WO2017155331A1 - 내마모성이 향상된 합금주철, 및 이를 포함하는 피스톤 링 - Google Patents

내마모성이 향상된 합금주철, 및 이를 포함하는 피스톤 링 Download PDF

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Publication number
WO2017155331A1
WO2017155331A1 PCT/KR2017/002573 KR2017002573W WO2017155331A1 WO 2017155331 A1 WO2017155331 A1 WO 2017155331A1 KR 2017002573 W KR2017002573 W KR 2017002573W WO 2017155331 A1 WO2017155331 A1 WO 2017155331A1
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WIPO (PCT)
Prior art keywords
cast iron
alloy cast
weight
piston ring
heat treatment
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.)
Ceased
Application number
PCT/KR2017/002573
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English (en)
French (fr)
Inventor
한금태
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.)
Samyoung Machinery Co Ltd
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Samyoung Machinery Co 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 Samyoung Machinery Co Ltd filed Critical Samyoung Machinery Co Ltd
Priority to EP17763592.7A priority Critical patent/EP3428486B1/en
Priority to US15/576,354 priority patent/US20180148808A1/en
Priority to DK17763592.7T priority patent/DK3428486T3/da
Priority to JP2018518560A priority patent/JP6712316B2/ja
Publication of WO2017155331A1 publication Critical patent/WO2017155331A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/40—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rings; for bearing races
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • 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
    • C21D5/00—Heat treatments of cast-iron
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/10—Cast-iron alloys containing aluminium or silicon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
    • 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
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/009—Pearlite

Definitions

  • the present invention relates to alloy cast iron with improved wear resistance and a piston ring including the same, in particular to maintain the confidentiality between the piston and the inner wall of the cylinder and to scrape the lubricant from the cylinder wall so that the lubricant does not enter the combustion chamber. Alloy cast iron and piston rings for improved wear resistance in grooves outside the piston.
  • engines for power-generating devices such as internal combustion engines
  • Pistons that are reciprocating in a straight line are equipped, and the piston rings are equipped with piston rings to minimize friction with the cylinder and maintain confidentiality.
  • Piston rings are generally coupled to the outer circumferential surface of the piston reciprocating inside the cylinder and are reciprocated along the cylinder liner and inner wall, and must be excellent in heat resistance and abrasion resistance as they are exposed to high temperature and high pressure and thus receive considerable heat and mechanical loads. do.
  • a chromium plated layer is placed on the outer circumferential surface of the piston ring.
  • the chromium-plated piston ring also has the disadvantage that the chromium-plated layer is difficult to form an oil film due to the difficulty of wetting the oil.
  • chromium-plated piston rings are increasingly regulated by the installation and operation of manufacturing facilities for chromium plating due to environmental problems.
  • the present invention provides an alloy with improved wear resistance and a pass-through ring including the same.
  • the purpose is to provide.
  • An aspect of the present invention for achieving the above object is a pillite base
  • Graphite structure and steady-type process structure precipitated in the filite base wherein the stete-type process structure comprises at least one element selected from boron (B) and vanadium (V), chromium (Cr) and molybdenum (Mo) One or more elements selected from) and alloy cast iron, including copper (Cu).
  • the cross-sectional ratio of steaded process tissue can be 65 to 85:10 to 30: 4 to 7 days.
  • the steady-type process structure includes phosphorus (P), carbon (Q, silicon (Si), manganese (Mn), magnesium (Mg), sulfur (S), nickel (Ni), and It can contain any one or more than one selected in the comment (Sn).
  • the alloy cast iron is selected from 0.02 to 0.1% by weight of at least one element selected from gross weight, boron (B) and banana (V), cr (Cr) and molybdenum (Mo). 0.1 to 1.2 wt% of one or more elements, 0.3 to 1 wt% of copper (Cu), 0.02 to 0.03 wt% of phosphorus (P), 3.2 to 3.8 wt% of carbon (C), 1.8 to 2.8 wt.
  • the width may be 5 to 30 / im.
  • the marginal tissue may be any one or two or more shapes selected from a sphere and a filling.
  • the spheroidal graphite tissue has an average particle diameter of 0.05 to 0.15 an, and the packed graphite tissue may have a length in a long axis direction of 50 to 100 and a width of 5 to 30 / ffli.
  • the alloy cast iron may be a surface hardened layer formed.
  • the alloy cast iron may satisfy the following equation 1.
  • H s is a micro-Vickers hardness (HMV) of the surface hardened layer of alloy cast iron, 3 ⁇ 4 it is a Brinell hardness (HB) of the inner layer of alloy cast iron).
  • the thickness of the surface hardened layer may be 1 to 2 kPa.
  • the surface hardened layer may be formed by laser heat treatment or high frequency heat treatment.
  • Another aspect of the present invention relates to a piston ring comprising the alloy cast iron.
  • Another aspect of the present invention relates to an engine including the piston ring.
  • the method of manufacturing the alloy cast iron may further include hardening the surface of the alloy cast iron by laser heat treatment or high frequency heat treatment.
  • the alloy cast iron according to the present invention has a structure in which graphite structures and steady-type process structures are precipitated in the phyrite matrix, thereby obtaining ductility characteristics from graphite structures and excellent strength from the stete-type process tissues. , Can produce alloy cast iron with excellent ductility and excellent wear resistance.
  • the performance of the engine decreases due to the wear of the piston rings within two to three years.
  • the piston rings according to the present invention have excellent ductility and wear resistance, but perform for more than five years. The advantage is that it can be used for a long time without any deterioration.
  • FIG. 1 is a cross-sectional micrograph (100 magnification) of a piston ring manufactured according to an example of the present invention
  • FIG. 2 is a cross-sectional micrograph (200 magnification) of a piston ring manufactured according to another example of the present invention
  • the black tissue is graphite tissue
  • the brightly bright part is a steady-like process tissue
  • the rest is a pilrite base.
  • Abrasion resistance is achieved by forming a chrome plated layer on the outer circumferential surface of the existing piston ring.
  • the chromium plating layer was difficult to form an oil film due to the wetness of the oil, and the chromium plating layer was abraded when the high pressure of 200 N / nurf was applied. There was a downside.
  • the present inventors have shown that they have excellent abrasion resistance even at high pressures of 200 N / mrf or more, and that the use of an oil film on the surface of the piston ring makes it possible to present a piston ring and alloy cast iron which can further prevent wear of the piston ring. do.
  • alloy cast iron according to an embodiment of the present invention is a pearlite matrix; And graphite structures and steadite-type process structures precipitated in the filament base, wherein the sterite type process structures are boron (B) and
  • It may include one or more elements selected from vanadium (V), one or more elements selected from chromium (Cr) and molybdenum (Mo), and copper (Cu).
  • the graphite structure and steadite process structure have a structure deposited in the expanded light base to secure the ductility characteristics from the graphite structure, With excellent strength from the process organization, it is possible to manufacture alloy cast iron with excellent ductility and excellent wear resistance. As a result, when manufacturing a piston ring containing alloy cast iron, it is possible to manufacture a ductile ring with excellent ductility and excellent abrasion resistance. In addition to eliminating the process of plating the chromium plated layer, it is possible to prevent the occurrence of foreign substances in the environment of the crack dust during the friction between the chrome plated layer and the cylinder liner.
  • the piston ring according to the present invention has a very good ductility and abrasion resistance, but it can be used for a long period of time without any deterioration in performance over 5 years.
  • the wear resistance of the cast iron and the piston ring including the same can be greatly improved by precipitating the stead type process structure in the pearlite base.
  • the practical factor that imparts very good wear resistance to alloy cast iron and piston rings is a steady-like process structure, having a micro-Vickers hardness (HMV) of about 200 and a standard chromium plating layer coated on the surface of the piston ring.
  • HMV micro-Vickers hardness
  • the steady-type process organization has a very high hardness of more than 900, preferably 1000 to 1400, more preferably 1200 to 1400, of the micro-viscus hardness (HMV).
  • the alloy cast iron according to the present invention is based on a low-strength fillite, but a very hardened stete-like process structure is formed between the bases of the piston.
  • the overall process of alloy cast iron and piston rings by rubbing the steady-like process structure during friction with the inner wall of the cylinder liner due to the reciprocating motion which can prevent wear.
  • the microbeaker hardness (HMV) is based on the measurement according to the standard test method ASTM E384-16.
  • the size and shape of the steep-like process structure may vary depending on the casting conditions, non-limiting specific examples, the steep-type process tissue has a length in the long axis direction of 50 to 100, a width of 5 It can be from 30 to 30 days, and more preferably, the length of the long axis is 70 to 90 and the thickness can be 15 to 20, but it is not necessarily limited.
  • the graphite tissue may be imparted with ductile or oil-hygroscopic power by depositing the graphite tissue in the filament base. More specifically, the graphite tissue may be any one or more shapes selected from the shape and fill of the graphite.
  • the graphite structure gives the alloy cast iron and the piston ring even more ductility, which prevents cracks caused by the laser heat treatment, and allows the surface to be uniformly thermally treated.
  • the filling means the insect shape, and the filling graphite tissue has excellent ability to wet the lubricant applied between the cylinder liner and the piston ring, so that the oil on the surface of the piston ring is prevented.
  • Curtain It can be easily formed and therefore has the advantage of preventing the wear of the cylinder liner as well as the piston ring.
  • the size and shape of the graphite tissue may vary depending on the casting conditions.
  • the spherical graphite tissue has an average particle diameter of 0.05 to 0.15 ⁇ , more preferably 0.06 to 0.12
  • Absolute tissues have a length of 50 to 100 in the longitudinal axis, 5 to 30 / in width, and more preferably, a length of 70 to 90 / m in the major axis and a thickness of 15 to 20, but are not necessarily limited.
  • the pearlite base Abram structure: the cross-sectional ratio of the steady-type process structure can be 65 to 85: 10 to 30: 4 to 7, and more preferably, 70 to 80: 15 25 to 5 to 6 days.
  • the cross-sectional ratio of the steady-type process structure is less than 4, the wear resistance may be reduced.
  • the cross-sectional ratio is more than 7, the elongation and elasticity are reduced, and thus the piston ring can be used as a piston ring. Problems may occur that cannot be solved properly, i.e., by satisfying the above range, excellent ductility and wear resistance can be obtained, and high performance piston rings can be manufactured. This may mean the percentage of the photo taken by the organization.
  • the steep-type process structure is composed of phosphorus (P), carbon (C), silicon (Si), and manganese (Mn). It may further include any one or more selected from magnesium (Mg), sulfur (S), nickel (Ni) and tin (Sn).
  • the alloy cast iron according to one embodiment of the present invention comprises at least 0.02 to 0.5% by weight of at least one element selected from gross weight, boron (B) and vanadium (V), chromium (Cr) and molybdenum ( At least one element selected from Mo) 0.1 to 1.2 weight copper (Cu) 0.3 to 1 weight%, phosphorus (P) 0.02 to 0.03 weight%, carbon (C) 3.2 to 3.8 weight%, silicon (Si) 1.8 to 2.8 weight %, Manganese (Mn) 0.2 to 1 weight%, Magnesium (Mg) 0.005 to 0.05 weight ⁇ 3 ⁇ 4, Sulfur (S) 0.05 or less weight%, Nickel (Ni) 0 to 0.75 weight% , It may contain tin (Sn) 0 to 0.1% by weight and the balance of iron (Fe). Within this range graphite and steady-like process tissues can be easily precipitated, providing ductile properties and very good hardness. have.
  • the composition and content of each component can be differently adjusted according to the shape of the graphite tissue to be precipitated.
  • the alloy cast iron including spherical graphite tissue is selected from the group consisting of boron (B).
  • Chromium (Cr) and molybdenum (Mo) are added to either 0.15 to 0.4% by weight of Cr (Cr), 0.25 to 0.5% by weight of molybdenum (Mo), or both elements satisfy 0.15 to 1% by weight It can be added together in such a range that within this range, graphite structures can be easily precipitated to obtain spheroidal alloys with ductile properties.
  • alloy cast iron containing layered graphite tissue may contain boron (B) and
  • the graphite structure can be easily precipitated in layers to obtain an alloy cast iron having oil absorption ability.
  • alloy cast iron according to an embodiment of the present invention may have a surface hardened layer formed as described in the method of manufacturing alloy cast iron, which will be described later.
  • the ferrite base on the surface is converted into cementite (Fe 3 C) structure, and the cementite base cementite structure of alloy cast iron is produced immediately after the cooling process.
  • the hardness of the alloy is higher than that of the alloy, which means that specially treated alloy cast iron may have a higher hardness than the uncured inner layer.
  • the alloy cast iron satisfies Equation 1 below.
  • H s is the microviscus of the surface hardened layer of alloy cast iron.
  • HMV Hardness
  • HB Brinell hardness
  • the surface hardening layer means a surface layer of surface hardened alloy cast iron.
  • the thickness of the surface hardened layer is not necessarily limited to, but may be 0.1 to 2 kPa, preferably 0.4 to 1 kPa, and it is possible to obtain a very excellent hardness of the alloy cast iron in such a range.
  • the layer may refer to the rest of the alloyed cast iron, except for the surface hardened layer.
  • This surface hardening layer forming method can be used without any particular limitation as long as it is commonly used in the art.
  • the surface hardening layer can be formed by laser heat treatment or high frequency heat treatment.
  • the surface hardened layer can be formed and the laser can be irradiated for 1.5 to 15 minutes with an output of 1 to 5 kW during laser heat treatment, in which case the laser used is not particularly limited if it is normally used for heat treatment.
  • These alloy cast irons can have tensile strengths of 600 to 620 N / mrf, yield strengths of 450 to 480 N / ⁇ 2 , elongation of 1.5 to 3%, and microviscus hardness (HMV) of 900 to 1400.
  • MicroVickers hardness (HMV) can range from 1000 to 1400 and better from 1200 to 1400, but is not necessarily limited to this.
  • alloy cast iron according to the present invention can be applied to the surface of the chromium plated layer substantially.
  • another aspect of the present invention may be directed to a piston ring comprising the above-described alloy cast iron, that is, a pearlite base; and a graphite structure and a stete-type process structure precipitated in the filament base;
  • the steady-like process structure comprises at least one element selected from boron (B) and vanadium (V), at least one element selected from chromium (Cr) and molybdenum (Mo), and copper (Cu) It may be about the piston ring.
  • another aspect of the present invention may relate to an engine including the piston ring described above.
  • an engine may include an engine cylinder, a piston and a piston ring, and more specifically, the engine cylinder may be reciprocated up and down. A piston in motion; and a plurality of piston rings on the circumference of the piston.
  • a piston reciprocating up and down the engine cylinder; and a plurality of piston rings formed around the piston, the piston ring is a pilrite base; and the graphite tissue precipitated in the pearlite base And a steight type process structure, wherein the steat type process structure comprises at least one element selected from boron (B) and vanadium (V), at least one element selected from chromium (Cr) and molybdenum (Mo), And copper (Cu).
  • the steat type process structure comprises at least one element selected from boron (B) and vanadium (V), at least one element selected from chromium (Cr) and molybdenum (Mo), And copper (Cu).
  • another aspect of the present invention relates to a method of manufacturing alloy cast iron, wherein the method of manufacturing alloy cast iron according to an embodiment of the present invention is one or more elements selected from boron (B) and banana (V). Injecting into the mold a melt comprising at least one element selected from cr (Cr) and molybdenum (Mo), copper (Cu), iron (Fe) and carbon (C); and Alternatively, the method may include the production of graphite cast iron and graphite structure in a pearlite base and a steady-type process tissue.
  • the method may include the production of graphite cast iron and graphite structure in a pearlite base and a steady-type process tissue.
  • the manufacturing of the molten metal can be used without any particular limitation as long as it is commonly used in the art.
  • the raw material which is the raw material of the casting
  • the raw material is put into a cupola or electric furnace, and then the raw material is melted.
  • Melting temperature can be varied according to the type and content of the added metal, and it is necessary to heat up the temperature above the melting temperature of all raw materials.
  • the method can be used without particular limitation as long as it is a method used in a normal casting process, in which case the mold may have a shape of a pipe ring having a piston ring shape or a cross section of a ring shape.
  • the method of manufacturing an alloy cast iron according to an embodiment of the present invention may further include the step of curing the surface of the alloy cast iron by laser heat treatment or high frequency rupture treatment when the cooling is completed.
  • the thickness of the piston ring was about 6 mm, which made the surface hard to harden due to the generation of cracks during laser heat treatment or high frequency heat treatment.
  • the alloy cast iron according to the present invention has increased hardness due to the steady process structure.
  • ductility is imparted by graphite tissue, preferably spheroidal graphite tissue, to prevent the occurrence of cracks, and accordingly, the surface hardening of the piston ring is possible through laser heat treatment or high frequency heat treatment.
  • This surface hardening process can form a surface hardening layer on the surface of the cast iron.
  • surface hardening is performed by surface heat treatment such as laser heat treatment or high frequency rupture treatment on the surface of alloy cast iron which is manufactured right after the cooling process, and some of the surface ferrite structure is converted into cementite (Fe 3 C) structure.
  • surface heat treatment such as laser heat treatment or high frequency rupture treatment
  • the content of the cementite structure in the base is greater than that of the cementite structure in the alloy cast iron produced immediately after the cooling process, which means that the hardness of the alloy cast iron hardened by the surface heat treatment is increased. It may have a higher hardness than the layer, and in one non-limiting example, the alloy cast iron may satisfy the following equation.
  • Equation 1 3 ⁇ 4 is the microviscus of the surface hardened layer of alloy cast iron.
  • HMV Hardness
  • HB Brinell hardness
  • the surface hardening layer means a surface layer of surface hardened alloy cast iron.
  • the thickness of the surface hardened layer is not necessarily limited, but may be from 2 mm to 2 mm, preferably 0.4 to 1 mm, and in such a range, it is possible to obtain a very excellent hardness of the alloy cast iron.
  • the layer may refer to the rest of the alloyed cast iron, except for the surface hardened layer.
  • the surface hardened layer can be formed by laser heat treatment, and the laser can be irradiated for 1.5 to 15 minutes at an output of 1 to 5 kW during laser heat treatment.
  • the laser used may be used without particular limitation, as long as it is commonly used for heat treatment, and may be, for example, C0 2 laser, Nd: YAG laser, or aximmer laser, but is not limited thereto.
  • the final content of the total weight of the casting is 0.030 weight of boron (B) « 3 ⁇ 4, 0.39 weight% of chromium (Cr), 0.0339 weight% of molybdenum (Mo), 0.348 weight% of copper (Cu), 0.025 weight of phosphorus (P) %, Carbon (C) 3.49 increase silicon (Si) 2.59 increase%, manganese (Mn) 0.71 weight%, magnesium (Mg) 0.025 weight%, sulfur (S) 0.008 weight%, nickel (Ni) 0.61 weight% and iron (Fe) )
  • the raw materials are melted at 1500 ° C with a medium frequency induction to maintain the remaining amount, and then the molten hot water is injected into the sand casting. Cooling to less than 300 ° C. was demolded.
  • a precipitated alloy cast iron was produced.
  • a casting is manufactured in the same manner as Example 1, but the final weight of the casting is final.
  • a casting is manufactured in the same manner as in Example 1, except that the final increase in the total amount of the casting is performed.
  • a casting was manufactured in the same manner as in Example 2, except that the final weight of the casting was final.
  • the chromium plated layer was immersed in an aqueous solution containing 150 gl £ anhydrous chromic acid and 1.5 g / lactic acid, and the aqueous solution was elevated to 55 ° C, and the current density was 40 A / dm 2 for 4 hours. Formed by electroplating.
  • the piston ring manufactured by the alloy cast iron according to the present invention has a very good hardness compared to Comparative Examples 1 to 3, and thus has excellent wear resistance.
  • piston rings manufactured in accordance with the present invention were characterized by a tensile strength of 607 N / mirf and
  • the yield strength was 466 N / mnf, and the tensile strength and yield strength characteristics of the comparative examples 1 to 3 were also very good.
  • the elongation was 2.1%, which resulted in no cracking during the laser heat treatment. When fitted, it prevented the piston ring from deforming.
  • Comparative Example 3 the hardness was good as it was plated with an excellent cream layer.
  • the chromium plating layer was difficult to form an oil film due to the difficulty of oil wetting.
  • the wear and tear of the engine is difficult to use for long periods of time.
  • environmental substances such as chrome dust can be generated, and the fine chromium particles that are peeled off are discharged through the exhaust gas.
  • the emissions can cause environmental pollution, and if the engine oil is mixed with fine chromium particles, waste engine oil can be difficult to process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

본발명은 필라이트 기지; 및 상기 펄라이트 기지 내 석출된 흑연조직 및 스테다이트형 공정조직;을 포함하며, 상기 스테다이트형 공정조직은 붕소 (B) 및 바나듐(V)에서 선택되는 하나 이상의 원소, 크롬(Cr) 및 몰리브덴 (Mo)에서 선택되는 하나 이상의 원소, 및 구리(Cu)를 포함하는 합금주철 및 이를 포함하는 피스톤 링에 관한 것이다.

Description

명세서
발명의명칭:내마모성이향상된합금주철，및이를포함하는 피스톤링
기술분야
[1] 본발명은내마모성이향상된합금주철및이를포함하는피스론링에관한 것으로，상세하게는피스톤과실린더내벽사이의기밀을유지하고실린더벽의 윤활유를긁어내려윤활유가연소실로들어가지않도록하기위하여피스톤 바깥둘레의홈에끼워지는내마모성을향상시킨합금주철및피스톤링에관한 것이다ᅳ
배경기술
[2] 내연기관과같은동력발생장치의엔진에는실린더와실린더의내부에서
직선으로왕복운동을하는피스톤이구비되며,피스톤에는실린더와의마찰을 최소화하고기밀을유지하기위하여피스톤링이장착된다.
[3] 피스톤링은일반적으로실린더의내부에서왕복되는피스톤의외주면에 결합되어실린더라이너와내벽을따라왕복되게구비되며，고온고압에 노출되어상당한열부하와기계적부하를받기때문에내열성과내마모성이 우수해야한다.
[4] 그러나,종래기술에따른피스톤링은내마모성이층분하지않아엔진실린더 라이너의내벽의마찰에의해마모되기때문에엔진의연소가스가하부의 크탱크실내부로유입될수있으며，이렇게연소가스가누출되면연소압력은 저하되고크탱크실로유입되는연소가스에의해엔진의출력도저하되는 문제가있었다.
[5] 이와같은문제를타파하기위해，피스톤링의외주면에크롬도금층을
형성하여내마모성을향상시킴으로써피스톤링이마모되는것을
방지하였다 (대한민국둥록특허제 10-1292978호).
[6] 그러나，크름으로도금된피스톤링또한크롬도금층은오일의습윤이어려워 오일막을형성할수없는약점이있었으며， 200 N/mnf 이상의높은고압이가해질 시크름도금층이마모되어엔진의장기간사용이어려운단점이있다.
[7] 또한,크롬으로도금된피스톤링은환경문제로인해크롬도금을위한제조 시설의설치와운영이점차규제되고있어크롬도금공정을수행하기
어려워지고있는추세이다.
[8] 아울러，피스톤링의왕복동작시크롬도금층과실린더라이너간의마찰
과정에서크롬분진등의환경이물질이발생될수있으며，박리되는미세크롬 입자들이배기가스를통해외부로배출되기때문에환경오염을일으킬수있고， 엔진오일에미세크롬입자들이섞일경우에는폐엔진오일의처리도곤란해질 수있다는문제점이있다. [9] 이에 , 200 N/!mrf 이상의높은고압환경에서도우수한내마모성을가지며， 피스톤링의표면에오일막의형성이용이하여피스톤링의마모를더욱방지할 수있는피스톤링에대한개발이필요한실정이다.
발명의상세한설명
기술적과제
[10] 본발명은내마모성이향상된합금주철，및이를포함하는파스론링을
제공하는것을목적으로한다.
과제해결수단
[11] 상기목적을달성하기위한본발명의일양태는필라이트기지；및상기
필라이트기지내석출된흑연조직및스테다이트형공정조직;을포함하며，상기 스테다이트형공정조직은붕소 (B)및바나듐 (V)에서선택되는하나이상의 원소，크롬 (Cr)및몰리브덴 (Mo)에서선택되는하나이상의원소,및구리 (Cu)를 포함하는，합금주철에관한것이다.
[12] 상기일양태에있어,상기합금주철의단면적에있어，펄라이트기지:
혹연조직:스테다이트형공정조직의단면적비는 65내지 85： 10내지 30 : 4내지 7일수있다.
[13] 상기일양태에있어，상기스테다이트형공정조직은인 (P),탄소 (Q,규소 (Si), 망간 (Mn),마그네슘 (Mg),황 (S),니켈 (Ni)및주석 (Sn)에서선택되는어느하나 또는둘이상올더포함할수있다.
[14] 상기일양태에있어,상기합금주철은전체중량증，붕소 (B)및바나듬 (V)에서 선택되는하나이상의원소 0.02내지 0.1중량 %，크름 (Cr)및몰리브덴 (Mo)에서 선택되는하나이상의원소 0.1내지 1.2중량 %，구리 (Cu) 0.3내지 1중량 %，인 (P) 0.02내지 0.03증량 %，탄소 (C) 3.2내지 3.8증량 %，규소 (Si) 1.8내지 2.8증량 망간 (Mn) 0.2내지 1중량 마그네슘 (Mg) 0.005내지 0.05중량 황 (S) 0.05 이하중량 %，니켈 (Ni) 0내지 0.75중량 %，주석 (Sn) 0내지 0.1중량 %및잔량의 철 (Fe)을포함할수있다.
[15] 상기일양태에있어 ,상기스테다이트형공정조직은장축방향의길이가 50 내지 100 //m이며，폭이 5내지 30 /im일수있다.
[16] 상기일양태에있어，상기혹연조직은구상및충상에선선택되는어느하나 또는둘이상의형상일수있다.
[17] 상기일양태에있어,상기구상흑연조직은평균입경이 0.05내지 0.15 an이고， 상기충상흑연조직은장축방향의길이가 50내지 100 이며，폭이 5내지 30 /ffli일수있다.
[18] 상기일양태에있어，상기합금주철은표면경화층이형성된것일수았다.
[19] 상기일양태에있어,상기합금주철은하기관계식 1을만족하는것일수있다.
[20] [관계식 1]
[21] 2 < Hs/Ht < 10 [22] (상기관계식 1에서， Hs는합금주철의표면경화층의마이크로비커스 경도 (HMV)이며, ¾는합금주철의내부층의브리넬경도 (HB)이다.)
[23] 상기일양태에있어，상기표면경화층의두께는으1내지 2匪일수있다.
[24] 상기일양태에있어,상기표면경화층은레이저열처리또는고주파열처리를 통해형성될수있다.
[25] 또한,본발명의다른일양태는상기합금주철을포함하는피스톤링에관한 것이다.
[26] 또한,본발명의또다른일양태는상기피스톤링을포함하는엔진에관한 것이다.
[27] 또한,본발명의또다른일양태는붕소 (Β)및바나듐 (V)에서선택되는하나 이상의원소,크롬 (Cr)및몰리브덴 (Mo)에서선택되는하나이상의원소, 구리 (Cu),철 (Fe)및탄소 (C)를포함하는용탕을주형에주입하는단계;및상기 주형에주입된용탕을냉각시켜필라이트기지내흑연조직및스테다이트형 공정조직이석출된합금주철을제조하는단계를포함하는,합금주철의 제조방법에관한것이다.
[28] 상기일양태에있어，상기합금주철의제조방법은，상기합금주철의표면을 레이저열처리또는고주파열처리하여표면경화시키는단계를더포함할수 있다.
발명의효과
[29] 본발명에따른합금주철은흑연조직및스테다이트형공정조직이필라이트 기지내석출된구조를가짐으로써，흑연조직으로부터연성특성을확보하고, 스테다이트형공정조직으로부터뛰어난강도를확보하여，연성이우수하면서도 내마모성이우수한합금주철을제조할수있다.
[3이 이에따라이합금주철을포함하는피스톤링제조시，연성이우수하면서도 내마모성이우수한피스톤링을제조할수있으며,피스톤링의표면에크름 도금층을도금하는과정을생략할수있을뿐만아니라,크롬도금층과실린더 라이너간의마찰시크름분진등의환경이물질발생올방지할수있다.
[31] 아울러,크롬도금된피스톤링의경우， 2년내지 3년이내피스톤링의마모에 의해엔진의성능이저하되는반면，본발명에따른피스톤링은연성및 내마모성이매우뛰어나 5년이상성능의저하없이장기간사용할수있다는 장점이있다.
도면의간단한설명
[32] 도 1은본발명의일예에따른제조된피스톤링의단면현미경사진 (100 배율)이며，도 2는본발명의다른일예에따라제조된피스톤링의단면현미경 사진 (200배율)이다.도 1및 2에있어,검은색조직은흑연조직이며，하얀색으로 밝게빛나는부분은스테다이트형공정조직이고，나머지부분은필라이트 기지이다. [33] (부호의설명)
[34] 200:펄라이트기지 '
[35] 300:구상흑연조직
[36] 400:층상흑연조직
[37] 500:스테다이트형공정조직
발명의실시를위한형태
[38] 이하첨부한도면들을참조하여본발명에따른내마모성이향상된합금주철, 및이를포함하는피스론링에대하여상세히설명한다.다음에소개되는 도면들은당업자에게본발명의사상이층분히전달될수있도록하기위해 예로서제공되는것이다.따라서，본발명은이하제시되는도면들에한정되지 않고다른형태로구체화될수도있으며，이하제시되는도면들은본발명의 사상을명확히하기위해과장되어도시될수있다.또한명세서전체에걸쳐서 동일한참조번호들은동일한구성요소들을나타낸다.
[39] 이때，사용되는기술용어및과학용어에있어서다른정의가없다면，이
발명이속하는기술분야에서통상의지식을가진자가통상적으로이해하고 있는의미를가지며，하기의설명및첨부도면에서본발명의요지를
불필요하게흐릴수있는공지기능및구성에대한설명은생략한다.
[40] 기존,피스톤링의외주면에크롬도금층을형성하여내마모성을
향상시킴으로써피스톤링이마모되는것을방지하고자하였으나，크롬 도금층은오일의습윤이어려워오일막을형성할수없는약점이 있었으며， 200 N/nurf 이상의높은고압이가해질시크롬도금층이마모되어엔진의장기간 사용이어려운단점이있었다.
[41] 또한，피스톤링의왕복동작시크롬도금층과실린더라이너간의마찰
과정에서크롬분진등의환경이물질이발생될수있으며,박리되는미세크롬 입자들이배기가스를통해외부로배출되기때문에환경오염을일으킬수있고， 엔진오일에미세크롬입자들이섞일경우에는폐엔진오일의처리도곤란해질 수있다는문제점이있었다.
[42] 이에，본발명자들은 200 N/mrf 이상의높은고압환경에서도우수한내마모성을 가지며,피스톤링의표면에오일막의형성이용이하여피스톤링의마모를더욱 방지할수있는피스톤링및합금주철에대하여제시하고자한다.
[43] 상세하게,본발명의일예에따른합금주철은펄라이트기지 (pearlite matrix); 및상기필라이트기지내석출된흑연조직및스테다이트형 (steadite-type) 공정조직 ;을포함하며,상기스테다이트형공정조직은붕소 (B)및
바나듐 (V)에서선택되는하나이상의원소，크롬 (Cr)및몰리브덴 (Mo)에서 선택되는하나이상의원소，및구리 (Cu)를포함하는것일수있다.
[44] 이처럼흑연조직및스테다이트형공정조직이펼라이트기지내석출된구조를 가짐으로써，흑연조직으로부터연성특성을확보하고，스테다이트형 공정조직으로부터뛰어난강도를확보하여,연성이우수하면서도내마모성이 우수한합금주철을제조할수있다.이에따라이합금주철을포함하는피스톤 링제조시，연성이우수하면서도내마모성이우수한피스톤링을제조할수 있으며，피스톤링의표면에크름도금층을도금하는과정을생략할수있을 뿐만아니라，크롬도금층과실린더라이너간의마찰시크름분진둥의환경 이물질발생을방지할수있다.아울러，크롬도금된피스톤링의경우， 2년내지 3년이내피스톤링의마모에의해엔진의성능이저하되는반면，본발명에따른 피스톤링은연성및내마모성이매우뛰어나 5년이상성능의저하없이장기간 사용할수있다는장점이있다.
[45] 상세하게，펄라이트기지내상기스테다이트형공정조직을석출시킴으로써 합금주철및이를포함하는피스톤링의내마모성을크게향상시킬수있다. 보다구체적으로,합금주철및피스톤링에매우우수한내마모성을부여하는 실질적인요소는스테다이트형공정조직으로써，펄라이트기지의마이크로 비커스경도 (HMV)가약 200이고，피스톤링의표면에코팅되는표준크롬 도금층의마이크로비커스경도 (HMV)가약 850인것과비교하여，스테다이트형 공정조직은마이크로비커스경도 (HMV)가 900이상，좋게는 1000내지 1400, 보다좋게는 1200내지 1400의매우높은경도를가짐에따라매우뛰어난 내마모성을확보할수있다.즉，본발명에따른합금주철은경도가약한 필라이트를기지로하고있으나，경도가매우뛰어난스테다이트형공정조직이 필라이트기지사이사이형성되어있음에따라，피스톤링의왕복동작에따른 실린더라이너내벽과의마찰과정에서스테다이트형공정조직이마모되지 않고버텨줌으로써합금주철및피스톤링의전반적인마모를방지할수있다. 이때,마이크로비커스경도 (HMV)는표준시험법인 ASTM E384-16에의거하여 측정된것을기준으로한다.
[46] 또한，상기스테다이트형공정조직의크기및모양은주조조건에따라달라질 수있으며，비한정적인일구체예로스테다이트형공정조직은장축방향의 길이가 50내지 100 이며，폭이 5내지 30 일수있으며，보다좋게는장축 방향의길이가 70내지 90 이며두께가 15내지 20 일수있으나，반드시이에 제한되는것은아니다.
[47] 아울러，필라이트기지내상기흑연조직을석출시킴으로써연성또는오일 흡습력등을부여할수있다.보다구체적으로，상기흑연조직은구상및 충상에선선택되는어느하나또는둘이상의형상일수있는데，구상
흑연조직은합금주철및피스톤링에층분한연성을부여하여레이저열처리에 의한크랙 (crack)을방지할수있으며，그표면이균일하게열처리되도록할수 있다.또한오랜기간동안사용하더라도피스톤링의모양이변형되거나 부러지는등의파손올방지할수있다.충상흑연조직에있어충상은벌레 형상을의미하는것으로，충상흑연조직은실린더라이너와피스톤링사이에 도포되는윤활유를습윤하는능력이우수하여피스톤링의표면에오일막이 용이하게형성될수있으며，이에따라피스톤링뿐만아니라실린더라이너의 마모또한방지할수있다는장점이있다.또한，오일막이엔진의
블로우바이 (blow-by)현상 (폭발가스가누출되어크탱크실로유입되는현상)을 막아주게되어엔진의효율이개선되도록할수있다.
[48] 이때，상기흑연조직의크기및모양은주조조건에따라달라질수있으며,비 한정적인일구체예로구상흑연조직은평균입경이 0.05내지 0.15 μη,보다 좋게는 0.06내지 0.12 이고，상기층상혹연조직은장축방향의길이가 50내지 100 이며，폭이 5내지 30 / ,보다좋게는장축방향의길이가 70내지 90 /m이며두께가 15내지 20 일수있으나，반드시이에제한되는것은아니다.
[49] 한편，합금주철의우수한내마모성확보를위하여필라이트기지，흑연조직및 스테다이트형공정조직의단면적비를적절하게조절하여주는것이좋다. 구체적으로예를들면，합금주철의단면적에있어，펄라이트기지：혹연조직: 스테다이트형공정조직의단면적비는 65내지 85： 10내지 30： 4내지 7일수 있으며，보다좋게는 70내지 80： 15내지 25： 5내지 6일수있다.반면， 스테다이트형공정조직의단면적비가 4미만일경우내마모성이저하될수 있으며，단면적비가 7초과일경우연신율및탄성력이저하되어피스톤링으로 웅용할시피스톤링으로서의기능을제대로발휘할수없는문제점이발생할수 있다.즉,상기범위를만족함으로써우수한연성특성및내마모성을확보할수 있으며,성능이우수한피스톤링을제조할수있다.이때,단면적비는 합금주철의단면을현미경으로촬영한사진상해당조직이차지하는비율을 의미하는것일수있다.
[5이 아울러,높은경도를가지는스테다이트형공정조직및흑연조직을펄라이트 기지내에석출시키기위해서는주조시첨가되는금속의종류및함량을 적절하게조절하여주는것이좋다.스테다이트형공정조직의석출을위해서는 상기언급한붕소 (B)및바나듐 (V)에서선택되는하나이상의원소，크롬 (Cr)및 몰리브덴 (Mo)에서선택되는하나이상의원소,및구리 (Cu)를반드시 포함해야한다.상기금속이첨가되지않을경우，스테다이트형조직이형성되지 않을수있다.
[51] 이외에도본발명의목적을헤치지않는범위내에서，향상시키고자하는 물성의확보를위해스테다이트형공정조직은인 (P),탄소 (C),규소 (Si), 망간 (Mn),마그네슘 (Mg),황 (S),니켈 (Ni)및주석 (Sn)등에서선택되는어느하나 또는둘이상을더포함할수있다.
[52] 바람직한일구체예로,본발명의일예에따른합금주철은전체중량증， 붕소 (B)및바나듐 (V)에서선택되는하나이상의원소 0.02내지 0.5중량 %， 크롬 (Cr)및몰리브덴 (Mo)에서선택되는하나이상의원소 0.1내지 1.2중량 구리 (Cu) 0.3내지 1증량 %，인 (P) 0.02내지 0.03중량 %,탄소 (C) 3.2내지 3.8 중량 %，규소 (Si) 1.8내지 2.8중량 %，망간 (Mn) 0.2내지 1중량 %,마그네슘 (Mg) 0.005내지 0.05중량 <¾,황 (S) 0.05이하중량 %，니켈 (Ni) 0내지 0.75중량 %， 주석 (Sn) 0내지 0.1중량 %및잔량의철 (Fe)을포함하는것일수있다.이와같은 범위에서흑연조직및스테다이트형공정조직이용이하게석출될수있으며, 연성특성및매우우수한경도를확보할수있다.
[53] 보다바람직하게는,석출하고자하는흑연조직의형상등에따라각성분의 조성및그함량을달리조절할수있다.구체적인일예로,구상혹연조직을 포함하는합금주철은전체증량중,붕소 (B)및바나듐 (V)에서선택되는하나 이상의원소 0.025내지 0.35중량 %,크롬 (Cr)및몰리브덴 (Mo)에서선택되는 하나이상의원소 0.15내지 1중량 구리 (Cu) 0.3내지 0.4중량 %，인 (P) 0.02 내지 0.03증량 %,탄소 (C) 3.2내지 3.6증량 %，규소 (Si) 2.2내지 2.8증량 망간 (Mn) 0.5내지 0.8중량 마그네슘 (Mg) 0.01내지 0.03중량 %，황 (S) 0.01 이하중량 %，니켈 (Ni) 0.3내지 0/75증량 %및잔량의철 (Fe)을포함하는것일수 있다.이때，붕소 (B)와바나듬 (V)은각각붕소 0.025내지 0.045중량 <¾，바나듐 (V) 0.12내지 0.3중량 %가되도록어느하나의원소가첨가되거나또는두원소가 상기으025내지 0.35증량 %를만족하는범위에서함께첨가될수있다.
크롬 (Cr)과몰리브덴 (Mo)은크름 (Cr) 0.15내지 0.4중량 %，몰리브덴 (Mo) 0.25 내지 0.5중량 %가되도록어느하나의원소가첨가되거나또는두원소가상기 0.15내지 1중량 %를만족하는범위에서함께첨가될수있다.이와같은 범위에서흑연조직이구상으로용이하게석출되어연성특성이부여된 합금주철을확보할수있다.
[54] 또는,층상혹연조직을포함하는합금주철은전체증량중,붕소 (B)및
바나듐 (V)에서선택되는하나이상의원소 0.025내지 0.35중량 %，크름 (Cr) 0.15 내지 0.4중량 %，구리 (Cu) 0.7내지 0.8중량 %，인 (P) 0.02내지 0.03중량 %， 탄소 (C) 3.4내지 3.8중량 <%,규소 (Si) 2내지 2.6중량 %,망간 (Mn) 0.2내지 1 증량 %，마그네슘 (Mg) 0.008내지 0.02중량 %,황 (S) 0.01이하중량 %,주석 (Sn) 0.05내지 0.1중량 %및잔량의철 (Fe)을포함하는것일수있다.이때,붕소 (B)와 바나듐 (V)은각각붕소 0.025내지 0.045중량 %,바나듐 (V) 0.12내지 0.3중량 %가 되도록어느하나의원소가첨가되거나또는두원소가상기 0.025내지 0.35 증량 %를만족하는범위에서함께첨가될수있다.이와같은범위에서
흑연조직이층상으로용이하게석출되어오일흡습력을가지는합금주철을 확보할수있다.
[55] 한편,본발명의일예에따른합금주철은，후술하는합금주철의제조방법에서 설명하는바와같이，표면경화층이형성된것일수있다.이때，표면경화란냉각 공정직후제조된합금주철의표면에특수처리실시시，표면의필라이트기지 증일부페라이트조직이시멘타이트 (Fe3C)조직으로변환되어,필라이트기지 내시멘타이트조직의함량이냉각공정직후제조된합금주철의펄라이트기지 내시멘타이트조직의함량보다많아져경도가증가하는것을의미한다ᅳ즉， 특수처리된합금주철은경화되지않은내부층보다높은경도를가질수있으며， 비한정적인일구체예로,합금주철은하기관계식 1을만족하는것일수있다. [56] [관계식 1]
Figure imgf000009_0001
[58] (상기관계식 1에서, Hs는합금주철의표면경화층의마이크로비커스
경도 (HMV)이며， ¾는합금주철의내부층의브리넬경도 (HB)이다.)
[59] 아울러,상기표면경화층은표면경화된합금주철의표면층을의미하는
것으로，상기표면경화층의두께는반드시이에제한되는것은아니나 , 0.1내지 2 隱,바람직하게는 0.4내지 1 腿일수있으며,이와같은범위에서합금주철이 매우뛰어난경도를확보할수있다.또한，상기내부층은표면경화층을제외한 함금주철의나머지부분을의미하는것일수있다.
[6이 표면경화층형성방법은당업계에서통상적으로사용되는방법이라면특별히 한정하지않고사용할수있으나，바람직하게는레이저열처리또는고주파 열처리를통해표면경화층을형성할수있다.특히바람직하게는레이저 열처리를통해표면경화층을형성할수있으며，레이저열처리시， 1내지 5 kW의 출력으로， 1.5내지 15분동안레이저를조사할수있다.이때，사용되는레이저는 열처리를위해통상적으로사용되는것이라면특별히한정하지않고사용할수 있으며 ,예를들면 C02레이저 , Nd:YAG레이저 ,다이오드레이저또는엑시머 레이저등일수있으나,이에한정되는것은아니다.
[61] 이와같은합금주철은 600내지 620 N/mrf의인장강도， 450내지 480 N/誦 2의 항복강도, 1.5내지 3 %의연신율및 900내지 1400의마이크로비커스 경도 (HMV)를가질수있으며，마이크로비커스경도 (HMV)는좋게는 1000내지 1400,보다좋게는 1200내지 1400일수있으나，반드시이에한정되는것은 아니다.
[62] 아울러,본발명에따른합금주철은크롬도금층을표면에실질적으로
포함하지않을수있다.그러나본발명의기술적사상을해치지않는범위 내에서크름도금층에의한부가적인효과의부여를위해크름도금층을 도입하는것까지배제하는것은아니다.
[63] 또한，본발명의다른일양태는상기설명한합금주철을포함하는피스톤링에 관한것일수있으며,즉,펄라이트기지;및상기필라이트기지내석출된 흑연조직및스테다이트형공정조직;을포함하며，상기스테다이트형 공정조직은붕소 (B)및바나듐 (V)에서선택되는하나이상의원소，크롬 (Cr)및 몰리브덴 (Mo)에서선택되는하나이상의원소,및구리 (Cu)를포함하는피스톤 링에관한것일수있다.
[64] 이에대한구체적인내용은합금주철에서설명한내용과동일한바，중복
설명은생략하도록한다ᅳ
[65] 또한，본발명의또다른일양태는상기설명한피스톤링을포함하는엔진에 관한것일수있다.
[66] 상세하게,본발명의일예에따른엔진은엔진실린더，피스톤및피스톤링 등올포함하는것일수있으며，보다상세하게,엔진실린더를상하로왕복 운동하는피스톤;및상기피스톤의둘레부에마련된복수의피스톤링을 포함하는것일수있다.
[67] 더욱상세하게，엔진실린더를상하로왕복운동하는피스톤;및상기피스톤의 둘레부에마련된복수의피스톤링을포함하며，상기피스톤링은필라이트 기지;및상기펄라이트기지내석출된흑연조직및스테다이트형공정조직;을 포함하며，상기스테다이트형공정조직은붕소 (B)및바나듐 (V)에서선택되는 하나이상의원소,크롬 (Cr)및몰리브덴 (Mo)에서선택되는하나이상의원소,및 구리 (Cu)를포함하는것일수있다.
[68] 또한,본발명의또다른일양태는합금주철의제조방법에관한것으로,본 발명의일예에따른합금주철의제조방법은붕소 (B)및바나듬 (V)에서 선택되는하나이상의원소,크름 (Cr)및몰리브덴 (Mo)에서선택되는하나 이상의원소,구리 (Cu),철 (Fe)및탄소 (C)를포함하는용탕을주형에주입하는 단계;및상기주형에주입된용탕을넁각시켜펄라이트기지내흑연조직및 스테다이트형공정조직아석출된합금주철을제조하는단계를포함할수있다.
[69] 먼저,용탕의제조는당업계에서통상적으로사용되는방법이라면특별히 한정하지않고사용할수있으며,구체적으로예를들면주물의원료가되는 원재료를큐폴라또는전기로에넣은후열을가하여원재료를용융시켜용탕을 제조할수있다.이때，용융온도는첨가되는금속의종류및함량에따라달라질 수있으며 ,원재료가모두용융되는온도이상으로열올가하는것이
바람직하다.
[7이 이후，원재료가용융된용탕을주형에주입할수있으며，주형에주입하는
방법은통상적인주조과정에서사용되는방법이라면특별히한정하지않고 사용할수있으며,이때，주형은바람직하게피스톤링의형상또는링형상의 단면을갖는파이프형상둥의형상을가진것일수있다.
[71] 다음으로，주형에주입된용탕을냉각시켜펄라이트기지내흑연조직및
스테다이트형공정조직이석출된합금주철을제조할수있다.이때냉각은 서서히이루어지는것이바람직하며，넁각속도가너무빠른경우，스테다이트형 공정조직의석출이어려울수있다.
[72] 아울러，본발명의일예에따른합금주철의제조방법은,냉각이완료되면， 합금주철의표면을레이저열처리또는고주파열처리하여표면경화시키는 단계를더포함할수있다.기존피스톤링으로웅용되는주철의경우,피스톤 링의두께가약 6 mm로너무얇아레이저열처리또는고주파열처리할시크랙의 발생으로인하여표면경화가매우어려웠으나,본발명에따른합금주철은 스테다이트형공정조직에의해경도가증가하고,흑연조직，바람직하게는구상 흑연조직에의해연성이부여되어크랙의발생을방지할수있으며,이에따라 레이저열처리또는고주파열처리를통해피스톤링의표면경화가가능하다는 장점이있다.
[73] 이와같은표면경화과정을통해합금주철의표면에표면경화층이형성될수 있다.이때，표면경화란냉각공정직후제조된합금주철의표면에레이저 열처리또는고주파열처리와같은표면열처리실시시，표면의펄라이트기지 중일부페라이트조직이시멘타이트 (Fe3C)조직으로변환되어 ,펄라이트기지 내시멘타이트조직의함량이냉각공정직후제조된합금주철의펄라이트기지 내시멘타이트조직의함량보다많아져경도가증가하는것을의미한다.즉， 표면열처리에의해경화된합금주철의표면은경화되지않은내부층보다높은 경도를가질수있으며，비한정적인일구체예로,합금주철은하기관계식 1을 만족하는것일수있다.
[74] [관계식 1]
[75] 2 < Hs/H[ < 10
[76] (상기관계식 1에서, ¾는합금주철의표면경화층의마이크로비커스
경도 (HMV)이며， ¾는합금주철의내부층의브리넬경도 (HB)이다.)
[77] 아울러，상기표면경화층은표면경화된합금주철의표면층을의미하는
것으로,상기표면경화층의두께는반드시이에제한되는것은아니나 , ι내지 2 mm,바람직하게는 0.4내지 1醒일수있으며，이와같은범위에서합금주철이 매우뛰어난경도를확보할수있다.또한，상기내부층은표면경화층을제외한 함금주철의나머지부분을의미하는것일수있다.
[78] 바람직하게는,레이저열처리를통해표면경화층을형성할수있으며，레이저 열처리시， 1내지 5 kW의출력으로， 1.5내지 15분동안레이저를조사할수있다. 이때,사용되는레이저는열처리를위해통상적으로사용되는것이라면특별히 한정하지않고사용할수있으며，예를들면 C02레이저 , Nd:YAG레이저또는 액시머레이저등일수있으나，이에한정되는것은아니다.
[79] 이하실시예를통해본발명에따른내마모성이향상된합금주철，및이를
포함하는피스톤링에대하여더욱상세히설명한다.다만하기실시예는본 발명을상세히설명하기위한하나의참조일뿐본발명이이에한정되는것은 아니며，여러형태로구현될수있다.또한달리정의되지않은한，모든기술적 용어및과학적용어는본발명이속하는당업자중하나에의해일반적으로 이해되는의미와동일한의미를갖는다.본원에서설명에사용되는용어는단지 특정실시예를효과적으로기술하기위함이고본발명을제한하는것으로 의도되지않는다.또한명세서및첨부된특허청구범위에서사용되는단수 형태는문맥에서특별한지시가없는한복수형태도포함하는것으로의도할수 있다.또한명세서에서특별히기재하지않은첨가물의단위는중량 %일수있다.
[80] [실시예 1]
[81] 주물의전체중량중최종함량이붕소 (B) 0.030중량 «¾,크롬 (Cr) 0.39증량 %， 몰리브덴 (Mo) 0.0339중량 %,구리 (Cu) 0.348중량 %,인 (P) 0.025중량 %,탄소 (C) 3.49증량 규소 (Si) 2.59증량 %，망간 (Mn) 0.71중량 %，마그네슘 (Mg) 0.025 중량 %，황 (S) 0.008중량 %，니켈 (Ni) 0.61중량 %및철 (Fe)잔량이되도록 원재료를중주파유도로 1500°C로용해한후,이용탕을사형주조에주입하여 300°C이하로냉각하여탈사 (demolding)하였다.
[82] 다음으로，탈사된주물올피스톤링의형상이되도록기계가공한후，피스톤링 형상의주물을회전시키면서그외주면을출력 3.0 kW의다이오드레이저로
10분동안레이저열처리하였다ᅳ
[83] 이를통해펄라이트기지내구상흑연조직및스테다미트형공정조직이
석출된합금주철을제조하였다.
[84] [실시예 2]
[85] 실시예 1과동일한방법으로주물을제조하되,주물의전체중량중최종
함량이붕소 (B) 0.030중량 크롬 (Cr) 0.39증량 %，구리 (Cu) 0.73중량 인 (P) 0.024중량 %，탄소 (C) 3.61중량 %,규소 (Si) 2.24중량 %，망간 (Mn) 0.32증량 %， 마그네슘 (Mg) 0.011중량 %,황 (S) 0.007중량 %，주석 (Sn) 0.083중량 %및철 (Fe) 잔량이되도록하였으며，이를통해펄라이트기지내층상혹연조직및 스테다이트형공정조직이석출된합금주철을제조하였다.
[86] [비교예 1]
[87] 실시예 1과동일한방법으로주물을제조하되，주물의전체증량중최종
함량이구리 (Cu) 0.348증량 %，인 (P) 0.025중량 %，탄소 (C) 3.49중량 %，규소 (Si) 2.59중량 %，망간 (Mn) 0.71증량 마그네슘 (Mg) 0.025중량 황 (S) 0.008 중량 %，니켈 (Ni) 0.61중량 <¾및철 (Fe)잔량이되도록하였으며,이를통해 필라이트기지내구상흑연조직만이석출된구상흑연주철을제조하였다.
[88] [비교예 2]
[89] 실시예 2와동일한방법으로주물을제조하되,주물의전체중량중최종
함량이구리 (Cu) 0.73증량 %,인 (P) 0.024중량 탄소 (C) 3.61중량 %,규소 (Si) 2.24중량 %，망간 (Mn) 0.32중량 %，마그네슴 (Mg) 0.011중량 %，황 (S) 0.007 중량 %,주석 (Sn) 0.083증량" ¾및철 (Fe)잔량이되도록하였으며，이를통해 필라이트기지내층상흑연조직만이석출된층상흑연주철을제조하였다.
[90] [비교예 3]
[91] 비교예 1과동일한방법으로레이저열처리되지않은구상흑연주철을제조한 후,주물의표면을크롬도금층으로코팅하였다.
[92] 이때，크롬도금층은무수크롬산 150 gl£및락트산 1.5 g/을함유하는수용액에 주물을침지한후，수용액의은도를 55°C로승은하고，전류밀도 40 A/dm2로 4시간 동안전기도금하여형성하였다.
[93] [경도측정]
[94] 상기실시예 1，2，비교예 1및 2에서제조된시편은레이저열처리전후각각의 경도를측정하였으며，레이저열처리전 (표면처리전)에는 ASTM E10-12에 의거하여크기 10 mm,하중 3000 kg인쇠구슬로브리넬경도 (HB)를
측정하였으며，레이저열처리후 (표면처리후)에는각도 136°,하중 50 kg인 피라미드형다이아몬드압자로 ASTM E384-16에의거하여마이크로비커스 경도 (HMV)를측정하였다.단,비교예 3의경우，크름층도금전을표면처리 전으로,크름층도금후를표면처리후로하여실시예와비교하였다.
[표 1]
Figure imgf000013_0001
[97] 상기표 1에기재된바와같이,본발명에따른합금주철로제조된피스톤링은 비교예 1내지 3대비매우우수한경도를가짐을알수있으며，이를통해매우 뛰어난내마모성을가짐을확인할수있었다.
[98] 이에더하여，본발명에따라제조된피스톤링은인장강도 607 N/mirf 및
항복강도 466 N/mnf로,비교예 1내지 3대비인장강도및항복강도특성또한 매우우수하였으며,연신율이 2.1%로우수하여레이저열처리시크랙이 발생하지않았으며，피스톤의둘레부홈에피스톤링을끼울시，피스톤링의 모양이변형되는것을방지할수있었다.
[99] 반면，비교예 1및 2의경우，경도가실시예 1및 2대비극히현저하게
떨어졌으며,비교예 3은경도가우수한크름층으로도금됨에따라경도는 좋았으나，크롬도금층은오일의습윤이어려워오일막을형성할수없는 약점이있으며 , 200 N/mrf 이상의높은고압이가해질시크롬도금층이마모되어 엔진의장기간사용이어려운단점이있다.또한，크롬이도금된피스톤링과 실린더라이너간의마찰과정에서크롬분진등의환경이물질이발생될수 있으며,박리되는미세크롬입자들이배기가스를통해외부로배출되기때문에 환경오염을일으킬수있고，엔진오일에미세크롬입자들이섞일경우에는폐 엔진오일의처리도곤란해질수있다는문제점이있다.
[100] 이상에서본발명의바람직한실시예를설명하였으나,본발명은다양한
변화와변경및균등물을사용할수있으며,상기실시예를적절히변형하여 동일하게웅용할수있음이명확하다.따라서상기기재내용은하기
특허청구범위의한계에의해정해지는본발명의범위를한정하는것이아니다.

Claims

청구범위
[청구항 1] 펄라이트기지;및상기펄라이트기지내석출된흑연조직및
스테다이트형공정조직;을포함하며,
상기스테다이트형공정조직은붕소 (B)및바나듐 (V)에서선택되는하나 이상의원소,크름 (Cr)및몰리브덴 (Mo)에서선택되는하나이상의원소, 및구리 (Cu)를포함하는，합금주철.
[청구항 2] 제 1항에있어서，
상기합금주철의단면적에있어，필라이트기지：혹연조직:스테다이트형 공정조직의단면적비는 65내지 85 : 10내지 30 : 4내지 7인,합금주철.
[청구항 3] 제 1항에있어서，
상기스테다이트형공정조직은인 (P),탄소 (C),규소 (Si),망간 (Mn), 마그네슘 (Mg),황 (S)，니켈 (Ni)및주석 (Sn)에서선택되는어느하나또는 둘이상을더포함하는，합금주철.
[청구항 4] 제 3항에있어서，
상기합금주철은전체중량중，붕소 (B)및바나듐 (V)에서선택되는하나 이상의원소 0.02내지 0.5중량 <¾,크름 (Cr)및몰리브덴 (Mo)에서 선택되는하나이상의원소 0.1내지 1.2중량 %,구리 (Cu) 0.3내지 1 증량 %，인 (P) 0.02내지 0.03중량 탄소 (C) 3.2내지 3.8중량 %»,규소 (Si) 1.8내지 2.8중량 %，망간 (Mn) 0.2내지 1중량 %，마그네슘 (Mg) 0.005내지 0.05중량 %，황 (S) 0.05이하중량 %，니켈 (Ni) 0내지 0.75중량 주석 (Sn) 0내지 0.1중량 %및잔량의철 (Fe)을포함하는,합금주철.
[청구항 5] 제 1항에있어서,
상기스테다이트형공정조직은장축방향의길이가 50내지 100卿이며， 폭이 5내지 30 인，합금주철.
[청구항 6] 제 1항에있어서,
상기혹연조직은구상및충상에선선택되는어느하나또는둘이상의 형상인,합금주철.
[청구항 7] 제 6항에있어서，
상기구상혹연조직은평균입경이 0.05내지 0.15 이고,상기층상 흑연조직은장축방향의길이가 50내지 100 이며,폭이 5내지 30 ;ΜΠ인， 합금주철.
[청구항 8] 제 1항에있어서，
상기합금주철은표면경화층이형성된것인，합금주철.
[청구항 9] 제 8항에있어서，
상기합금주철은하기관계식 1을만족하는것인，합금주철.
[관계식 1]
2 < Hs/H, < 10 (상기관계식 1에서， ¾는합금주철의표면경화층의마이크로비커스 경도 (HMV)이며, ¾는합금주철의내부층의브리넬경도 (HB)이다.)
[청구항 10] 제 8항에있어서，
상기표면경화층의두께는 0.1내지 2匪인，합금주철.
[청구항 11] 제 8항에있어서，
상기표면경화층은레이저열처리또는고주파열처리를통해형성되는， 합금주철.
[청구항 12] 제 1항내지제 11에서선택되는어느한항의합금주철을포함하는
피스톤링.
[청구항 13] 제 12항의피스톤링을포함하는엔진.
[청구항 14] 붕소 (B)및바나듐 (V)에서선택되는하나이상의원소，크름 (Cr)및
몰리브덴 (Mo)에서선택되는하나이상의원소,구리 (Cu),철 (Fe)및 탄소 (C)를포함하는용탕을주형에주입하는단계;및
상기주형에주입된용탕을넁각시켜펄라이트기지내흑연조직및 스테다이트형공정조직이석출된합금주철을제조하는단계를포함하는 합금주철의제조방법ᅳ
[청구항 15] 제 I4항에있어서，
상기합금주철의제조방법은,상기합금주철의표면올레이저열처리 또는고주파열처리하여표면경화시키는단계를더포함하는, 합금주철의제조방법.
PCT/KR2017/002573 2016-03-09 2017-03-09 내마모성이 향상된 합금주철, 및 이를 포함하는 피스톤 링 Ceased WO2017155331A1 (ko)

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DK17763592.7T DK3428486T3 (da) 2016-03-09 2017-03-09 Legeret støbejern med en forbedret slidstyrke, og stempelring omfattende dette
JP2018518560A JP6712316B2 (ja) 2016-03-09 2017-03-09 耐摩耗性が向上した合金鋳鉄、およびこれを含むピストンリング

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