US3899319A - Powder mixture for the production of alloy steel with a low content of oxide inclusions - Google Patents

Powder mixture for the production of alloy steel with a low content of oxide inclusions Download PDF

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Publication number
US3899319A
US3899319A US518474A US51847474A US3899319A US 3899319 A US3899319 A US 3899319A US 518474 A US518474 A US 518474A US 51847474 A US51847474 A US 51847474A US 3899319 A US3899319 A US 3899319A
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United States
Prior art keywords
powder
mole
alloying elements
oxides
formation
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US518474A
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English (en)
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Per Folke Lindskog
Per Gunnar Arbstedt
Erik Goran Wastenson
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Hoganas AB
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Hoganas AB
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0264Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0207Using a mixture of prealloyed powders or a master alloy

Definitions

  • a powder mixture for manufacturing of alloy steel wherein the metal powder portion consists of a mixture of two powders, viz. a first atomized prealloyed steel powder and a second non atomized alloy powder comminuted from a solidified melt.
  • the alloying elements are distributed in such a way that elements, the oxides of whichare easily reducible preferably nickel, copper, molybdenum and/or cobalt substantially enter into the atomized prealloyed steel powder and the oxidation sensitive elements especially chromium and manganese enter into the finely communited powder.
  • the present invention relates to metal powders for the manufacture of alloy steel and especially low alloy steel. Such manufacturing can be carried out by means of the conventional powder metallurgical method (pressing and sintering) or by means of the developing hot forging method.
  • oxide impurities present in the powder have a much more damaging influence on the mechanical properties than they have in products compressed and sintered in conventional manner.
  • Powders for the production of such alloy steel products can be divided into two principally different groups. First. it is possible to mix different powders each consisting of one or more but not all of the alloying elements of the finished product.
  • each powder particle is homoge neously alloyed with the same proportions of alloying elements as desired in the end product.
  • this alloying method has some disadvantages which in some cases make it directly unsuitable.
  • the heating of green compacts in reducing atmosphere before the forging offers a further possibility of reducing remaining oxides in the powder. since this heating is carried out to a higher temperature than the one used for the annealing of the powder.
  • the present technique it is possible to produce substantially oxide free forged materials provided that the steel powder only contains alloying elements. the oxides of which are relatively easily reduced. i.e. have a free energy of formation with an absolute value lower than 120 kcaI/mole O (502 kJ/mole 0 at IO0U C.,Values of the free energy of formation for oxides of some of the alloying elements most commonly present in steel calculated according to Kubaschewsky, O. & Evan. L. I... Metallurgical Thermochemistry, London I956. are given in the table below.
  • these oxides then cause a strong impairment of ductility and toughness. These properties. however, are also dependent of the size of the oxide inclusions as shown by experiments. At predetermined total oxygen content in the end product the material obtains considerably impaired mechanical prop erties when the oxygen is present in the form of coarse impurities in comparison with material where the oxide impurities are small but therefore more numerous. This critical size of the oxide inclusions, above which they cause a strong impairment of the properties of the material is between 20 um and 100 am.
  • the present invention provides for a solution of the problem of avoiding the above mentioned difficulties by means of a suitable powder mixture.
  • the metal powder portion consists of a mixture of two powders. viz.. a first atomized prealloyed steel powder and a second non atomized alloy powder comminuted from a solidified melt.
  • the alloying elements are distributed in such a way that elements. the oxides of which are easily reducible (preferably nickel. copper. molybdenum and- /or cobalt) substantially enter into the atomized prealloyed steel powder and the oxidation sensitive elements (especially chromium and manganese) enter into the finely comminuted powder.
  • the atomized prealloyed powder is produced by melting iron and ().2l ()7: of alloying elements. the oxides of which have an absolute value of the free energy of formation below 120 kcal/mole O 502 kJ/mole O- at 1000 C. water atomization of the melt and finally annealing in a reducing atmosphere (suitably cracked ammonia).
  • the atomized prealloyed powder can contain up to 0.4% accessory elements. the oxides of which have an absolute value of the free energy of formation above 120 kcal/mole O (502 kJ/mole at 1000 C. The content of such accessory elements.
  • the oxides of which have an absolute value of the free energy of formation above 150 kcal/mole O- (627 kJ/mole O- at 1000 C, should not exceed 0.1%.
  • the contents of silicon. titanium and aluminum should not exceed 0.04%. 0.03% and 0.03%. respectively.
  • the powder should have such a particle size distribution that more than 90% and preferably more than 97% of the powder passes a sieve having a mesh opening of 175 .1.m (80 Tyler mesh; Method for sieve analysis ofgranu lar metal powders. MPlF Standard 5-46. Metal Powder Industries Federation. New York. USA).
  • alloying elements the oxides of which have an absolute value of the free energy of formation exceeding 120 kcal/mole O (502 kJ/mole 0 at 1000 C, are molten possibly under addition of at most 75% preferably at most 50% iron and/or other metals with easily re ducible oxides and carbon. and is cast. The ingot is crushed and comminuted to a fine alloy powder. The total content of elements. the oxides of which have an absolute value of the free energy of formation exceeding 150 kcal/mole O (627 kJ/mole 0 at 1000 C. should not be higher than 1% in the finely comminuted alloy powder.
  • the two components are now mixed in the proportions 80-99% atomized prealloyed powder and l% finely comminuted alloy powder.
  • a powder mixture produced in this way provides a material having small and few oxide particles which is shown by the following example.
  • EXAMPLE l Two powders were produced. one by atomizing by means of water and subsequent annealing in cracked ammonia (A). the other by mixing finely ground ferro alloy powder and water atomized. molybdenumalloyed steel powder (B).
  • the two powders (A) and (B) had the composition of 1% Mn. 1% Cr. 0.5% Mo. balance Fe.
  • the ferroalloy powder used in powder (B) had the composition Mn. 25% Cr. 7% C. balance Fe. and an average particle size of 4 am according to Fischer (Methods for determination of average particle size of metal powder by the Fischer sub-sieve sizer. MPlF Standard 32-60. Metal Powder Industries Feder ation. New York. USA). In both cases graphite was added in such an amount that the carbon content of the powders amounted to 0.5%.
  • Green compacts in the form of cylinders with 25 mm diameter and mm length were pressed from both powders.
  • the compacts were heated, one group at 1 120 C in hydrogen gas atmosphere with a dew point of 20 C and maintained at these temperatures for 30 minutes. From the furnace the compacts were ripidly brought to a die where the cylinders at the elevated temperature were compressed to full density.
  • the alloying elements are to a large extent homogeneously distributed in the finished product.
  • the component of the mixture containing the oxidation sensitive alloying elements according to the invention must be comminuted to a small particle size. This is illustrated in the followmg example.
  • EXAMPLE 2 Three powder mixtures were produced. all of them with the composition 1% chromium. 2% nickel and 0.5% molybdenum. balance iron. in all of the mixtures the components consisted of water atomized prealloyed steel powder comprising 2% nickel and 0.5% molybdenum. and ferro-chromium powder comprising chromium and 0.3% carbon.
  • the ferrochromium powder had an average particle size according to Fischer of 33 ,um.
  • D 20 um
  • E third case
  • 0.5% graphite powder and 0.8% zinc stearate were mixed into the three powders.
  • a further improvement in this respect is obtained if the mixture is subjected to a heat treatment at 65()900 C for a period of minutes to 2 hours in reducing atmosphere with subsequent cautious disintegration of the cake formed.
  • this treatment the finely comminuted alloy powder particles are sintercd to the steel powder particles which effectively counteracts segregation.
  • This cautious sintering treatment can be carried out on powder to which the above mentioned oil has been added as well as on powder without the addition of such oil.
  • this finely comminuted powder can advantageously be mixed with only part of the steel powder to form a concentrate.
  • This concentrate is then subjected to one of the above described processes for diminishing the risk of segregation. Finally this concentrate is mixed with such a quantity of steel powder that the desired composition is obtained.
  • the mixtures according to the above specification can contain a suitable lubricant. c.g. zinc stearate.
  • a suitable lubricant c.g. zinc stearate.
  • the addition of lubricant should not exceed 1%.
  • a powder mixture for manufacturing of alloy steel articles having small and few oxide inclusions comprising a metal powder portion which consists of a mixture of two powders. viz. an atomized prealloyed steel powder and a finely comminuted powder containing alloying elements. wherein alloying elements. the oxides of which have a free energy of formation with an absolute value less than 120 kcal/mole O (502 kJ/molc 0 at 1()O() C substantially are contained in the atomized prealloyed powder while all alloying elements. the oxides of which have a free energy of formation with an absolute value exceeding 120 kcal/mole O (502 kJ/mole 0 at 1()0O C. are completely contained in the finely comminuted powder.
  • a powder mixture according to claim 1. consisting of to 99% of an atomized prealloyed powder of iron and (1.2 to 10% of said alloying elements, the oxides of which have a free energy of formation with an absolute value of less than kcal/mole O (502 kJ/mole 0 at 10()() C. and ofa finely comminuted powder consisting of a total of at least 25% and preferably at least 50% of said alloying elements.
  • a powder mixture according to claim I in which that the finely comminuted powder consists of a ferro alloy with a total of at least 25% and preferably at least 50% of said alloying elements.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
US518474A 1973-11-29 1974-10-29 Powder mixture for the production of alloy steel with a low content of oxide inclusions Expired - Lifetime US3899319A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE7316117A SE378260B (xx) 1973-11-29 1973-11-29

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US3899319A true US3899319A (en) 1975-08-12

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US (1) US3899319A (xx)
JP (1) JPS5429171B2 (xx)
AT (1) AT344763B (xx)
CA (1) CA1036389A (xx)
DE (1) DE2455850C3 (xx)
FR (1) FR2253101B1 (xx)
GB (1) GB1491726A (xx)
IT (1) IT1023230B (xx)
SE (1) SE378260B (xx)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370385A (en) * 1979-07-18 1983-01-25 Kirin Beer Kabushiki Kaisha Masking of abrasion injury on glass articles
DE3421858A1 (de) * 1983-06-15 1985-01-03 Nippon Dia Clevite Co., Ltd., Narashino, Chiba Verfahren zum herstellen eines poroesen koerpers aus rostfreiem stahl
US4552719A (en) * 1980-12-03 1985-11-12 N.D.C. Co., Ltd. Method of sintering stainless steel powder
WO1986006748A1 (en) * 1985-05-17 1986-11-20 Aluminum Company Of America Alloy toughening method
US4946499A (en) * 1987-09-30 1990-08-07 Kawasaki Steel Corp. Method of preparing iron base powder mixture for pm
US5482530A (en) * 1993-12-21 1996-01-09 H,C. Starck Gmbh & Co. Kg Cobalt metal powder and composite sintered articles produced therefrom
US6332904B1 (en) * 1999-09-13 2001-12-25 Nissan Motor Co., Ltd. Mixed powder metallurgy process
WO2011097736A1 (en) * 2010-02-15 2011-08-18 Corporation De L'ecole Polytechnique De Montreal A master alloy for producing sinter hardened steel parts and process for the production of sinter hardened parts
CN105834435A (zh) * 2015-12-30 2016-08-10 中国航空工业集团公司北京航空材料研究院 一种镍基高温烯合金粉末湿混制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE408435B (sv) * 1976-11-03 1979-06-11 Hoeganaes Ab Sett att framstella ett kopparhaltigt jernpulver
DE3043321A1 (de) * 1979-11-26 1981-05-27 Gould Inc., Rolling Meadows, Ill. Sinterprodukt aus metall-legierung und dessen herstellung
SE445715B (sv) * 1984-11-30 1986-07-14 Hoeganaes Ab Mangansulfidhaltig jernpulverblandning
EP0846782A1 (en) * 1992-09-09 1998-06-10 STACKPOLE Limited Powder metal alloy process
CA2104605C (en) * 1992-09-09 2000-05-02 Peter Jones Powder metal alloy process
AU3154793A (en) * 1992-12-21 1994-07-19 Stackpole Limited As sintered coining process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424572A (en) * 1966-09-13 1969-01-28 Niranjan M Parikh Alloyed metallic powder process
US3716354A (en) * 1970-11-02 1973-02-13 Allegheny Ludlum Ind Inc High alloy steel
US3725142A (en) * 1971-08-23 1973-04-03 Smith A Inland Inc Atomized steel powder having improved hardenability

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424572A (en) * 1966-09-13 1969-01-28 Niranjan M Parikh Alloyed metallic powder process
US3716354A (en) * 1970-11-02 1973-02-13 Allegheny Ludlum Ind Inc High alloy steel
US3725142A (en) * 1971-08-23 1973-04-03 Smith A Inland Inc Atomized steel powder having improved hardenability

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370385A (en) * 1979-07-18 1983-01-25 Kirin Beer Kabushiki Kaisha Masking of abrasion injury on glass articles
US4552719A (en) * 1980-12-03 1985-11-12 N.D.C. Co., Ltd. Method of sintering stainless steel powder
DE3421858A1 (de) * 1983-06-15 1985-01-03 Nippon Dia Clevite Co., Ltd., Narashino, Chiba Verfahren zum herstellen eines poroesen koerpers aus rostfreiem stahl
WO1986006748A1 (en) * 1985-05-17 1986-11-20 Aluminum Company Of America Alloy toughening method
US4946499A (en) * 1987-09-30 1990-08-07 Kawasaki Steel Corp. Method of preparing iron base powder mixture for pm
US5482530A (en) * 1993-12-21 1996-01-09 H,C. Starck Gmbh & Co. Kg Cobalt metal powder and composite sintered articles produced therefrom
US6332904B1 (en) * 1999-09-13 2001-12-25 Nissan Motor Co., Ltd. Mixed powder metallurgy process
WO2011097736A1 (en) * 2010-02-15 2011-08-18 Corporation De L'ecole Polytechnique De Montreal A master alloy for producing sinter hardened steel parts and process for the production of sinter hardened parts
CN102933731A (zh) * 2010-02-15 2013-02-13 费德罗-摩格尔公司 一种用于制造烧结硬化钢零件的中间合金以及该烧结硬化零件的制造工艺
US10618110B2 (en) 2010-02-15 2020-04-14 Tenneco Inc. Master alloy for producing sinter hardened steel parts and process for the production of sinter hardened parts
CN105834435A (zh) * 2015-12-30 2016-08-10 中国航空工业集团公司北京航空材料研究院 一种镍基高温烯合金粉末湿混制备方法
CN105834435B (zh) * 2015-12-30 2020-01-21 中国航空工业集团公司北京航空材料研究院 一种镍基高温烯合金粉末湿混制备方法

Also Published As

Publication number Publication date
SE7316117L (xx) 1975-05-30
SE378260B (xx) 1975-08-25
DE2455850A1 (de) 1975-06-05
FR2253101B1 (xx) 1982-02-19
DE2455850B2 (de) 1979-01-25
IT1023230B (it) 1978-05-10
CA1036389A (en) 1978-08-15
JPS5429171B2 (xx) 1979-09-21
AT344763B (de) 1978-08-10
ATA908974A (de) 1977-12-15
FR2253101A1 (xx) 1975-06-27
GB1491726A (en) 1977-11-16
DE2455850C3 (de) 1979-09-20
JPS50113402A (xx) 1975-09-05

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