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EP0438560A4 - A ferrochromium alloy - Google Patents

A ferrochromium alloy

Info

Publication number
EP0438560A4
EP0438560A4 EP19900911863 EP90911863A EP0438560A4 EP 0438560 A4 EP0438560 A4 EP 0438560A4 EP 19900911863 EP19900911863 EP 19900911863 EP 90911863 A EP90911863 A EP 90911863A EP 0438560 A4 EP0438560 A4 EP 0438560A4
Authority
EP
European Patent Office
Prior art keywords
alloy
chromium
matrix
primary
microstructure
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.)
Granted
Application number
EP19900911863
Other versions
EP0438560B1 (en
EP0438560A1 (en
Inventor
Kevin Francis Dolman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Warman International Ltd
Original Assignee
Warman International Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Warman International Ltd filed Critical Warman International Ltd
Publication of EP0438560A1 publication Critical patent/EP0438560A1/en
Publication of EP0438560A4 publication Critical patent/EP0438560A4/en
Application granted granted Critical
Publication of EP0438560B1 publication Critical patent/EP0438560B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • 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
    • C22C38/36—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.7% by weight of carbon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • C22C37/08—Cast-iron alloys containing chromium with nickel

Definitions

  • the present invention relates to a ferrochromium alloy and more particularly to an erosion and corrosion resistant ferrochromium alloy.
  • the present invention is designed for use in thn formation of parts for lining pumps, pipes, nozzles, mixers and similar devices which, in service, can be subjected to mixtures containing a corrosive fluid and abrasive particles.
  • Typical applications for such parts include flue gas desulphurization, in which the parts are exposed to sulphuric acid and limestone, and fertiliser production, in which the parts are exposed to phosphoric acid, nitric acid and gypsum.
  • An object of the present invention is to provide a ferrochromium alloy which has improved erosion and corrosion resistance compared with the alloys disclosed in the Abex U.S. patents.
  • the present invention is based on the realization that by increasing both the chromium and carbon concentrations of alloys of the type disclosed in the Abex U.S. patents it is possible to increase the volume fraction of the chromium carbide phase, and thereby improve the wear resistance characteristics of the ferrochromium alloys, while maintaining the matrix at a chromium concentration which is at a level that will not lead to the formation of significant amounts of sigma phase. It can be appreciated that by improving the wear resistance of the ferrochromium alloys, in view of the mechanism by which erosion and corrosion occurs, as noted above, it is possible to realize an improvement in the erosion and corrosion resistance of the ferrochromium alloys.
  • an erosion and corrosion resistant ferrochromium alloy comprising the following composition, in wt. %.
  • micro-alloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium and tungsten, and balance, iron and incidental impurities, with a microstructure comprising eutectic chromium carbides in a matrix comprising one or more of ferrite, retained austenite and martensite, as herein defined.
  • ferrous is herein understood to mean body-centred cubic iron (in the alpha and/or delta forms) containing a solid solution of chromium.
  • the ternA"austenite is herein understood to mean face-centred cubic iron containing solid solutions of carbon ajtd chromium.
  • austenite is herein understood to mean a transformation product of austenite.
  • the matrix contains a 25-35 wt. % solid solution of chromium.
  • the microstructure further comprises one of primary chromium carbides, primary ferrite or primary austenite in the matrix.
  • the preferred amount in wt %. of the elements chromium, carbon, manganese, silicon, molybdenum, nickel and copper is as follows:
  • the matrix contains a 29-32 wt. % solid solution of chromium.
  • increasing both the chromium and carbon contents of the ferrochromium alloy above the levels disclosed in the Abex U.S. patents permits the formation of a greater volume fraction of hard carbides to enhance wear resistance. More specifically, and preferably, a stoichiometric balance in the increase in chromium and carbon contents permits the formation of a greater volume fraction of chromium carbides without increasing the chromium content of the matrix to a critical level above which sigma phase embrittlement occurs.
  • The_ alloy of the present invention has a diff-arent microstructure to that of the alloys disclosed in the Abex U.S. patents. The difference is illustrated in the accompanying figures which comprise photocopies of photomicrographs of an alloy disclosed in the Abex U.S. patents and preferred alloys of the present invention.
  • Figure 1 shows the microstructure of an Abex alloy which comprises 28.4% chromium, 1.94% carbon, 0.97% manganese, 1.48% silicon, 2.10% molybdenum, 2.01% nickel and 1.49% copper, the balance substantially iron.
  • the microstructure consists of primary austenite dendrites (50% volume) and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite, retained austenite and martensite.
  • Figure 2 shows the microstructure of one preferred alloy of the present invention which comprises 35.8% chromium, 1.94% carbon, 0.96% manganese, 1.48% silicon, 1.94% carbon, 0.96% manganese, 1.48% silicon, 2.06% molybdenum, 2.04% nickel, 1.48% copper, the balance substantially iron.
  • the microstructure is hypereutectic with primary ferrite dendrites (20% volume) and a eutectic structure comprising finely dispersed eutectic carbides in a matrix of eutectic ferrite. It is noted that when compared with the microstructure of the Abex U.S.
  • the microstructure of Figure 2 reflects that there is a reduced volume of primary dendrites and an increased volume of the eutectic matrix and since the eutectic matrix has a relatively high proportion of carbides there is an overall increase in the volume fraction of hard carbides in the alloy when compared with the Abex alloy. It is noted that the foregoing phenomenon is also apparent to a greater extent from a comparison of the microstructures shown in Figs. 3 to 5 and Fig. 1.
  • Figure 3 shows the microstructure of another preferred alloy of the present invention which comprises 40.0% chromium, 1.92% carbon, 0.96% manganese, 1.59% silicon, 1.95% molybdenum, 1.95% nickel, 1.48% copper, the balance substantially iron.
  • the microstructure consists of eutectic carbides in a matrix of eutectic ferrite.
  • Figure 4 shows the microstructure of another preferred alloy of the present invention which comprises 40.0% chromium, 2.30% carbon, 2.77% manganese, 1.51% silicon, 2.04% molybdenum, 1.88% nickel, 1.43% copper, the balance substantially iron.
  • the microstructure is hypereutectic with primary M 7 C 3 carbides and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite.
  • Figure 5 shows the micr structure of another preferred alloy of the present invention which comprises 43% chromium, 2.02% carbon, 0.92 manganese, 1.44% silicon, 1.88% molybdenum, 1.92% nickel, 1.2% copper, the balance substantially iron.
  • the microstructure in this case is hypereutectic with trace amounts of primary M C carbides and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite.
  • any suitable conventional casting and heat treatment technology may be used to produce the alloys of the present invention.
  • the alloys are formed by casting and then heat treating at a temperature in the range of 600 to 1000°C followed by air cooling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Soft Magnetic Materials (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)
  • Chemically Coating (AREA)
  • Braking Arrangements (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Heat Treatment Of Articles (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Earth Drilling (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Physical Vapour Deposition (AREA)
  • Hard Magnetic Materials (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

An erosion and corrosion resistant ferrochromium alloy comprising the following composition, in wt. %, 34 - 50 chromium, 1.5 - 2.5 carbon, up to 5 manganese, up to 5 silicon, up to 5 molybdenum, up to 10 nickel, up to 5 copper, up to 1 % of each of one or more micro-alloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium and tungsten, and balance, iron and incidental impurities. The alloy has a microstructure comprising eutectic chromium carbides in a matrix comprising one or more of ferrite, retained austenite and martensite, as herein defined. Optionally, the microstructure further comprises one of primary chromium carbides, primary ferrite or primary austenite in the matrix.

Description

A FERROCHROMIUM ALLOY
The present invention relates to a ferrochromium alloy and more particularly to an erosion and corrosion resistant ferrochromium alloy.
The present invention is designed for use in thn formation of parts for lining pumps, pipes, nozzles, mixers and similar devices which, in service, can be subjected to mixtures containing a corrosive fluid and abrasive particles. Typical applications for such parts include flue gas desulphurization, in which the parts are exposed to sulphuric acid and limestone, and fertiliser production, in which the parts are exposed to phosphoric acid, nitric acid and gypsum.
U.S. patents, 4,536,232 and 4,080,198, assigned to Abex Corporation (the "Abex U.S. patentsA), disclose ferrochromium alloys containing approximately 1.6 wt. % carbon and 28 wt. % chromium which are characterized by primary chromium carbide and ferrite islands in a martensite or austenite matrix containing a solid solution of chromium. The level of chromium in the alloys suggests that the alloys should exhibit good corrosion resistance characteristics. However, the performance of such alloys from the corrosion resistance viewpoint is not entirely satisfactory.
An object of the present invention is to provide a ferrochromium alloy which has improved erosion and corrosion resistance compared with the alloys disclosed in the Abex U.S. patents.
The mechanism for erosion and corrosion of alloys of the type disclosed in the Abex U.S. patents in acidic envi.ronments is by accelerated corrosion due to the continuous removal of the passive corrosion-resistant layer by erosive particles in the fluid stream.
In order to replenish the passive layer it is necessary to have the chromium concentration at as high a level as possible in the matrix.
However, simply increasing the chromium content to improve corrosion resistance tends to cause the formation of the sigma phase which is undesirable in view of the embrittlement problems associated with the sigma phase.
The present invention is based on the realization that by increasing both the chromium and carbon concentrations of alloys of the type disclosed in the Abex U.S. patents it is possible to increase the volume fraction of the chromium carbide phase, and thereby improve the wear resistance characteristics of the ferrochromium alloys, while maintaining the matrix at a chromium concentration which is at a level that will not lead to the formation of significant amounts of sigma phase. It can be appreciated that by improving the wear resistance of the ferrochromium alloys, in view of the mechanism by which erosion and corrosion occurs, as noted above, it is possible to realize an improvement in the erosion and corrosion resistance of the ferrochromium alloys.
According to the present invention there is provided an erosion and corrosion resistant ferrochromium alloy comprising the following composition, in wt. %.
34 - 50 chromium
1.5 - 2.5 carbon up to 5 manganese up to 5 silicon up to 5 molybdenum up to 10 nickel up to 5 copper up to 1% of each of one or more micro-alloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium and tungsten, and balance, iron and incidental impurities, with a microstructure comprising eutectic chromium carbides in a matrix comprising one or more of ferrite, retained austenite and martensite, as herein defined.
The term "ferrite" is herein understood to mean body-centred cubic iron (in the alpha and/or delta forms) containing a solid solution of chromium.
The ternA"austenite" is herein understood to mean face-centred cubic iron containing solid solutions of carbon ajtd chromium.
The term "martensite" is herein understood to mean a transformation product of austenite.
It is preferred that the matrix contains a 25-35 wt. % solid solution of chromium.
It is preferred that the microstructure further comprises one of primary chromium carbides, primary ferrite or primary austenite in the matrix.
The preferred amount in wt %. of the elements chromium, carbon, manganese, silicon, molybdenum, nickel and copper is as follows:
36 - 40 chromium
1.9 - 2.1 carbon
1 - 2 manganese
0.5 - 1.5 silicon
1 - 2 molybdenum
1 - 5 nickel
1 - 2 copper
With the foregoing preferred composition it is preferred that the matrix contains a 29-32 wt. % solid solution of chromium.
In accordance with the invention, increasing both the chromium and carbon contents of the ferrochromium alloy above the levels disclosed in the Abex U.S. patents permits the formation of a greater volume fraction of hard carbides to enhance wear resistance. More specifically, and preferably, a stoichiometric balance in the increase in chromium and carbon contents permits the formation of a greater volume fraction of chromium carbides without increasing the chromium content of the matrix to a critical level above which sigma phase embrittlement occurs.
It has been found that preferred alloys of the present invention exhibit superior corrosion and erosion resistance to the alloys disclosed in the Abex U.S. patents. This is illustrated in Table 1 below which lists the results of laboratory scale potentiodynamic corrosion and disc wear tests on alloys disclosed in the Abex U.S. patents and preferred alloys of the present invention. The compositions of the alloys are listed in Table 2 below.
Table It Corrosion and Erosion Test Results
Corrosion * Erosion ** (mm/yr) (mm-Vhr)
488 614 370 444 * 10% Sulphuric Acid, 25°C to ASTM G61 ** 40 weight % Silica Sand Slurry @ 18 m/s
Table 2t Composition of Alloys of Table 1
Cr Mn Si Mo Ni Cu Fe
ABEX Alloy #1* 28.4 1.94 0.97
ABEX Alloy #2** 27.5 1.65 1.21
Casting # 1 35.8 1.95 0.96
Casting # 2 40.0 1.92 0.96
* As-cast alloy with composition within range of U.S. Patent 4,536,232
** Heat treated alloy with composition within range of U.S. Patent 4,536,232
It will be noted from Table 1 that the corrosion and erosion resistance of the preferred alloys of the present invention is significantly better than that of the Abex alloys.
The_ alloy of the present invention has a diff-arent microstructure to that of the alloys disclosed in the Abex U.S. patents. The difference is illustrated in the accompanying figures which comprise photocopies of photomicrographs of an alloy disclosed in the Abex U.S. patents and preferred alloys of the present invention. Figure 1 shows the microstructure of an Abex alloy which comprises 28.4% chromium, 1.94% carbon, 0.97% manganese, 1.48% silicon, 2.10% molybdenum, 2.01% nickel and 1.49% copper, the balance substantially iron. The microstructure consists of primary austenite dendrites (50% volume) and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite, retained austenite and martensite.
Figure 2 shows the microstructure of one preferred alloy of the present invention which comprises 35.8% chromium, 1.94% carbon, 0.96% manganese, 1.48% silicon, 1.94% carbon, 0.96% manganese, 1.48% silicon, 2.06% molybdenum, 2.04% nickel, 1.48% copper, the balance substantially iron. The microstructure is hypereutectic with primary ferrite dendrites (20% volume) and a eutectic structure comprising finely dispersed eutectic carbides in a matrix of eutectic ferrite. It is noted that when compared with the microstructure of the Abex U.S. patent shown in Figure 1 the microstructure of Figure 2 reflects that there is a reduced volume of primary dendrites and an increased volume of the eutectic matrix and since the eutectic matrix has a relatively high proportion of carbides there is an overall increase in the volume fraction of hard carbides in the alloy when compared with the Abex alloy. It is noted that the foregoing phenomenon is also apparent to a greater extent from a comparison of the microstructures shown in Figs. 3 to 5 and Fig. 1.
Figure 3 shows the microstructure of another preferred alloy of the present invention which comprises 40.0% chromium, 1.92% carbon, 0.96% manganese, 1.59% silicon, 1.95% molybdenum, 1.95% nickel, 1.48% copper, the balance substantially iron. The microstructure consists of eutectic carbides in a matrix of eutectic ferrite.
Figure 4 shows the microstructure of another preferred alloy of the present invention which comprises 40.0% chromium, 2.30% carbon, 2.77% manganese, 1.51% silicon, 2.04% molybdenum, 1.88% nickel, 1.43% copper, the balance substantially iron. The microstructure is hypereutectic with primary M7C3 carbides and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite.
Figure 5 shows the micr structure of another preferred alloy of the present invention which comprises 43% chromium, 2.02% carbon, 0.92 manganese, 1.44% silicon, 1.88% molybdenum, 1.92% nickel, 1.2% copper, the balance substantially iron. The microstructure in this case is hypereutectic with trace amounts of primary M C carbides and a eutectic structure comprising eutectic carbides in a matrix of eutectic ferrite.
Any suitable conventional casting and heat treatment technology may be used to produce the alloys of the present invention. However, it is preferred that the alloys are formed by casting and then heat treating at a temperature in the range of 600 to 1000°C followed by air cooling.
Many modifications may be made to the alloy described above without departing from the spirit and scope of the invention.

Claims

CLAIMS :
1. An erosion and corrosion resistant ferrochromium alloy comprising the following composition, in wt. %.
34 - 50 chromium
1.5 - 2.5 carbon up to 5 manganese up to 5 silicon up to 5 molybdenum up to 10 nickel up to 5 copper up to 1% of each of one or more micro-alloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium and tungsten, and balance, iron and incidental impurities, with a microstructure comprising eutectic chromium carbides in a matrix comprising one or more of ferrite, retained austenite and martensite, as herein defined.
2. The alloy defined in claim 1, wherein the microstructure further comprises one of primary chromium carbides, primary ferrite or primary austenite in the matrix.
3. The alloy defined in claim 1, wherein the matrix contains a 25-35 wt. % solid solution of chromium.
4. The alloy defined in any one of the preceding claims comprising in wt %: - 10 -
36 - 40 , chromium 1.9 - 2.1 carbon 1 - 2 manganese 0.5 - 1.5 silicon 1 - 2 molybdenum 1 - 5 nickel 1 - 2 copper.
5. A method of producing the alloy defined in any one of the preceding claims, comprising heat treating the alloy at a temperature in the range of 600 - 1000°C and air cooling the alloy.
EP90911863A 1989-08-04 1990-08-03 A ferrochromium alloy Expired - Lifetime EP0438560B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPJ562889 1989-08-04
AU5628/89 1989-08-04
PCT/AU1990/000331 WO1991002101A1 (en) 1989-08-04 1990-08-03 A ferrochromium alloy

Publications (3)

Publication Number Publication Date
EP0438560A1 EP0438560A1 (en) 1991-07-31
EP0438560A4 true EP0438560A4 (en) 1992-01-15
EP0438560B1 EP0438560B1 (en) 1996-04-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90911863A Expired - Lifetime EP0438560B1 (en) 1989-08-04 1990-08-03 A ferrochromium alloy

Country Status (11)

Country Link
EP (1) EP0438560B1 (en)
KR (1) KR940003890B1 (en)
CN (1) CN1029692C (en)
AT (1) ATE137274T1 (en)
CA (1) CA2037921C (en)
DE (1) DE69026701T2 (en)
ES (1) ES2087159T3 (en)
HK (1) HK1006859A1 (en)
HU (1) HU212085B (en)
TW (1) TW208044B (en)
WO (1) WO1991002101A1 (en)

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DE4409278A1 (en) * 1994-03-18 1995-09-21 Klein Schanzlin & Becker Ag Corrosion and wear resistant chilled cast iron
ES2111405T3 (en) * 1994-05-17 1998-03-01 Ksb Ag HARD CAST IRON WITH HIGH CORROSION AND WEAR RESISTANCE.
DE19512044A1 (en) * 1994-05-17 1995-11-23 Klein Schanzlin & Becker Ag Chilled cast iron with high corrosion and wear resistance
SE522667C2 (en) * 2000-05-16 2004-02-24 Proengco Tooling Ab Process for the preparation of an iron-based chromium carbide containing dissolved tungsten and such an alloy
CN1353204B (en) * 2000-11-09 2012-05-23 国立清华大学 High Entropy Multicomponent Alloys
CN101466914B (en) * 2006-04-21 2014-10-01 国际壳牌研究有限公司 Time sequenced heating of multiple layers in a hydrocarbon containing formation
RU2329324C1 (en) * 2006-11-24 2008-07-20 Открытое акционерное общество "ГАЗ" (ОАО "ГАЗ") Iron
US8479700B2 (en) * 2010-01-05 2013-07-09 L. E. Jones Company Iron-chromium alloy with improved compressive yield strength and method of making and use thereof
US9080229B2 (en) 2012-05-07 2015-07-14 Ut-Battelle, Llc Nano-composite stainless steel
CN102747304A (en) * 2012-06-23 2012-10-24 昆明嘉和科技股份有限公司 Corrosion-resistant abrasion-resistant alloy material and preparation method thereof
CN102828182A (en) * 2012-09-20 2012-12-19 丹阳宏图激光科技有限公司 Laser cladding repair process for gear
CN103436800A (en) * 2013-07-18 2013-12-11 襄阳五二五泵业有限公司 Iron-chromium alloy having high wear and corrosion resistance and corrosion resistance
JP6151304B2 (en) 2015-05-26 2017-06-21 山陽特殊製鋼株式会社 Projection material for shot peening using hard powder with high productivity and corrosion resistance
CN105003758A (en) * 2015-06-15 2015-10-28 淄博滕坤工贸有限公司 High alloy wear-resistant double-layer composite straight pipe used for concrete pump truck
CN105483558A (en) * 2015-12-08 2016-04-13 襄阳五二五泵业有限公司 High-chromium alloy material for flue gas desulfurization pump and manufacturing method of high-chromium alloy material
CN105755362B (en) * 2016-02-23 2017-09-01 湖南省冶金材料研究院 A kind of high carbon and chromium powder metallurgy high-abrasive material and preparation method thereof
CN107747055A (en) * 2017-09-28 2018-03-02 江苏晶王新材料科技有限公司 A kind of wear-resistant light metal material
CN107988540A (en) * 2017-12-01 2018-05-04 张海江 A kind of wear-resisting rare earth alloy and preparation method thereof
CN108397086B (en) * 2018-02-28 2019-04-30 苏州盈腾五金制品有限公司 A kind of corrosion-resistant plastic-steel door and window
CN112226671A (en) * 2020-09-29 2021-01-15 安徽索立德铸业有限公司 Wear-resistant corrosion-resistant alloy for water pump casting and preparation method thereof
CN113215479A (en) * 2021-05-07 2021-08-06 福建辉丰环境工程科技有限公司 Preparation method of high-wear-resistance steel
CN115537683B (en) * 2021-06-30 2024-03-12 叶均蔚 High-strength corrosion-resistant ferrochrome block and application thereof
CN117051315A (en) * 2023-08-23 2023-11-14 河北技投机械设备有限公司 High-corrosion-resistance wear-resistant high-chromium cast iron and preparation method and application thereof

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Also Published As

Publication number Publication date
TW208044B (en) 1993-06-21
EP0438560B1 (en) 1996-04-24
CN1050569A (en) 1991-04-10
ATE137274T1 (en) 1996-05-15
CA2037921C (en) 2006-11-21
ES2087159T3 (en) 1996-07-16
EP0438560A1 (en) 1991-07-31
CN1029692C (en) 1995-09-06
HUT57285A (en) 1991-11-28
DE69026701D1 (en) 1996-05-30
KR940003890B1 (en) 1994-05-04
WO1991002101A1 (en) 1991-02-21
HK1006859A1 (en) 1999-03-19
DE69026701T2 (en) 1996-12-12
KR920701499A (en) 1992-08-11
CA2037921A1 (en) 1991-02-04
HU212085B (en) 1996-02-28
HU906124D0 (en) 1991-07-29

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