EP0971047B1 - Boriermittel - Google Patents

Boriermittel Download PDF

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Publication number
EP0971047B1
EP0971047B1 EP99111057A EP99111057A EP0971047B1 EP 0971047 B1 EP0971047 B1 EP 0971047B1 EP 99111057 A EP99111057 A EP 99111057A EP 99111057 A EP99111057 A EP 99111057A EP 0971047 B1 EP0971047 B1 EP 0971047B1
Authority
EP
European Patent Office
Prior art keywords
weight
boriding
boron
boriding agent
agent according
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
Application number
EP99111057A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0971047A1 (de
Inventor
Ulrich Dr. Baudis
Stefan Dr. Wigger
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.)
Durferrit GmbH Thermotechnik
Original Assignee
Durferrit GmbH Thermotechnik
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Filing date
Publication date
Application filed by Durferrit GmbH Thermotechnik filed Critical Durferrit GmbH Thermotechnik
Publication of EP0971047A1 publication Critical patent/EP0971047A1/de
Application granted granted Critical
Publication of EP0971047B1 publication Critical patent/EP0971047B1/de
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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/68—Boronising
    • C23C8/70—Boronising of ferrous surfaces

Definitions

  • the invention relates to a Borierstoff for the production of Boride coatings on metallic materials. This serves in particular for the production of single-phase, hard and adherent Borid füren on iron materials to increase wear resistance and improve the Corrosion resistance of corresponding workpieces.
  • Boring for wear protection of iron, steel and refractory metals is a well-known process.
  • dense, uniform layers of the respective boride for example the borides FeB, Fe 2 B are formed on iron.
  • the borides have considerably changed properties compared to the pure metals Most Boride very hard, corrosion resistant and therefore extremely wear-resistant. Due to their generation by diffusion and solid state reaction, the boride layers are firmly bonded to the base material.
  • boron-treated steels are sometimes superior to steels treated by nitriding or carburizing.
  • Bie boration is usually used at temperatures between 800 and 1100 ° C and in particular between 850 and 950 ° C. carried out.
  • the achievable layer thicknesses of Boride layers are in the range between 30 and 300 microns.
  • Suitable activating substances are chlorides or Fluoride-donating compounds such as alkali and Alkaline earth chlorides or fluorides. Especially common as activators are fluoroborates such as in particular Potassium tetrafluoroborate.
  • Typical extenders are Alumina, silica and silicon carbide. Boriering agents of this type are for example in DE-PS 17 96 216 described. A typical composition which has proven itself to date as Borierstoff contains about 5 wt.% Boron carbide, 5 wt.% Potassium tetrafluoroborate and 90% by weight silicon carbide.
  • Borierstoff of the type mentioned are usually used as powder mixtures. she but also as granules (for example DE-OS 21 27 096) or be formulated as pastes (e.g., DE-OS 26 33 137). In the event of granules and pastes contain the compositions still minor amounts of binders or water.
  • the boron-rich FeB phase is much more brittle than the Fe 2 B phase, which has a negative effect on the wear resistance of the borated components.
  • boride layers of more than 50 ⁇ m it is also very easy to form a FeB boundary layer, which should be avoided as far as possible for the stated reason.
  • the invention therefore an object of the invention to develop a Borierstoff, with the use of ferrous materials virtually exclusively single-phase, Fe 2 Benthaltende Borid harshen can be generated. Furthermore, the content of water-soluble fluorides should be lowered in this Borierstoff and associated with normal use, a reduced fluorine emission.
  • the invention relates to a boriding agent as characterized above for producing boride layers on metallic workpieces, in particular for producing single-phase, Fe 2 B-containing boride layers on workpieces made of iron materials.
  • the boriding agent according to the invention contains as activating substance a combination of 1 to 5% by weight of potassium tetrafluoroborate (KBF 4 ) and 10 to 40% by weight of calcium fluoride (CaF 2 ), the quantities referring to the total amount of boriding agent.
  • the boriding agent according to the invention preferably comprises as activator substance a combination of 2 to 4% by weight, in particular about 2.5% by weight, of potassium tetrafluoroborate and 10 to 30% by weight, in particular about 25% by weight, of calcium fluoride.
  • the boriding agent according to the invention may contain the customary boron-emitting substances, such as amorphous or crystalline ferroboron and in particular boron carbide (B 4 C). Preferably, it contains from 2 to 10% by weight of boron carbide.
  • the boriding agent according to the invention contains the usual extenders in the remainder, in particular silicon carbide (SiC).
  • the boriding agent according to the invention preferably contains boron-emitting substance 2 to 10 wt.% Boron carbide, as activating substance 1 to 5 wt.% Potassium tetrafluoroborate and 10 to 40% by weight of calcium fluoride and as extender in the balance of silicon carbide.
  • a particularly preferred composition consists of 3 to 5 wt.% Boron carbide, 2 to 4 wt.% Potassium tetrafluoroborate, 10 to 30 wt.% Calcium fluoride and 61 to 85 Wt.% Silicon carbide.
  • a typical composition consists of 4% by weight B 4 C, 2.5% by weight KBF 4 , 25% by weight CaF 2 and 68.5% by weight SiC.
  • the boriding agent according to the invention typically comes in the form of a powder mixture for use.
  • a powder mixture for use of such a powder mixture are only the powdered starting materials, if necessary after Milling, intimately mixed.
  • the particle size of such Powder mixtures are typically in the range 10 to 250 microns.
  • the inventive Borierstoff formulate in the form of granules.
  • the corresponding powder mixture for example pasted with water and optionally a binder and then made a granulate in a known manner become.
  • the particle size is typical in the range 0.1 to 2.5 mm.
  • the boring agent as To formulate paste. This can be done by adding Water and possibly minor amounts of Auxiliaries, such as Binder, from the corresponding Powder mixture are produced.
  • the boriding agent according to the invention can be used very advantageously for the production of boride layers on metallic workpieces.
  • a reduced KBF 4 content is furthermore advantageous in the intended use of the composition since correspondingly lower fluorine gas emissions occur.
  • a particular advantage of the boriding agent according to the invention is that it is possible to easily produce single-phase, Fe 2 B-containing boride layers on workpieces made of iron materials.
  • the surface of the workpieces is covered with the boriding agent and then treated at temperatures between 800 and 1100 ° C until a boride layer of the desired thickness has formed ,
  • packing the parts in a known manner in closed iron boxes in a powder mixture or granules of boriding agent according to the invention, so that the surfaces of the parts are completely covered.
  • the surface of the parts can also be painted with a boriding agent paste. This is advantageous when a partially borated surface is desired.
  • the boriding is preferably carried out at temperatures between 850 and 950 ° C over a period of 20 minutes to 2 hours.
  • single-phase Fe 2 B layers of a thickness of 30 to 150 ⁇ m can be obtained.
  • a 42CrMo4 component was borated at 920 ° C for 30 minutes in a prior art boriding agent of the following composition: 4% by weight B 4 C 5% by weight KBF 4 91% by weight SiC.
  • the component was moderately easy to remove from the boriding agent, the Borierstoff difficult to grind between the fingers to powder.
  • the boride layer had a layer thickness of 45-50 ⁇ m, with FeB tips up to 16 ⁇ m deep. Fluorine gas emissions of about 4 g / kg boric acid were measured.
  • a component of 42CrMo4 was borated at 920 ° C. for 30 minutes in a boriding agent according to the invention having the following composition: 4% by weight B 4 C 5% by weight KBF 4 10% by weight CaF 2 81% by weight SiC.
  • the component was moderately easy to remove from the boriding agent, the boriding agent moderately easy to grind between the fingers to powder.
  • the boride layer had a thickness of about 50 microns and was completely FeB-free.
  • the layer structure was significantly more uniform than in the layer from Example 1. Fluoro gas emissions of about 4 g / kg boric acid were measured.
  • a component of 42CrMo4 was borated at 920 ° C. for 30 minutes in a boriding agent according to the invention having the following composition: 4% by weight B 4 C 2% by weight KBF 4 30% by weight CaF 2 64% by weight SiC.
  • the component was easily removed from the boriding agent Remove the boric acid slightly between your fingers Grate powder.
  • the boride layer had a thickness of 50-55 ⁇ m, was completely FeB-free and had a very good uniform, compact construction.
  • the fluorine emissions amounted to only 2 g / kg Borierstoff.
  • a 42CrMo4 component was borated at 920 ° C. for 30 minutes in a boring agent having the following composition: 4% by weight B 4 C 2% by weight KBF 4 94% by weight SiC.
  • the component was moderately easy to remove from the boriding agent, the Borierstoff quite easily grind between the fingers to powder.
  • the boride layer had a thickness of 40-50 ⁇ m.
  • a component of 42CroMo4 was borated for 30 minutes at 920 ° C. in a mixture of the following composition: 10% by weight B 4 C 30% by weight CaF 2 60% by weight SiC.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Ceramic Products (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Chemically Coating (AREA)
  • Fireproofing Substances (AREA)
  • Laminated Bodies (AREA)
EP99111057A 1998-07-09 1999-06-15 Boriermittel Expired - Lifetime EP0971047B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19830654A DE19830654C2 (de) 1998-07-09 1998-07-09 Boriermittel, seine Verwendung und Verfahren zur Erzeugung einphasiger, Fe¶2¶B-haltiger Boridschichten
DE19830654 1998-07-09

Publications (2)

Publication Number Publication Date
EP0971047A1 EP0971047A1 (de) 2000-01-12
EP0971047B1 true EP0971047B1 (de) 2003-01-08

Family

ID=7873432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99111057A Expired - Lifetime EP0971047B1 (de) 1998-07-09 1999-06-15 Boriermittel

Country Status (10)

Country Link
US (1) US6245162B1 (xx)
EP (1) EP0971047B1 (xx)
JP (1) JP4209043B2 (xx)
AT (1) ATE230809T1 (xx)
CA (1) CA2277006A1 (xx)
CZ (1) CZ295205B6 (xx)
DE (2) DE19830654C2 (xx)
ES (1) ES2189316T3 (xx)
TR (1) TR199901596A3 (xx)
ZA (1) ZA994445B (xx)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10163107C1 (de) * 2001-12-24 2003-07-10 Univ Hannover Magnesium-Werkstück und Verfahren zur Ausbildung einer korrosionsschützenden Deckschicht eines Magnesium-Werkstücks
WO2003074758A1 (en) * 2002-03-01 2003-09-12 Stichting Voor De Technische Wetenschappen Method of forming a diamond coating on an iron-based substrate and use of such an iron-based substrate for hosting a cvd diamond coating
CA2502575A1 (en) * 2002-11-15 2004-06-03 University Of Utah Research Foundation Integral titanium boride coatings on titanium surfaces and associated methods
CN1293227C (zh) * 2004-10-29 2007-01-03 武汉理工大学 金属表面渗硼层的快速制备方法
US7459105B2 (en) * 2005-05-10 2008-12-02 University Of Utah Research Foundation Nanostructured titanium monoboride monolithic material and associated methods
JP2009512778A (ja) * 2005-09-22 2009-03-26 スカフコ エンジニアリング アンド マニュファクチャリング， インコーポレイテッド プラズマホウ化方法
MX2008013386A (es) * 2006-04-20 2009-01-26 Skaff Corp Of America Inc Partes mecanicas que tienen resistencia incrementada contra el desgaste.
WO2008116159A2 (en) * 2007-03-22 2008-09-25 Skaff Corporation Of America, Inc. Mechanical parts having increased wear-resistance
US20100176339A1 (en) * 2009-01-12 2010-07-15 Chandran K S Ravi Jewelry having titanium boride compounds and methods of making the same
US8894770B2 (en) * 2012-03-14 2014-11-25 Andritz Iggesund Tools Inc. Process and apparatus to treat metal surfaces
CN103938150B (zh) * 2014-04-01 2016-02-17 山东建筑大学 一种低温固体渗硼活化剂
US20170320171A1 (en) * 2016-05-06 2017-11-09 Siemens Energy, Inc. Palliative superalloy welding process
US11192792B2 (en) 2017-03-14 2021-12-07 Bwt Llc Boronizing powder compositions for improved boride layer quality in oil country tubular goods and other metal articles
US10870912B2 (en) 2017-03-14 2020-12-22 Bwt Llc Method for using boronizing reaction gases as a protective atmosphere during boronizing, and reaction gas neutralizing treatment
DE102019202477A1 (de) * 2019-02-25 2020-08-27 Robert Bosch Gmbh Reibbremskörper für eine Reibbremse eines Kraftfahrzeugs, Verfahren zum Herstellen eines Reibbremskörpers
CN114703447A (zh) * 2022-04-01 2022-07-05 江苏科技大学 一种具有单相Fe2B组织的渗硼剂及其制备方法与应用
CN115571891B (zh) * 2022-09-28 2023-12-05 中国科学院南京土壤研究所 一种S掺杂Fe2B复合材料的制备方法及应用

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1796212B1 (de) * 1968-09-21 1972-05-31 Inst Haerterei Technik Verfahren zum borieren von titan und seinen legierungen
US3634145A (en) * 1968-12-09 1972-01-11 Triangle Ind Inc Case-hardened metals
DE2126379C3 (de) * 1971-05-27 1979-09-06 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Verfahren zum Borieren von Metallen, insbesondere von Stahl
DE2127096C3 (de) * 1971-06-01 1980-11-06 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Verfahren zum Borieren von Metallen, insbesondere von Stahl und Eisen
DE2146472C3 (de) * 1971-09-16 1979-01-11 Elektroschmelzwerk Kempten Gmbh, 8000 Muenchen Pulverförmiges Borierungsmittel
DE2208734C3 (de) * 1972-02-24 1980-07-31 Elektroschmelzwerk Kempten Gmbh, 8000 Muenchen Pulverförmiges Borierungsmittel
BE789036A (fr) * 1971-09-24 1973-03-20 Kempten Elektroschmelz Gmbh Agent de boruration
US3936327A (en) * 1972-09-07 1976-02-03 Elektroschmelzwerk Kempten Gmbh Boriding composition
GB1436945A (en) * 1973-01-08 1976-05-26 Borax Cons Ltd Boriding compositions
PL90793B1 (xx) * 1974-06-19 1977-01-31
DE2633137C2 (de) * 1976-07-23 1983-12-01 Degussa Ag, 6000 Frankfurt Borierungsmittel zum Borieren von Massenteilen aus Eisen und Nichteisenmetallen
SU834241A1 (ru) * 1979-11-13 1981-05-30 Белорусский Ордена Трудового Красногознамени Политехнический Институт Смесь дл борировани стальных изделий
DE3431044A1 (de) * 1984-08-23 1986-03-06 Elektroschmelzwerk Kempten GmbH, 8000 München Verfahren zum borieren von metall und metall-legierungen mittels fester boriermittel
CN1003944B (zh) * 1986-11-05 1989-04-19 山东省新材料研究所 渗硼用胶膜

Also Published As

Publication number Publication date
ATE230809T1 (de) 2003-01-15
EP0971047A1 (de) 2000-01-12
CA2277006A1 (en) 2000-01-09
DE19830654A1 (de) 2000-01-13
TR199901596A2 (xx) 2000-02-21
CZ243999A3 (cs) 2000-03-15
DE59903955D1 (de) 2003-02-13
US6245162B1 (en) 2001-06-12
TR199901596A3 (tr) 2000-02-21
DE19830654C2 (de) 2002-06-27
JP4209043B2 (ja) 2009-01-14
CZ295205B6 (cs) 2005-06-15
ES2189316T3 (es) 2003-07-01
JP2000038651A (ja) 2000-02-08
ZA994445B (en) 2000-01-13

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