EP2518176B1 - Martensite stainless steel for an injection-moulding mould having improved corrosion resistance - Google Patents

Martensite stainless steel for an injection-moulding mould having improved corrosion resistance Download PDF

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Publication number
EP2518176B1
EP2518176B1 EP10839728.2A EP10839728A EP2518176B1 EP 2518176 B1 EP2518176 B1 EP 2518176B1 EP 10839728 A EP10839728 A EP 10839728A EP 2518176 B1 EP2518176 B1 EP 2518176B1
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EP
European Patent Office
Prior art keywords
stainless steel
steel
corrosion resistance
added
elongation
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.)
Not-in-force
Application number
EP10839728.2A
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German (de)
English (en)
French (fr)
Other versions
EP2518176A2 (en
EP2518176A4 (en
Inventor
Ki-Hoon Jo
Dong-Chul Chae
Chung-Ho Nam
Young-Tae Kim
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.)
Posco Holdings Inc
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Posco Co Ltd
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Filing date
Publication date
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Publication of EP2518176A2 publication Critical patent/EP2518176A2/en
Publication of EP2518176A4 publication Critical patent/EP2518176A4/en
Application granted granted Critical
Publication of EP2518176B1 publication Critical patent/EP2518176B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C22C38/18—Ferrous alloys, e.g. steel 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
    • C22C38/001—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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • 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
    • C22C38/18—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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • An aspect of the present invention relates to a martensitic stainless steel for injection-molding mold having improved corrosion resistance, and more particularly, to a martensitic stainless steel used to produce an injection-molding mode or mode base.
  • ASTM420 series stainless steel has been used as the stainless steel for producing components of the plastic injection-molding machine.
  • the hardness of the ASTM420 series stainless steel is high, it is not easy to perform mechanical processing. Since chromium carbide is formed through a reaction between chromium and carbon of a base material, the corrosion resistance is lowered, and the weldability is not satisfactory. For this reason, the use of the ASTM420 series stainless steel is gradually decreased.
  • US Patent No. 6045633 has disclosed a stainless steel having improved corrosion resistance by limiting the content of carbon to 0.03 to 0.06% and adding 0.5 to 1.3% copper.
  • more than 1% copper is excessively added, the hot workability of the stainless steel is lowered, and therefore, surface cracks are caused.
  • Another example for a martensitic stainless steel suitable for plastic molding tools is disclosed in US 2007/0006949 A1 .
  • an object of the present invention is to provide an alloy design for improving the corrosion resistance and machinability of a martensitic stainless steel used as a material of a plastic injection-molding machine.
  • the stainless steel may have a ferrite fraction of less than 15%.
  • the hardness of the stainless steel may have a range of 25 to 40HRC.
  • a martensitic stainless steel according to the present invention contains, as percentages by weight, 0.03 to 0.12% carbon, 0.02 to 0.08% nitrogen, 0.3 to 0.7% silicon, 0.6 to 2% manganese, 0.001 to 0.03% phosphorus, 0.1 to 0.3% sulfur, 11.5 to 15% chromium, 0.05 to 1% copper, 0.6 to 3% nickel and 0.0005 to 0.003% calcium, and iron and other unavoidable impurities as remnants.
  • the present inventor has found that in the production of a steel used for a plastic injection-molding mold, the structure of manganese sulfide (MnS) existing in a martensitic cutting steel is improved by adding calcium (Ca), and the corrosion resistance of a base material is improved by adding nickel (Ni), so that the martensitic cutting steel has outstanding corrosion resistance.
  • MoS manganese sulfide
  • the nitrogen contributes to the strength and corrosion resistance of the martensitic stainless steel, more than 0.02% nitrogen is added. However, if the nitrogen is excessively added, pores may be generated by the nitrogen in molding. Therefore, the maximum content of the nitrogen is limited to 0.08%.
  • the silicon is an element essentially added for the purpose of its deoxidation, more than 0.3% silicon is added. However, the silicon is excessively added, the machinability and thermal conductivity of the martensitic stainless steel are lowered. Therefore, the maximum content of the silicon is limited to 0.7%.
  • the manganese is an element added together with the sulfur so as to improve cuttability.
  • the added sulfur forms CrS or FeS, and hence has bad influence on workability. Therefore, more than 0.6% manganese is added.
  • the content of the manganese is 2% or more, its valid effect is lost. Therefore, the maximum content of the manganese is limited to 2%.
  • the phosphorus is an element unavoidably added in the production of stainless steel, more than 0.001% phosphorus is added. If the phosphorus is excessively added, the machinability of the martensitic stainless steel is lowered. Therefore, the maximum content of the phosphorus is limited to 0.03%.
  • the sulfur is a representative element added to improve the cuttability of stainless steel, more than 0.1% sulfur is added to secure the cuttability of the martensitic stainless steel.
  • the content of the sulfur exceeds 0.3%, the effect of the added sulfur is saturated, and the excessive addition of the sulfur lowers the workability of the martensitic stainless steel. Therefore, the maximum content of the sulfur is limited to 0.3%.
  • the chromium is a basic element for securing corrosion resistance, more than 11.5% chromium is added. However, when the chromium is excessively added, the chromium promotes the formation of ferrite. Therefore, the maximum content of the chromium is limited to 15%.
  • the copper functions to improve corrosion resistance and thermal conductivity, more than 0.05% copper is added. When the copper is excessively added, the copper causes the lowering of hot workability. Therefore, the maximum content of the copper is limited to 1%.
  • the nickel is an element that increases the corrosion resistance of stainless steel. Since the nickel functions to improve tension, more than 0.6% nickel is added. Therefore, the maximum content of the nickel is limited to 3% so as to prevent an excessive increase in production cost.
  • the calcium acts as a nuclear generation site of MnS in ingot casting or continuous casting, the MnS is easily formed, and more than 0.0005% calcium is added to obtain an effect for suppressing the tension of Mn.
  • the calcium is excessively added, the calcium lowers corrosion resistance. Therefore, the maximum content of the calcium is limited to 0.003%.
  • a desired structure of the martensitic stainless steel is produced by making a casting slab through continuous casting or ingot casting and performing a rolling and forging process of the casting slab. Then, a heat treatment process using a standard method is performed to obtain an appropriate property of the steel suitable for its usage.
  • the ratio of elongation to anisotropy is preferably controlled to 0.5 or less.
  • the ratio of elongation to anisotropy may be obtained by (rolling direction elongation - width direction elongation)/(rolling direction elongation).
  • An ordinary steel for plastic injection-molding machine is not used by being machined to have a specific direction such as a rolling direction or width direction but used by being machined to have various directions. In this case, as the difference in mechanical property between directions increases, the deformation of the steel due to stress caused in the machining of the steel increases, and the difference in durability with respect to a high pressure applied in injection molding increases.
  • the mechanical anisotropy (rolling direction experimental value - width direction experimental value)/(rolling direction experimental value)] is most obviously shown in the elongation among the several experimental values. Therefore, in steel having compositions of the inventive steel, the elongation anisotropy is preferably controlled to 50% or less.
  • the inventive steel has the ideal structure of ferrite and martensite.
  • the difference in hardness between the structures of the ferrite and the martensite is great.
  • the structure of the martensite has a solid and strong property, and the structure of the ferrite has a soft and tough property.
  • the ferrite functions to provide toughness.
  • the maximum content of the ferrite is preferably limited to 15% or less.
  • the hardness of the inventive steel has a range of 25 to 40HRC.
  • the hardness of an ordinary material has influence on machining quality and machinability (machining speed or tool lifetime) at the same time. If the hardness of the material increases, the resistance against machinability increases, and therefore, the machining speed decreases. Further, the abrasion of the tool increases, and therefore, the machinability is deteriorated. However, the quality of a machined surface is increased. On the other hand, if the hardness of the material is low, the machining speed and tool lifetime are increased, but the quality of the machined surface is lowered. Therefore, the hardness of the material is preferably 25HRC or more so as to secure the machining quality. The maximum hardness of the material is preferably less than 40HRC so as to secure the machinability in consideration of productivity.
  • inventive steels and two comparative steels are produced by means of chemical formulae of Table 1. All samples are produced as ingots of 50Kg using a vacuum melting device and then rolled to a thickness of 25mm.
  • Comparative steel 1 is compared with the inventive steel in the state in which nickel and copper are not added to Comparative steel 1.
  • FIG. 1 is a scanning electron microscope (SEM) photograph showing a structure of MnS in an ingot sample having calcium added thereto. As can be seen in FIG. 1 , calcium oxide is placed at a central portion of the MnS. In this case, the distribution of the MnS is detailed, and the elongation of the MnS is suppressed in a rolling process.
  • SEM scanning electron microscope
  • FIG. 2 is a graph showing a length distribution of MnS in Comparative steel 1 having no Ca added thereto.
  • FIG. 3 shows a length distribution of MnS in Embodiment 7 of the inventive steel.
  • the number of coarse MnS is decreased by 20 or more as compared with the steel having no calcium added thereto. It can be seen that the average length and maximum length of the MnS are different from each other.
  • the calcium is added, the elongation of the MnS is limited to a certain degree in a rolling process.
  • the portion at which the MnS is added to the steel acts as a port weak to corrosion in a real use environment.
  • the corrosion resistance will increase.
  • each of the samples was machined in the shape of a sheet of 150mm*70mm*1mm, and an experiment was performed in a complex corrosion environment of salt water spray, dry and humidity.
  • the detailed experimental conditions are shown in Table 2.
  • Table 3 shows a result obtained by performing experiments of corrosion resistance. After the experiments of corrosion resistance, the samples were estimated by dividing the corrosion grade into 1 to 10 according to a degree of formation of rust on the surface of the sample. '1' means that corrosion is formed in 50% of the area of the sample, and '10' means that rust is not formed at all.
  • FIG. 4 illustrates samples of an embodiment used in the corrosion experiment and a comparative example having rust formed on the surface thereof.
  • the corrosion grade of the inventive steel having the compositions of the present invention is high.
  • Table 3 it can be seen that the corrosion resistance of steel having a similar content of chromium having the most influence on the corrosion resistance of stainless steel is improved through the compositions of the present invention.
  • the addition of calcium has effective influence on the anisotropy of a mechanical property.
  • the difference in mechanical property between the elongation direction of the MnS and the non-elongation direction of the MnS is great. This is because the MnS acts as a portion weak to an external force in the material. As the structure of the MnS for each direction is equalized, the anisotropy is decreased.
  • Table 4 shows a result obtained by measuring a mechanical property for each direction. It can be seen that the mechanical strength of stainless steel is increased by adding calcium. Particularly, the mechanical strength and elongation in the width direction are remarkably increased.
  • Table 4 Kind of Steel Direction TS (Mpa) E1 (%) Inventive Steel 7 Rolling Direction 1020 14 Width Direction 1010 11 Comparative Steel 1 Rolling Direction 1000 14.5 Width Direction 940 6

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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)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
EP10839728.2A 2009-12-22 2010-12-20 Martensite stainless steel for an injection-moulding mould having improved corrosion resistance Not-in-force EP2518176B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090128883A KR101268764B1 (ko) 2009-12-22 2009-12-22 내식성을 향상시킨 사출성형 몰드용 마르텐사이트 스테인리스강
PCT/KR2010/009107 WO2011078531A2 (ko) 2009-12-22 2010-12-20 내식성을 향상시킨 사출성형 몰드용 마르텐사이트 스테인리스강

Publications (3)

Publication Number Publication Date
EP2518176A2 EP2518176A2 (en) 2012-10-31
EP2518176A4 EP2518176A4 (en) 2016-11-23
EP2518176B1 true EP2518176B1 (en) 2018-05-16

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EP10839728.2A Not-in-force EP2518176B1 (en) 2009-12-22 2010-12-20 Martensite stainless steel for an injection-moulding mould having improved corrosion resistance

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EP (1) EP2518176B1 (zh)
KR (1) KR101268764B1 (zh)
CN (2) CN102686761A (zh)
WO (1) WO2011078531A2 (zh)

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KR20160082630A (ko) 2014-12-26 2016-07-08 주식회사 포스코 내구성이 우수한 사출성형 몰드용 마르텐사이트 스테인리스강 및 그 제조방법
CN105562691A (zh) * 2015-12-23 2016-05-11 华中科技大学 一种注塑模具的3d打印制备方法
CN107747063B (zh) * 2017-11-29 2019-08-23 郑州永通特钢有限公司 一种高强韧马氏体不锈钢
KR102237412B1 (ko) 2019-05-03 2021-04-07 유근광 Iot 스마트 비상벨장치
KR102283434B1 (ko) 2019-12-02 2021-07-29 (주)에이엘씨 Ip카메라를 구비한 sos비상벨 운용시스템
KR102283440B1 (ko) 2019-12-02 2021-07-29 (주)에이엘씨 이중화된 무선망을 이용한 sos비상벨 운용시스템
KR102358188B1 (ko) 2020-01-06 2022-02-07 (주)에이엘씨 위치기반 안전방범을 구현한 스마트 가로등 운용시스템

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Publication number Priority date Publication date Assignee Title
US6045633A (en) * 1997-05-16 2000-04-04 Edro Engineering, Inc. Steel holder block for plastic molding
SE516622C2 (sv) * 2000-06-15 2002-02-05 Uddeholm Tooling Ab Stållegering, plastformningsverktyg och seghärdat ämne för plastformningsverktyg
US8808472B2 (en) * 2000-12-11 2014-08-19 Uddeholms Ab Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details
AT409636B9 (de) * 2001-02-14 2002-12-27 Boehler Edelstahl Gmbh & Co Kg Stahl für kunststoffformen und verfahren zur wärmebehandlung desselben
FR2872825B1 (fr) * 2004-07-12 2007-04-27 Industeel Creusot Acier inoxydable martensitique pour moules et carcasses de moules d'injection

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Also Published As

Publication number Publication date
CN104561833A (zh) 2015-04-29
KR20110072089A (ko) 2011-06-29
KR101268764B1 (ko) 2013-05-29
WO2011078531A3 (ko) 2011-11-17
EP2518176A2 (en) 2012-10-31
EP2518176A4 (en) 2016-11-23
WO2011078531A2 (ko) 2011-06-30
CN102686761A (zh) 2012-09-19

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