG
Krupp VDM GmbH
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Bayer AG
Krupp VDM GmbH
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Publication of EP0657556A1 publication Critical patent/EP0657556A1/de
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • the invention relates to high-chromium, corrosion-resistant, austenitic alloys and their use.
  • Table A shows an example of the state of the art for handling metallic materials that come into question from oxidizing acids (Nickel alloys and high-alloy special stainless steels, 2nd edition, Expert Verlag, 1993). With the exception of the super ferrite, they are so-called austenitic alloys, i.e. around those with a cubic surface-centered lattice structure.
  • the alloys according to the prior art shown in Table A are within a range of between about 17 and 29% by weight Bandwidth for the main alloy element chrome. In terms of corrosion resistance compared to max. 67% nitric acid is already proportionate low-alloy materials can be used.
  • a corresponding material is Cronifer 1809 LCLSi, with the addition LSi to a limited silicon content (low silicon) indicates.
  • Nickel-rich materials such as Nicrofer, which is also listed in Table A. 6030 offer advantages if halogen compounds are present or with nitric acid / Hydrofluoric acid mixtures, such as the Refurbishment of nuclear reactor fuel elements.
  • the molybdenum-containing material Nicrofer 3127 hMo (1.4562) according to EP 0 292 061 With its chromium content of 26 to 28%, it is of interest where, in addition to being proportionate great resistance to nitric acid special emphasis on high resistance against pitting and crevice corrosion.
  • a typical removal rate in boiling azeotropic nitric acid (Huey test) for this material is approx. 0.11 mm / year.
  • the Cronifer 1815 alloyed with about 4% silicon shows oxidizing conditions LCSi (1.4361) excellent resistance to the boiling point of nitric acid.
  • the materials suitable for urea production have similar ones Composition like the particularly corrosion-resistant against nitric acid Steels.
  • Alloys with, for example, approximately 31% chromium and approximately 46% chromium have been examined with regard to their corrosion resistance in nitric acid-hydrofluoric acid mixtures ("Materials and Corrosion" 43 , (1992) pp. 191-200). These alloys with high chromium contents could no longer be produced as austenitic materials and could only be processed using special processes such as powder metallurgy.
  • EP-A 0 261 880 describes alloys with 27 to 31% chromium, 7 to 11% Iron and the rest essentially nickel.
  • EP-A 0 130 967 describes the suitability of nickel alloys and stainless steels for hot sulfuric acid of 99% -101% at> 120 ° C in heat exchangers.
  • the alloys are selected using the following formula: 0.35 (Fe-Mn) + 0.70 (Cr) + 0.30 (Ni) - 0.12 (Mo)> 39.
  • the above Stainless steels containing molybdenum have a maximum of 28% chromium.
  • EP-A 0 200 862 contains molybdenum-free chromium and nickel alloys made of 21-35% chromium, 30-70% iron, 2-40% nickel and 0-20% manganese as well usual accompanying elements as materials for objects against sulfuric acid above 96% to 100% and resistant to oleum.
  • EP-A 249 792 claims the use of alloys consisting of 21 to 55% chromium, 0 to 30% iron, 0 to 5% tungsten and 45 to 79% Ni in concentrated Sulfuric acid.
  • an alloy for the handling of phosphoric acid consisting of 26-35% chromium, 2-6% molybdenum, 1-4% tungsten, 0.3-2% (Niobium + tantalum), 1-3% copper, 10-18% iron, up to 1.5% manganese, up to 1% Silicon, rest essentially nickel suggested.
  • the Chromium content is 30%.
  • DE-A 2 154 126 describes the use of austenitic nickel alloys With 26-48% nickel, 30-34% chromium, 4-5.25% molybdenum, 4-7.5% cobalt, 3-2.5% Iron, 1-3.5% manganese etc. as a resistant material for objects in hot sulfuric acid above 65%.
  • High chromium levels are according to US Pat. No. 3,565,611 Resistance of nickel-chromium-iron alloys to alkali-induced Stress corrosion cracking is important in hot alkaline solutions. In doing so the chromium content is at least 18%, preferably at least 26 to 27%, to Max. 35% and the iron content to max. 7% be restricted.
  • the Alloy 690 is particularly resistant to 29% chromium and 9% iron alkali-induced stress corrosion cracking.
  • US 4,853,185 describes in the high temperature range corrosion-resistant alloys consisting of approximately 30% to 45% nickel, approximately 12 to 32% chromium, at least one of the elements niobium with 0.01% to 2.0%, tantalum with 0.2 to 4 , 0% and vanadium with 0.05 to 1.0%, further up to 0.20% carbon, approximately 0.05 to 0.50% nitrogen, an addition of titanium of up to 0.20, which is effective for high-temperature strength %, Balance iron and impurities, where the sum of free carbon and nitrogen (C + N) F must be> 0.14 and ⁇ 0.29.
  • (C + N) F C + N - Nb 9 - V 4.5 - Ta 18th - Ti 3.5
  • EP-A 340 631 describes a high-temperature-resistant steel tube with a low silicon content, which contains no more than 0.1% by weight of carbon, no more than 0.15% by weight of silicon, no more than 5% by weight of manganese, 20 to 30 wt% chromium, 15 to 30 wt% nickel, 0.15 to 0.35 wt% nitrogen, 0.1 to 1.0 wt% niobium and not more than 0.005 wt% Oxygen, at least one of the metals aluminum and magnesium in an amount of 0.020 to 1.0 wt .-% and 0.003 to 0.02 wt .-% and balance iron and unavoidable impurities.
  • the object of the present invention was to provide alloys which can be used in a variety of ways and are easy to process and their corrosion rates are low.
  • alloys according to the invention are high in chromium and still easy to process. she have only a low molybdenum content or no molybdenum and have contrary to expectations, high corrosion resistance in hot, oxidizing acids.
  • Alloys with 0.5 to 2% by weight of molybdenum and 0.3 to 1% by weight are preferred Copper.
  • These preferred alloys are preferably used as wrought materials for manufacture of semi-finished products, e.g. Sheets, strips, rods, wires, forgings, Pipes, used.
  • These preferred alloys are preferably used as materials for manufacture castings, e.g. Pumps and fittings.
  • the alloys can contain up to 0.08% by weight of rare metals Earth, up to 0.015% by weight calcium and / or up to 0.015% by weight magnesium included as manufacturing-related admixtures.
  • the alloys according to the invention are also used as materials for objects can be used compared to mixtures of sulfuric acid and sodium dichromate and / or chromic acid, from 0.1 to 40% by weight, preferably 0.3 to 20% by weight Nitric acid and 50 to 90 wt .-% sulfuric acid up to 130 ° C or from 0.01 to 15% by weight of hydrofluoric acid and 80-98% by weight of sulfuric acid up to 180 ° C or from up to 25 %
  • By weight of nitric acid and up to 10% by weight of hydrofluoric acid are stable up to 80 ° C.
  • the alloys according to the invention can also be used as materials for objects are used, which compared to cooling water to boiling temperature and opposite Sea water are stable up to 50 ° C.
  • the Alloys according to the invention as a material for the production of components for use in marine technology plants, in environmental technology, space travel, Reactor technology and used in chemical process technology.
  • the alloys according to the invention are in the available plants of the stainless steel producers Can be produced by the known processes and show good processability.
  • the overall corrosion behavior of the alloys according to the invention is excellent.
  • Expensive alloy elements such as tungsten, niobium, tantalum can be used without loss the good properties are waived.
  • the alloys according to the invention also offer the advantage of an unusual universal corrosion resistance. So the alloys on the acid on one side of the apparatus and on the other side of the apparatus with chloride-containing cooling and heating media, e.g. in heat exchangers. It two completely different corrosion resistances are required at the same time, namely acid resistance on the one hand and pitting, crevice and stress corrosion cracking resistance on the other hand.
  • the exceptional durability profile compares with a Economical alloy budget achieved, otherwise only with expensive NiCrMo alloys (see Table B) or only on the acid side with highest alloyed, specially developed materials for special applications (see Table C).
  • the alloys according to the invention are notable for their processability compared to materials from the prior art by an unusual Elimination inertia from thermal stress. This behavior is in the manufacture of semi-finished products and their further processing, e.g. of the Forming of bobbin-case bottoms and making welded connections extremely positive. This is particularly evident from the time-temperature sensitization diagrams (Fig. 1, 2). This is significant Material properties also for the behavior of weld seams that none be subjected to final heat treatment after the apparatus has been manufactured and for the production of mold parts.
  • Example 2 shows the corrosion behavior in sulfuric acid (98-99.1% H 2 SO 4 ) for different temperatures.
  • the alloys according to the invention have excellent corrosion resistance up to 200 ° C. Under flowing conditions, which dominate in operational practice, even lower corrosion rates are determined (example 12).
  • Alloy according to the invention also has excellent corrosion resistance.
  • Example 3 it is that of the high nickel ones Materials Alloy 201, 400, 600 and 690 (17, 15, 16, 11) practically equivalent, while the material 12 (Alloy G-30) drops sharply here. Even at lower ones Alkali concentrations and temperatures rise according to the invention Alloys from the known positive (Example 13).
  • Example 5 the mass loss rates determined in boiling azeotropic nitric acid are compared with one another. It can be seen that the alloys according to the invention suffer only very little corrosion removal. This is lower than that of the well-known materials AISI 310 L (4) and Alloy 28 (7). In super-azeotropic nitric acids, the corrosion behavior of the alloys according to the invention is more favorable than the behavior of "HNO 3 special alloys" (Example 14).
  • Example 7 shows the corrosion behavior in mixed acids from sulfuric acid and nitric acid.
  • the alloy according to the invention is superior to the known alloys both at low and at high H 2 SO 4 contents.
  • Example 8 shows a comparison of the mass loss rates in sulfuric acid-hydrofluoric acid solutions.
  • the alloys according to the invention are highly alloyed with chromium Materials AISI 310 L (4), Alloy 28 (7), Alloy G-30 (12) and 1.4465 (5) compared. It can be seen that the alloys according to the invention have one have less corrosion removal than that corresponding to the prior art Materials.
  • Example 9 A comparison of the mass loss rates was also made in phosphoric acid solutions performed. The results obtained are shown in Example 9.
  • the Alloys according to the invention are made with materials which according to State of the art specifically used for handling phosphoric acid solutions are compared. While in solution 1 the corresponding to the prior art Material Alloy 904 L (3) can be considered sufficient, this is not the case in solution 2.
  • the corrosion resistance of the invention Alloys are not of the Alloy G-30 (12) material significantly different, the low corrosion removal in the inventive Alloys are made with much less expensive alloy additives reached.
  • Example 10 shows the corrosion behavior in nitric acid / hydrofluoric acid mixtures.
  • the alloys according to the invention are far superior to the prior art.
  • Example 15 demonstrates the favorable corrosion behavior of the inventive Alloys compared to known alloys in chromic acid.
  • the alloy 2 'according to the invention is according to Figs. 1 and 2 also after one to 8 hours of thermal stress in the temperature range between 600 and 1000 ° C resistant to intergranular corrosion, both in the case an examination according to SEP 1877 II as well as in the Huey test.
  • the alloys according to the invention are widely applicable, and they can preferably be used in the following areas: Production of sulfuric acid, especially in the area of absorption, Processing of sulfuric acid, eg sulfonation, sulfonation and nitration as well as concentration, Production of azeotropic nitric acid and processing and storage of nitric acid, Production of hydrofluoric acid from sulfuric acid and fluorspar, processing of hydrofluoric acid and processes using hydrofluoric acid as a catalyst Use of etching baths containing hydrofluoric acid, sulfuric acid, nitric acid, e.g.
  • the steels of Table 1 were tested on a 100 kg scale in a vacuum induction furnace melted from known raw materials and cast into blocks. The blocks were formed into 5 (12) mm thick sheets. The final one Solution annealing was carried out at at least 1120 ° C. with subsequent quenching. There was a fully austenitic, excretion-free, homogeneous structure in front.
  • the mechanical properties of the alloys indicate good cold formability.
  • the materials 17, 15, 16 are typical materials for this application.
  • Solution 1 75% by weight H 3 PO 4 ; 80 ° C, 14 days
  • Solution 2 75% by weight H 3 PO 4 , 0.63% by weight F - , 0.3% by weight Fe 3+ , 14 mmol / l Cl - ; 80 ° C, 14 days Material number.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Glass Compositions (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP94118682A 1993-12-10 1994-11-28 Austenitische Legierungen und deren Verwendung Expired - Lifetime EP0657556B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4342188 1993-12-10
DE4342188A DE4342188C2 (de) 1993-12-10 1993-12-10 Austenitische Legierungen und deren Verwendung

Publications (2)

Publication Number Publication Date
EP0657556A1 EP0657556A1 (de) 1995-06-14
EP0657556B1 true EP0657556B1 (de) 1999-02-10

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EP94118682A Expired - Lifetime EP0657556B1 (de) 1993-12-10 1994-11-28 Austenitische Legierungen und deren Verwendung

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US (1) US5695716A (da)
EP (1) EP0657556B1 (da)
JP (1) JP3355510B2 (da)
KR (1) KR950018592A (da)
AT (1) ATE176690T1 (da)
AU (1) AU694456B2 (da)
CA (1) CA2137522C (da)
DE (2) DE4342188C2 (da)
DK (1) DK0657556T3 (da)
ES (1) ES2128495T3 (da)
FI (1) FI107168B (da)
PL (1) PL179404B1 (da)
TW (1) TW363084B (da)
ZA (1) ZA949832B (da)

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DE102004041250A1 (de) * 2004-08-26 2006-03-02 Degussa Ag Herstellung von 2-Hydroxy-4-Methylthiobuttersäure
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US8430075B2 (en) 2008-12-16 2013-04-30 L.E. Jones Company Superaustenitic stainless steel and method of making and use thereof
EP2228578A1 (en) * 2009-03-13 2010-09-15 NV Bekaert SA High nitrogen stainless steel wire for flexible pipe
JP6582904B2 (ja) * 2015-11-12 2019-10-02 東洋インキＳｃホールディングス株式会社 電磁誘導加熱用ホットメルト接着シート、それを用いた接着構造物、及び接着構造物の製造方法
GB2546809B (en) * 2016-02-01 2018-05-09 Rolls Royce Plc Low cobalt hard facing alloy
GB2546808B (en) * 2016-02-01 2018-09-12 Rolls Royce Plc Low cobalt hard facing alloy
EP3438304B1 (en) * 2016-03-30 2021-04-14 Hitachi, Ltd. Cr-BASED TWO-PHASE ALLOY AND PRODUCT THEREOF
WO2017168640A1 (ja) * 2016-03-30 2017-10-05 株式会社日立製作所 クロム基二相合金製造物およびその製造方法
CN110295276A (zh) * 2018-03-21 2019-10-01 吉林常春高氮合金研发中心有限公司 提高高氮钢船舰用螺旋桨耐腐蚀性能的方法
EP3844311A1 (en) * 2018-08-29 2021-07-07 Chemetics Inc. Austenitic stainless alloy with superior corrosion resistance
CN109338345A (zh) * 2018-11-30 2019-02-15 中国科学院金属研究所 一种医用高氮无镍不锈钢的环保型表面钝化处理方法
DE102018133255A1 (de) 2018-12-20 2020-06-25 Voestalpine Böhler Edelstahl Gmbh & Co Kg Superaustenitischer Werkstoff
CN112941413A (zh) * 2021-02-01 2021-06-11 南京理工大学 一种抗辐照核电反应堆压力容器合金

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Also Published As

Publication number Publication date
DE4342188C2 (de) 1998-06-04
DE4342188A1 (de) 1995-06-14
CA2137522C (en) 2004-04-27
JP3355510B2 (ja) 2002-12-09
CA2137522A1 (en) 1995-06-11
FI945771A (fi) 1995-06-11
PL306180A1 (en) 1995-06-12
DK0657556T3 (da) 1999-09-20
FI107168B (fi) 2001-06-15
AU694456B2 (en) 1998-07-23
KR950018592A (ko) 1995-07-22
ATE176690T1 (de) 1999-02-15
DE59407804D1 (de) 1999-03-25
AU8030794A (en) 1995-06-15
JPH07197181A (ja) 1995-08-01
EP0657556A1 (de) 1995-06-14
TW363084B (en) 1999-07-01
PL179404B1 (pl) 2000-08-31
ZA949832B (en) 1995-08-22
ES2128495T3 (es) 1999-05-16
US5695716A (en) 1997-12-09
FI945771A0 (fi) 1994-12-08

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