WO2011021751A1 - Alliage de rechargement dur, à base de fer, exempt de chrome, présentant une excellente résistance à l'abrasion - Google Patents

Alliage de rechargement dur, à base de fer, exempt de chrome, présentant une excellente résistance à l'abrasion Download PDF

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Publication number
WO2011021751A1
WO2011021751A1 PCT/KR2009/007578 KR2009007578W WO2011021751A1 WO 2011021751 A1 WO2011021751 A1 WO 2011021751A1 KR 2009007578 W KR2009007578 W KR 2009007578W WO 2011021751 A1 WO2011021751 A1 WO 2011021751A1
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alloy
iron
carbide
boro
content
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PCT/KR2009/007578
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English (en)
Korean (ko)
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김선진
이재건
김기남
김지희
박명철
신경수
조재환
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한양대학교 산학협력단
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    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon

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  • the present invention relates to a mirror-treated alloy, which does not contain Cr, which is harmful to the human body, but by appropriately controlling the contents of C and B to form iron-boride carbides, similar to or superior in hardness and wear resistance to mirror-treated alloys including Cr. It relates to a chromium-free iron-based mirror surface alloy having a.
  • Hardfacing is a process of fusing and welding parts that are worn out because they have a lot of contact with the outside to increase the lifespan of metals, which are more resistant to corrosion, heat, abrasion, and impact than base metal. Can be extended and high quality parts manufactured and repaired at low cost. In addition, the maintenance time is short, the downtime due to the repair is short, and the use of inexpensive base materials can be used to reduce the overall cost.
  • Hardfacing is performed by domestic steel and steel companies, and it is applied to blast furnace equipment of steel mills, slab production equipment, plate equipment, and various rolls and equipment of hot rolling and cold rolling mills. Recently, the field of application is expanding to thermal power plants, cement plants, paper mills, and semiconductors due to technological advances and applications. It can also be applied to pump impeller housing, bucket teeth, auger, crusher, etc., flux cored arc welding, shielded metal arc welding, etc. It is carried out by the method of.
  • a special alloy such as cemented carbide, stellite (about 30% chromium, 20% tungsten, 0.1 to 0.3% carbon, or other cobalt alloy) is welded on the surface of the metal material, and the surface is treated with tungsten carbide (WC).
  • WC tungsten carbide
  • Korean Patent Publication No. 2007-0106978 (2007.11.06) has a micro structure substantially containing austenite and M 7 C 3 carbide in the non-heat treatment state to precipitate hard carbide within the process composition range , Discloses an alloy having excellent wear resistance in which martensite is formed at an interface between precipitates and matrix phases.
  • the chromium carbide-based welding material such as the prior art contains a high content of Cr in order to obtain the required properties, which provides a cause of the generation of a large amount of toxic Cr vapor in the welding process.
  • Cr vapor is not only a carcinogen that can cause laryngeal cancer and lung cancer, but also an element known to cause industrial disasters such as nasal septum perforation in the cartilage of the nasal cartilage.
  • the price of welding materials containing expensive Cr is inevitable.
  • US Patent Publication No. 20040206726 (October 21, 2004) is a weight%, C: 0.45 ⁇ 0.8%, B: 3.5 ⁇ 4.5%, Nb: 4.5 ⁇ 6.5%, Ni: 2.0 ⁇ 2.5%, Mn: 0.8 ⁇ 25%, Si: 0.6 ⁇ 0.8%, remainder Fe and other unavoidable impurity and suggest a wear-resistant welding alloy having boride and process structure with excellent wear resistance, the content of C is 0.45 ⁇ 0.8% Low carbon-based, the B content is 3.5 ⁇ 4.5% of the alloy using the boride itself to improve the hardness, which is incompatible with the component system and composition range intended in the present invention, and economic efficiency is low.
  • the composition of C, Mn, B, Si, etc. is properly controlled, and iron boron carbide (Fe boro-carbide) is used, which is similar to Cr-based mirror-treated alloys without containing Cr, and has no hardness and wear resistance. It is intended to provide a chromium iron-based mirror surface alloy.
  • iron boron carbide Fe boro-carbide
  • the present invention provides an iron-based mirror-treated alloy containing, in weight percent, C: 2 to 4.0%, Mn: 1 to 5%, B: 0.05 to 0.7% or less, Si: 0.2 to 2.0%, balance Fe and other unavoidable impurities. do.
  • the alloy preferably contains iron boro-carbide.
  • the alloy structure may be one of subprocess structures, process structures, and hyperprocess structures.
  • the structure of the alloy preferably includes at least one of eutectic iron-boride carbide and primary iron-boride carbide in the case of overprocessing.
  • the form of the primary iron-boride carbide when the content of Mn is 2.5 to 3.5% by weight, preferably in the form of a block (block) and the average diameter of the primary iron-boride carbide ranges from 10 to 80 ⁇ m, aspect ratio is 1: It is preferable that it is the range of 0.33-1.
  • the volume fraction of the total iron-boride carbide in the alloy is 50 to 70%.
  • the volume fraction of primary iron-boride carbide in the alloy is 40 to 60%.
  • the iron-boride carbide is preferably Fe 3 C 0.3 B 0.7 .
  • the alloy is preferably abrasion amount of 20 ⁇ 50mg as a result of a dry sand & rubber wheel test.
  • the hardness of the said alloy is 45-65HRc.
  • the present invention does not use expensive Cr, W, Nb, etc., and is excellent in economic efficiency, and in particular, it is possible to prevent harmful Cr gas generated during welding because it does not contain Cr.
  • Fe boro-carbide was formed to increase the hardness of the material itself. It is possible to prevent cracking of hard precipitates and to increase the weldability of the material by including Si.
  • Fig. 1 (a) is an electron micrograph of a subprocess structure of Inventive Example 1
  • Fig. 1 (b) is an electron micrograph of a process structure of Inventive Example 2
  • Fig. 1 (c) is an electron microscope structure of an overprocess of Invention Example 3 Picture;
  • Figure 2 (a) is an optical micrograph of Example 10
  • Figure 2 (b) is an optical micrograph of Example 11
  • Figure 2 (c) is an optical micrograph of Example 3
  • Figure 2 (d) is an Invention Example 8, optical micrograph;
  • Example 3 is a microscopic histogram of Inventive Example 3.
  • Figure 6 is a graph showing the hardness and wear according to the change in the content of Mn
  • Figure 7 is a graph showing the hardness and wear amount according to the change in the content of B;
  • FIG. 9 (a) is an optical micrograph of the wear surface of Inventive Example 1
  • FIG. 9 (b) is an optical micrograph of the wear surface of Inventive Example 2
  • FIG. 9 (c) is an optical microscope picture of the wear surface of Inventive Example 3 ;
  • FIG. 10 is an optical micrograph of a wear surface of Comparative Example 5.
  • the present invention may exhibit hardness and wear resistance similar to that of high Cr mirrored alloys including iron boro-carbide, and in particular, the content of C, Mn, B, and Si may be appropriately controlled and overprocessed.
  • Hard iron-boride carbide prevents the process from being swept away by abrasion, thereby improving hardness and wear resistance.
  • C is an element that forms carbide and serves to improve the hardness and wear resistance of the material by precipitation strengthening and interstitial solid solution hardening effect.
  • the content of C absolutely contributes to the wear resistance. It is preferable that it is 2.0 weight% or more in order to achieve the said effect.
  • the content of C exceeds 4.0% by weight, the brittleness is excessively increased and segregation of C which is not completely dissolved occurs, which is not only easily damaged by a small external impact, but also due to the increase of the content of C having a low density.
  • the content of C is preferably limited to 2.0 to 4.0% by weight.
  • the hardness and wear amount of the alloy of the present invention according to the content of C is shown in FIG.
  • Mn is an element capable of stabilizing austenite, and in the case of a growth welding material, Mn is added to prevent brittle fracture caused by high hardness. And, as can be seen in Figure 2, according to the Mn content to form a rod-shaped super (block) in the form of a block (block) to prevent the micro-cracks that may occur during external impact or scratch wear can improve the wear resistance have.
  • the content of Mn is less than 1% by weight, the above effects are insignificant and it is preferable to add 1% by weight or more.
  • the content of Mn is preferably limited to 1 to 5% by weight.
  • the content of Mn is more preferably limited to 2.5 to 3.5% by weight, and rod-shaped super phases in the above range may be made in a block form.
  • the hardness and wear amount of the alloy of the present invention according to the content of Mn is shown in FIG.
  • B generally exhibits a strengthening effect at 0.002% by weight or less. When added in excess of the content, grain boundary segregation may occur, and coarse pores or voids are formed in the cast structure. It is known to have a problem.
  • the content of B is preferably limited to 0.05 to 0.7% by weight.
  • the hardness and wear amount of the alloy of the present invention according to the content of B is shown in FIG.
  • Si is dissolved in Fe to increase hardness and abrasion resistance, and it contains Si, which increases the flowability of the melt, reduces defects such as incomplete castings during casting, and increases the spreadability of the weld bead, thereby making the work more efficient. It is possible to improve weldability and castability. It is also possible to reduce the amount of C added by reducing the process C content.
  • the content of Si is less than 0.2% by weight, the low hardness does not contribute to the improvement of abrasion resistance. If the content of Si exceeds 2.0% by weight, spherical graphite is precipitated and the wear resistance rapidly deteriorates. Therefore, the content of Si is preferably limited to 0.2 to 2.0% by weight.
  • the hardness and wear amount of the alloy of the present invention according to the content of Si is shown in FIG.
  • the alloy of the present invention may comprise a boride carbide, iron boro-carbide (Fe boro-carbide) may be present in the form of Fe 3 C 0.3 B 0.7 .
  • the iron-boride carbide may improve the wear resistance of the alloy by preventing the process structure from being washed out.
  • the structure of the alloy of the present invention can be represented as sub-process structure, process structure, hyper-process structure according to the component system and composition range.
  • 1 (a), (b) and (c) are photographs showing subprocess structures, process structures, and hyperprocess structures, respectively.
  • the alloy structure When the alloy structure is hyper-processed, it may include primary iron-boride carbide.
  • the primary iron-boride carbide can play a role of supporting the process is not easily wiped out by the external wear in the over-process, as can be seen in Figures 1 and 9.
  • the super-normal is not formed integrally, but appears in a discontinuous form broken several times in the middle. This shape prevents the propagation of cracks that can occur in hard boride carbides by external impacts when worn.
  • the form of the primary iron-boride carbide is characterized in that the block (block) form, the average diameter of the primary iron-boride carbide is in the range of 10 ⁇ 80 ⁇ m, It is preferable that ratio (aspect ratio) of the long axis and short axis is 0.33-1.
  • the volume fraction of the total iron boride carbide in the alloy is preferably 50 to 70%. And it is more preferable that the volume fraction of primary iron-boride carbide is 40 to 60%.
  • the total iron-boride carbide includes the process iron-boride carbide and primary iron-boride carbide.
  • the wear amount in the dry sand & rubber wheel test is 20mg, it can be used as an excellent hardened alloy, and the alloy having a wear amount in the range of 20 ⁇ 50mg is suitable as a mirrored alloy.
  • the mirror-treated alloy of the present invention exhibits abrasion amount within the above range.
  • the hardness of the alloy of this invention shows 45-65HRc.
  • An alloy specimen having the component system and composition shown in Table 1 was prepared by using a high frequency induction heating method in an argon atmosphere. In order to measure the wear resistance, the specimens were processed to 75 mm long, 24 mm long and 5 mm high, respectively, and the surface was ground using # 320 SiC abrasive paper.
  • the grinding wear test equipment used for the experiment was a dry sand & rubber wheel test manufactured according to ASTM G 65-94 (Standard Test Equipment) standard. Experimental conditions are sand ejection speed 300 ⁇ 400g / min, applied load 130N, rotational speed 200rpm and the wear test was carried out for 10 minutes and the amount of wear after the test is shown in Table 1 below.
  • FIG. 10 In addition, electron micrographs of Inventive Examples 1 to 3 are shown in Fig. 1, and photographs of wear surfaces are shown in Fig. 9. And, in order to observe the tissue according to the content of Mn electron micrographs of Inventive Examples 10, 11, 3, 8 are shown in FIG. Regarding the iron boride carbide, micrographs and transmission electron micrographs of Inventive Example 3 are shown in FIGS. 3 and 4. In order to observe the shape of the conventional chromium carbide, an optical micrograph of Comparative Example 5 is shown in FIG. 10.
  • the content of C should be more than the content that can absolutely contribute to the wear resistance
  • Comparative Example 1 is the content of C is 1.5% by weight
  • the hardness value is less than the content of C intended for the present invention
  • Inventive Examples 1 to 18 It is similar to, but wear amount is 76mg, it can be confirmed that the wear resistance is poor.
  • Comparative Example 2 the C content is 5% by weight, so that the brittleness is excessively large and the segregation of C, which is not completely dissolved, is easily damaged by small external shocks, and the volume is increased due to the increase of the C content having a low density. There is a problem in that the manufacturing cost incurred in the production of welding wire and product to increase to have a certain component content.
  • Comparative Example 3 when the content of Si is less than 0.2% by weight does not contribute to the improvement of wear resistance, Comparative Example 3 does not include Si, it can be seen that the wear amount is 91mg. And Comparative Example 4 is not the improvement of wear resistance as the case in which the present invention exceeds the content of Si intended.
  • Comparative Example 5 is a conventional high Cr-based mirror surface alloy, the hardness and the wear amount was 59 and 18.
  • Comparative Example 6 since the content of B is high and other expensive elements are added, it shows a hardness and abrasion similar to that of the present invention, but the economy is inferior.
  • Inventive Examples 1 to 18 having a component system controlled by the present invention show that the hardness and wear amount are 45 to 67 and 20 to 48, and thus have a hardness value and wear amount similar to those of the conventional high Cr-based mirror-treated alloy.

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Abstract

La présente invention porte sur un alliage de rechargement dur, à base de fer, exempt de chrome, qui ne contient pas Cr, contrôle de façon appropriée le système de composants de C, Mn, B, Si et similaire et utilise le boro-carbure de Fe. L'alliage de rechargement dur, à base de fer, exempt de chrome, est excellent en ce qui concerne le rendement économique en raison du fait que Cr, W, Nb et similaires qui sont coûteux, ne sont pas utilisés et, spécifiquement la génération de Cr gazeux nuisible dans le cas d'une soudure peut être empêchée parce que l'alliage ne contient pas Cr. Le boro-carbure de fer est formé par contrôle approprié de la teneur en C et B, permettant ainsi d'augmenter la dureté de l'alliage lui-même, on peut empêcher le craquage de précipités d'une dureté élevée qui peuvent être générés par impact externe, en faisant varier la forme de la phase primaire par le fait qu'elle contient Mn, et la propriété de soudure de l'alliage est accrue par le fait qu'il contient Si.
PCT/KR2009/007578 2009-08-18 2009-12-17 Alliage de rechargement dur, à base de fer, exempt de chrome, présentant une excellente résistance à l'abrasion WO2011021751A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012054789A1 (fr) * 2010-10-21 2012-04-26 Stoody Company Consommable de soudage de rechargement dur sans chrome
WO2016100374A3 (fr) * 2014-12-16 2016-10-27 Scoperta, Inc. Alliages ferreux tenaces et résistants à l'usure contenant de multiples phases dures
WO2017040775A1 (fr) * 2015-09-04 2017-03-09 Scoperta, Inc. Alliages résistant à l'usure sans chrome et à faible teneur en chrome
US9738959B2 (en) 2012-10-11 2017-08-22 Scoperta, Inc. Non-magnetic metal alloy compositions and applications
US9802387B2 (en) 2013-11-26 2017-10-31 Scoperta, Inc. Corrosion resistant hardfacing alloy
US10100388B2 (en) 2011-12-30 2018-10-16 Scoperta, Inc. Coating compositions
US10173290B2 (en) 2014-06-09 2019-01-08 Scoperta, Inc. Crack resistant hardfacing alloys
US10851444B2 (en) 2015-09-08 2020-12-01 Oerlikon Metco (Us) Inc. Non-magnetic, strong carbide forming alloys for powder manufacture
US10954588B2 (en) 2015-11-10 2021-03-23 Oerlikon Metco (Us) Inc. Oxidation controlled twin wire arc spray materials
CN113458646A (zh) * 2021-07-09 2021-10-01 昆山京群焊材科技有限公司 一种无铬之碳化硼型自保护药芯焊丝
US11279996B2 (en) 2016-03-22 2022-03-22 Oerlikon Metco (Us) Inc. Fully readable thermal spray coating
US11939646B2 (en) 2018-10-26 2024-03-26 Oerlikon Metco (Us) Inc. Corrosion and wear resistant nickel based alloys

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US20040206726A1 (en) * 2003-04-21 2004-10-21 Daemen Roger Auguste Hardfacing alloy, methods, and products
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10052725B2 (en) 2010-10-21 2018-08-21 Stoody Company Chromium-free hardfacing welding consumable
AU2011316958B2 (en) * 2010-10-21 2015-06-04 Stoody Company Chromium-free hardfacing welding consumable
US9314880B2 (en) 2010-10-21 2016-04-19 Stoody Company Chromium free hardfacing welding consumable
WO2012054789A1 (fr) * 2010-10-21 2012-04-26 Stoody Company Consommable de soudage de rechargement dur sans chrome
US11085102B2 (en) 2011-12-30 2021-08-10 Oerlikon Metco (Us) Inc. Coating compositions
US10100388B2 (en) 2011-12-30 2018-10-16 Scoperta, Inc. Coating compositions
US9738959B2 (en) 2012-10-11 2017-08-22 Scoperta, Inc. Non-magnetic metal alloy compositions and applications
US9802387B2 (en) 2013-11-26 2017-10-31 Scoperta, Inc. Corrosion resistant hardfacing alloy
US10173290B2 (en) 2014-06-09 2019-01-08 Scoperta, Inc. Crack resistant hardfacing alloys
US11130205B2 (en) 2014-06-09 2021-09-28 Oerlikon Metco (Us) Inc. Crack resistant hardfacing alloys
US11111912B2 (en) 2014-06-09 2021-09-07 Oerlikon Metco (Us) Inc. Crack resistant hardfacing alloys
WO2016100374A3 (fr) * 2014-12-16 2016-10-27 Scoperta, Inc. Alliages ferreux tenaces et résistants à l'usure contenant de multiples phases dures
CN107532265A (zh) * 2014-12-16 2018-01-02 思高博塔公司 含多种硬质相的韧性和耐磨铁合金
EP3234209A4 (fr) * 2014-12-16 2018-07-18 Scoperta, Inc. Alliages ferreux tenaces et résistants à l'usure contenant de multiples phases dures
US10329647B2 (en) 2014-12-16 2019-06-25 Scoperta, Inc. Tough and wear resistant ferrous alloys containing multiple hardphases
CN107532265B (zh) * 2014-12-16 2020-04-21 思高博塔公司 含多种硬质相的韧性和耐磨铁合金
WO2017040775A1 (fr) * 2015-09-04 2017-03-09 Scoperta, Inc. Alliages résistant à l'usure sans chrome et à faible teneur en chrome
US10105796B2 (en) 2015-09-04 2018-10-23 Scoperta, Inc. Chromium free and low-chromium wear resistant alloys
US11253957B2 (en) 2015-09-04 2022-02-22 Oerlikon Metco (Us) Inc. Chromium free and low-chromium wear resistant alloys
US10851444B2 (en) 2015-09-08 2020-12-01 Oerlikon Metco (Us) Inc. Non-magnetic, strong carbide forming alloys for powder manufacture
US10954588B2 (en) 2015-11-10 2021-03-23 Oerlikon Metco (Us) Inc. Oxidation controlled twin wire arc spray materials
US11279996B2 (en) 2016-03-22 2022-03-22 Oerlikon Metco (Us) Inc. Fully readable thermal spray coating
US11939646B2 (en) 2018-10-26 2024-03-26 Oerlikon Metco (Us) Inc. Corrosion and wear resistant nickel based alloys
CN113458646A (zh) * 2021-07-09 2021-10-01 昆山京群焊材科技有限公司 一种无铬之碳化硼型自保护药芯焊丝

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