EP0388816A1 - Passivation de métaux pyrophoriques - Google Patents

Passivation de métaux pyrophoriques Download PDF

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Publication number
EP0388816A1
EP0388816A1 EP90105021A EP90105021A EP0388816A1 EP 0388816 A1 EP0388816 A1 EP 0388816A1 EP 90105021 A EP90105021 A EP 90105021A EP 90105021 A EP90105021 A EP 90105021A EP 0388816 A1 EP0388816 A1 EP 0388816A1
Authority
EP
European Patent Office
Prior art keywords
guanidine
weight
metal
agent
pyrophoric
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
EP90105021A
Other languages
German (de)
English (en)
Other versions
EP0388816B1 (fr
Inventor
Helmut Dr. Lischka
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.)
Skw Stahl-Technik degussa AG GmbH
Original Assignee
SKW Trostberg AG
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 SKW Trostberg AG filed Critical SKW Trostberg AG
Priority to AT90105021T priority Critical patent/ATE71866T1/de
Publication of EP0388816A1 publication Critical patent/EP0388816A1/fr
Application granted granted Critical
Publication of EP0388816B1 publication Critical patent/EP0388816B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/10—Making spheroidal graphite cast-iron
    • C21C1/105—Nodularising additive agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/146—Nitrogen-containing compounds containing a multiple nitrogen-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention relates to a process for the passivation of pyrophoric metals, in particular magnesium.
  • pyrophoric metals such as magnesium, calcium or the alloys of these metals pose particular problems in handling, especially when these pyrophoric substances are used in finely divided form.
  • magnesium powder which is blown into liquid pig iron alone or in combination with calcium carbide or lime for the purpose of desulfurization with the aid of a refractory immersion lance, cannot easily be used due to the flammability and the severity of the fire behavior. Rather, it must first be passivated using suitable means or methods.
  • the invention is therefore based on the object of developing a method for passivating pyrophoric metals, in particular magnesium, by coating with a passivating agent which does not have the disadvantages of the prior art mentioned, but rather provides the pyrophoric metals with a coating without great technical outlay , which effectively suppresses the easy ignitability of these metals and at the same time does not pose any environmental problems.
  • This object is achieved in that 0.5 to 5% by weight of an s-triazine and / or guanidine derivative, based on the weight of the metal to be passivated, is used as the passivating agent.
  • the pyrophoric metal which can be, in particular, magnesium, calcium or an alloy of these metals, is coated with a passivating agent based on s-triazine and / or guanidine derivatives.
  • a passivating agent based on s-triazine and / or guanidine derivatives.
  • the passivating agent is used in amounts of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the weight of the metal. In principle, it is possible to use larger quantities, but this excess quickly becomes uneconomical because it has no additional effect.
  • melamine is particularly preferred due to its low cost availability.
  • the s-triazine derivatives ammeline and ammelide and the guanamines benzoguanamine or acetoguanamine are also readily available and easy to use.
  • Compounds which have several s-triazine structural units can also be used for the purpose according to the invention. These include polymeric s-triazines and more highly condensed s-triazine compounds such as Melam, Melem or Melon.
  • condensation products of s-triazines for example melamine and / or benzoguanamine, condensation products with formaldehyde being preferred.
  • guanidines In principle, a large number of compounds from the group of guanidines can also be used, the unsubstituted free guanidine itself and also substituted guanidines, if appropriate in the form of salts, being suitable as guanidines.
  • guanidines will be used, which are relatively easy to manufacture and therefore inexpensive to obtain are.
  • the substituted guanidines this is especially the case with cyanoguanidine (dicyandiamide) and with guanylurea or with guanylurea phosphate, which is why these compounds are used with preference.
  • Simple guanidine salts can also be used, the anions of which do not contain any interfering components such as Contain chlorides.
  • Preferred are guanidine phosphates, guanidine sulfamates and guanidine cyanurates, which are also readily available.
  • a wetting agent which is preferably anhydrous and is used in an amount of 0.1 to 0.5% by weight, based on the weight of the metal .
  • the usual products can be used as water-free wetting agents, the use of highly viscous oils, in particular silicone and / or mineral oils, having proven particularly advantageous.
  • the production of the coatings on the pyrophoric metals can be carried out easily and in a technically simple manner.
  • the finely divided passivating agents e.g. in the form of powders, first optionally sprayed with the wetting agent in an inert gas atmosphere and then using customary methods, e.g. Mix, the passivating agent applied to the surface of the pyrophoric metals.
  • the passivating agents must be in the finest possible form to ensure complete coating and satisfactory adhesion.
  • the passivating agents are therefore preferably used with a particle size of ⁇ 50 ⁇ m, preferably ⁇ 10 ⁇ m.
  • the passivated metals produced by the process according to the invention are also notable for their high flammability and favorable fire behavior. They are therefore particularly suitable as treatment agents for metallurgical melts, preferably for the desulphurization of pig iron, especially since no undesired or disruptive decomposition products are formed during the thermal decomposition of the passivating agents.
  • Example 1 99 parts by weight of metallic magnesium powder (magnesium content 99.8%) with a grain size of 0.2-0.8 mm were coated with 1 part by weight of finely divided cyanoguanidine (particle size 98% ⁇ 10 ⁇ m).
  • Example 1 97 parts by weight of metallic magnesium powder (magnesium content 99.8%) with a grain size of 0.2-0.8 mm were passivated with 3 parts by weight of finely divided melamine (particle size 99% ⁇ 60 ⁇ m).
  • test substance is shaped in a commercial form into an approximately 250 mm long, 20 mm wide and 10 mm high continuous bed and placed on a cold impermeable surface with low thermal conductivity.
  • the fill is ignited at one end with the help of a Bunsen burner.
  • the observed burn-up time is a measure of the pyrophoric character of the test substance.
  • Burning and ignition attempts attempt composition Burn-up time for 200 mm measuring section 1 comparison 100% by weight of Mg 99.8% 8 minutes 2 comparison 88 wt% Mg alloy 90% 10 mins 12% by weight coating 10 wt .-% Al2O3 2 wt .-% SiO2 3 comparison 73 wt% Mg alloy 90% 7 minutes 15% by weight of Al powder 12% by weight coating 10 wt .-% Al2O3 2 wt .-% SiO2 4 comparison 50 wt.% Mg 99.8% 11 minutes 50 wt .-% ball mill dust 35 wt .-% Al2O3 13.5% by weight of Al 1.5% by weight NaCl + KCl 5 97% by weight of Mg 99.8% extinguishes after ignition 3% by weight cyanoguanidine 6 99% by weight Mg 99.8% 27 minutes 1% by weight cyanoguanidine 7 97% by weight of Mg 99.8% 32 minutes 3% by weight melamine

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Fireproofing Substances (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Powder Metallurgy (AREA)
  • Luminescent Compositions (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Semiconductor Lasers (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)
EP90105021A 1989-03-17 1990-03-16 Passivation de métaux pyrophoriques Expired - Lifetime EP0388816B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90105021T ATE71866T1 (de) 1989-03-17 1990-03-16 Passivierung von pyrophoren metallen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3908815 1989-03-17
DE3908815A DE3908815A1 (de) 1989-03-17 1989-03-17 Verfahren zur passivierung von pyrophoren metallen

Publications (2)

Publication Number Publication Date
EP0388816A1 true EP0388816A1 (fr) 1990-09-26
EP0388816B1 EP0388816B1 (fr) 1992-01-22

Family

ID=6376597

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90105021A Expired - Lifetime EP0388816B1 (fr) 1989-03-17 1990-03-16 Passivation de métaux pyrophoriques

Country Status (8)

Country Link
US (1) US5089049A (fr)
EP (1) EP0388816B1 (fr)
JP (1) JPH0768564B2 (fr)
KR (1) KR0137936B1 (fr)
AT (1) ATE71866T1 (fr)
CA (1) CA2011785C (fr)
DE (3) DE8915539U1 (fr)
FI (1) FI90211C (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0546351A2 (fr) * 1991-11-21 1993-06-16 SKW Trostberg Aktiengesellschaft Fil fourré contenant un métal pyrophore passivé et son application
DE102020102628A1 (de) 2020-02-03 2021-08-05 Eos Gmbh Verfahren zur Moderation einer Reaktion von Metallpartikeln

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5342430A (en) * 1993-07-28 1994-08-30 Grocela Kathe Teresa A Passivation of methylchlorosilane fines
DE102007061236A1 (de) * 2007-12-19 2009-07-09 Ecka Granulate Gmbh & Co. Kg Transportform für unedle Metallteilchen und Verwendung derselben
JP5361784B2 (ja) * 2010-04-15 2013-12-04 日本マテリアル株式会社 金属カルシウムの保護方法及び保護された金属カルシウム
JP5542088B2 (ja) * 2011-04-06 2014-07-09 日本マテリアル株式会社 鉄系金属の脱硫剤、その製造方法及び脱硫方法
JP6595808B2 (ja) * 2015-06-05 2019-10-23 久幸 末松 マグネシウム金属微粒子及びマグネシウム金属微粒子の製造方法
JP7191590B2 (ja) * 2018-08-24 2022-12-19 三星電子株式会社 有機無機複合組成物、ならびにこれを含む成形品および光学部品

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2496354A (en) * 1947-09-11 1950-02-07 Cities Service Oil Co Method of inhibiting hydrogen sulfide corrosion of metals
US3096147A (en) * 1960-10-06 1963-07-02 Gen Mills Inc Process for inhibiting corrosion in acid solutions with guanamine-propylene oxide condensation product
US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
EP0046139B1 (fr) * 1980-08-13 1984-07-18 Ciba-Geigy Ag Utilisation d'acides triazinecarboxyliques comme inhibiteurs de corrosion pour systèmes aqueux
EP0129491A1 (fr) * 1983-06-21 1984-12-27 Pechiney Electrometallurgie Procédé de passivation à sec de magnésium à l'état divisé
US4541867A (en) * 1984-03-20 1985-09-17 Amax Inc. Varnish-bonded carbon-coated magnesium and aluminum granules

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329168A (en) * 1980-07-01 1982-05-11 Rubio Charles A Amine treatment for passivating sponge iron
US4814007A (en) * 1986-01-16 1989-03-21 Henkel Corporation Recovery of precious metals

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2496354A (en) * 1947-09-11 1950-02-07 Cities Service Oil Co Method of inhibiting hydrogen sulfide corrosion of metals
US3096147A (en) * 1960-10-06 1963-07-02 Gen Mills Inc Process for inhibiting corrosion in acid solutions with guanamine-propylene oxide condensation product
US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
EP0046139B1 (fr) * 1980-08-13 1984-07-18 Ciba-Geigy Ag Utilisation d'acides triazinecarboxyliques comme inhibiteurs de corrosion pour systèmes aqueux
EP0129491A1 (fr) * 1983-06-21 1984-12-27 Pechiney Electrometallurgie Procédé de passivation à sec de magnésium à l'état divisé
US4541867A (en) * 1984-03-20 1985-09-17 Amax Inc. Varnish-bonded carbon-coated magnesium and aluminum granules

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 1, Nr. 102 (C-77)[2288], 10. September 1977, Seite 2288 C 77; & JP-A-52 63 811 (UBE KOSAN K.K.) 26-05-1977 *
PATENT ABSTRACTS OF JAPAN, Band 13, Nr. 354 (E-802)[3702], 8. August 1989, Seite 11 E 802; & JP-A-01 114 006 (SANKYO SEIKI Mfg CO., LTD) 02-05-1989, (Kat. P) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0546351A2 (fr) * 1991-11-21 1993-06-16 SKW Trostberg Aktiengesellschaft Fil fourré contenant un métal pyrophore passivé et son application
EP0546351A3 (en) * 1991-11-21 1993-12-29 Sueddeutsche Kalkstickstoff Cored wire containing a passivated pyrophoric metal and its application
TR26635A (tr) * 1991-11-21 1995-03-15 Sueddeutsche Kalkstickstoff PASIFLESTIRILMIS PIROFORIK METAL IHTIVA EDEN NüVELI TEL VE BUNUN KULLANILMASI
DE102020102628A1 (de) 2020-02-03 2021-08-05 Eos Gmbh Verfahren zur Moderation einer Reaktion von Metallpartikeln

Also Published As

Publication number Publication date
FI90211B (fi) 1993-09-30
DE8915539U1 (fr) 1990-10-04
JPH02282402A (ja) 1990-11-20
CA2011785C (fr) 1995-12-19
US5089049A (en) 1992-02-18
KR900014640A (ko) 1990-10-24
JPH0768564B2 (ja) 1995-07-26
ATE71866T1 (de) 1992-02-15
DE59000035D1 (de) 1992-03-05
EP0388816B1 (fr) 1992-01-22
FI901342A0 (fi) 1990-03-16
KR0137936B1 (ko) 1998-07-15
FI90211C (fi) 1994-01-10
DE3908815A1 (de) 1990-09-20
CA2011785A1 (fr) 1990-09-17

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