CN107614158A - The sintered body of its making of ferrous based powder metallurgical mixed powder and its manufacture method and use and the manufacture method of sintered body - Google Patents
The sintered body of its making of ferrous based powder metallurgical mixed powder and its manufacture method and use and the manufacture method of sintered body Download PDFInfo
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- CN107614158A CN107614158A CN201680029964.6A CN201680029964A CN107614158A CN 107614158 A CN107614158 A CN 107614158A CN 201680029964 A CN201680029964 A CN 201680029964A CN 107614158 A CN107614158 A CN 107614158A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
- C22C33/0221—Using a mixture of prealloyed powders or a master alloy comprising S or a sulfur compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/25—Oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The ferrous based powder metallurgical of the present invention is included with mixed powder：Iron-based powder；With, CaS material powders, the CaS material powders contain selected from one or more of group being made up of type III dead plaster, II types dead plaster, calcium sulphate dihydrate, calcium sulfide and half-H 2 O calcium sulphate, wherein, the CaS material powders are covered by any one of lubricant and binding agent or both.
Description
Technical field
Sintered body and burning the present invention relates to ferrous based powder metallurgical mixed powder and its manufacture method and using its making
The manufacture method of knot body, more particularly to comprising the vulcanization calcium powder covered by any one of lubricant and binding agent or both or
The ferrous based powder metallurgical mixed powder of sulfate hemihydrate calcium powder and its manufacture method and the sintered body and sintering using its making
The manufacture method of body.
Background technology
Powder metallurgy is widely used as the industrialized preparing process of various mechanical parts.The step of ferrous based powder metallurgical
In, first, by by the alloy such as iron-based powder and copper (Cu) powder, nickel (Ni) powder with powder, graphite powder, mix lubricant and
Prepare mixed powder.Then, the mixed powder is filled into mould simultaneously extrusion molding, is sintered, thus makes sintered body.Most
Afterwards, such as Drilling operation, turnery processing machining are implemented to the sintered body, is derived from the mechanical part of desired shape.
Preferable powder metallurgy, it is to regard the sintered body as mechanical part energy not implement machining for sintered body
The mode that enough uses is processed.But above-mentioned sintering can make material powder produce uneven contraction sometimes.In recent years, machine
Dimensional accuracy required by tool part is high, and component shape complicates.Therefore, sintered body implementation machining is had become must
Need.Under such technical background, machinability is imparted for sintered body, smoothly to process the sintered body.
As the scheme for assigning above-mentioned machinability, there is the method being added to manganese sulfide (MnS) powder in mixed powder.Sulphur
The addition for changing manganese powder end is effective for the machining of such as relative low speeds such as drilling.But the addition of manganese sulfide powder is deposited
In following problem：In high-speed cutting processing in recent years may not also effectively, occur sintering body pollution, mechanical strength decline etc..
Patent document 1 (Japanese Laid Open Patent examined patent publication 52-16684) discloses a kind of adding for above-mentioned manganese sulfide
It is subject to outer, to assign machinability method.Patent document 1 discloses a kind of sintered steel, it carrys out self-contained iron powder, the desired amount of
The iron system raw material powder of carbon and copper, and containing 0.1~1.0% calcium sulfide (CaS), 0.1~2% carbon (C) and 0.5~
5.0% copper (Cu).
The scheme for making iron system raw material powder include calcium sulfide disclosed in patent document 1, the intensity that mechanical part be present significantly drop
Low, mixed-powder rheological parameters' change with time and the problems such as unstable quality (product quality).In addition, processed using cutting element
Disclosed in patent document 1 during sintered steel, chip is difficult to by fine Ground Split.Due to the reason, it is difficult to say disclosed in patent document 1
Sintered steel is excellent to the degree for meeting current chip treatability requirement.
The present invention makes in view of the above problems, its object is to：A kind of ferrous based powder metallurgical mixed powder is provided,
The sintered body with stable quality and performance can be made.
Prior art literature
Patent document
Patent document 1：Japanese Laid Open Patent examined patent publication 52-16684
The content of the invention
The ferrous based powder metallurgical mixed powder of the present invention, comprising：Iron-based powder；With, CaS material powders, the CaS raw materials
Powder contains selected from by type III dead plaster, II types dead plaster, calcium sulphate dihydrate, calcium sulfide and half-H 2 O calcium sulphate structure
Into one or more of group, wherein, the CaS material powders are covered by any one of lubricant and binding agent or both.
The sintered body of the present invention, it is made by sintering the ferrous based powder metallurgical with mixed powder.
The manufacture method of the ferrous based powder metallurgical mixed powder of the present invention, including：CaS material powders is with lubricator and viscous
The step of tying any one of agent or both covering, the CaS material powders contain selected from by type III dead plaster, II types
One or more of group that dead plaster, calcium sulphate dihydrate, calcium sulfide and half-H 2 O calcium sulphate are formed；And by described through covering
The step of CaS material powders and iron-based powder mixing of lid.
The manufacture method of the sintered body of the present invention, including：Sinter the ferrous based powder metallurgical made by the manufacture method
With mixed powder, the step of thus obtaining sintered body, wherein, the sintered body contain weight rate for more than 0.01 weight % and
Below 0.1 weight % CaS.
Embodiment
In order to achieve the above object, why can be over time present inventors studied sintered body disclosed in patent document 1
Process and quality and hydraulic performance decline.Also, the present inventor has found out：If sintered body include calcium sulfide and half-H 2 O calcium sulphate (with
It is lower to be denoted as both compositions " CaS compositions "), then the quality and hydraulic performance decline of the sintered body.That is, the inventors discovered that：CaS
The moisture in air is absorbed into branch and becomes calcium sulfate dihydrate (CaSO4·2H2O)；Also, CaS passes through hardening into branch
React and be gathered into more than 63 μm of coarse grain.Accordingly, specify that：CaS compositions in mixed powder or sintered body uneven dispersion and
The machinability of sintered body can be made reduce；Also, the moisture that CaS compositions are adsorbed expands in sintering forms water vapour, so as to
The intensity decreases of sintered body can be made.
The present inventor is based on above-mentioned opinion, is further deeply ground to being not easy to absorb the composition of CaS compositions of moisture
Study carefully, so as to complete the present invention as shown below.
According to the present invention it is possible to provide a kind of ferrous based powder metallurgical mixed powder, can make with stable quality and
The sintered body of performance.
Hereinafter, the ferrous based powder metallurgical of the present invention is specifically described with mixed powder and its manufacture method.
＜ ferrous based powder metallurgicals mixed powder ＞
The ferrous based powder metallurgical of the present invention is the mixing that mixes iron-based powder and CaS material powders with mixed powder
Powder, the CaS material powders contain selected from by type III dead plaster, II types dead plaster, calcium sulphate dihydrate, calcium sulfide
One or more of group formed with half-H 2 O calcium sulphate.The CaS material powders are characterised by：By in lubricant and binding agent
Either or both covering.Can be properly added in above-mentioned mixed powder as 3 yuan be oxide, 2 yuan be oxide, alloy powder
The various additives such as end, powdered graphite, lubricant, binding agent.In addition to these, in the system of ferrous based powder metallurgical mixed powder
During making, the mixed powder can also include micro inevitable impurity.The ferrous based powder metallurgical of the present invention is mixed
Powder is filled into mould etc. and is formed, and followed by sinters, it is hereby achieved that sintered body.To the sintered body thus made
Implement machining, it is possible to for various mechanical parts.The purposes and manufacture method of the sintered body will be described below.
＜ iron-based powders ＞
Iron-based powder is the main composition for forming ferrous based powder metallurgical mixed powder, is used relative to ferrous based powder metallurgical
Mixed powder it is overall preferably with more than 60 weight % weight rate come by comprising.It should be noted that the weight of the iron-based powder
Amount % refers in the ferrous based powder metallurgical in addition to lubricant with ratio shared in mixed powder gross weight.Hereinafter, providing
During the weight % of each composition, it is provided all referring in the institute in mixed powder gross weight of the ferrous based powder metallurgical in addition to lubricant
The weight rate accounted for.
As above-mentioned iron-based powder, can use：Such as atomized iron powder, reduced iron powder straight iron powder；Part diffusion-alloying
Comminuted steel shot；Complete alloyed steel powder；Or make alloying component in complete alloyed steel powder partly diffusion obtained by mixed type comminuted steel shot
Deng.Preferably more than 50 μm, more preferably more than 70 μm of the volume average particle size of iron-based powder.In the volume average particle size of iron-based powder
In the case of for more than 50 μm, treatability is excellent.In addition, preferably less than 200 μm of the volume average particle size of iron-based powder, more preferably
Less than 100 μm.In the case where the volume average particle size of iron-based powder is less than 200 μm, the shaping of precise shape is easily carried out
And obtain sufficient intensity.
＜ CaS material powders ＞
The ferrous based powder metallurgical mixed powder of the present invention is characterised by：Comprising CaS material powders, the CaS raw materials powder
End is contained to be selected to be made up of type III dead plaster, II types dead plaster, calcium sulphate dihydrate, calcium sulfide and half-H 2 O calcium sulphate
One or more of group, also, the CaS material powders are covered by any one of lubricant and binding agent or both.Pass through
Using the CaS material powders covered by lubricant and/or binding agent, the water imbibition of CaS material powders can be suppressed, therefore can be with
Improve with making the various stable performances of sintered body.
In the past, CaS raw material was turned into as being sintered, addition calcium sulfide (CaS), dihydrate gypsum (CaSO4·
2H2O), type III dead plaster (type III CaSO4), semi-hydrated gypsum (CaSO4·1/2H2O) etc..But above-mentioned each composition with
The process of time and absorb moisture, make the machinability of sintered body reduce sometimes.In addition, it is sintered and turns into CaS original
Moisture absorbed in material expands in sintering and forms water vapour sometimes, makes the density of sintered body reduce, or high temperature
Iron-based powder in sintered body is aoxidized and makes the intensity decreases of sintered body by water vapour.It is relative and this, in the present invention, due to such as
The upper CaS material powders added describedly by lubricant or binding agent covering, therefore even if to be contained in ferrous based powder metallurgical
Taken care of one period with the state of mixed powder, CaS material powders are not easy to absorb moisture.By the effect, default sintering
Each characteristic (sintered density, pressure ring intensity, machinability etc.) being stabilized of body.Also, the above-mentioned CaS raw materials through covering
Powder becomes CaS after sintering, can improve the machinability of sintered body.
CaS material powders preferably comprise any one of calcium sulfide and half-H 2 O calcium sulphate or both and are used as main component, also
Calcium sulphate dihydrate (CaSO can be contained4·2H2O), II types dead plaster (II types CaSO4), type III dead plaster (III
Type CaSO4) etc..
Here, " CaS material powders are covered by any one of lubricant and binding agent or both " includes：CaS raw material powder
The mode that the complete individual surface at end is covered by any one of lubricant and binding agent or both；With the mode being locally capped.On
As long as state thickness type III dead plaster, calcium sulphate dihydrate, calcium sulfide and the half-H 2 O calcium sulphate of lubricant and/or binding agent
The thickness for not contacting the air of outside is not particularly limited.It is preferred that above-mentioned thickness is uniform on the surface of CaS material powders,
But can also part or thin part of the locality in the presence of thickness.
The addition of above-mentioned lubricant can suitably be set, and be preferably with the weight of mixed powder relative to ferrous based powder metallurgical
More than 0.1 weight % and below 1.5 weight %.In addition, the addition of binding agent can suitably be set, relative to iron-based powder smelting
Gold with the weight of mixed powder is preferably more than 0.02 weight % and below 0.5 weight %.Lubricant and binding agent is being excessively added
In the case of, compressibility during extrusion molding reduces, so as to which density reduces.On the contrary, in the addition of lubricant and binding agent
In the case of few, above-mentioned CaS material powders easily atmosphere or extrusion molding with outside when be difficult to from mold releasability, because
This is possible to damage mould.
CaS material powders can be by being mixed together by the above-mentioned covering using lubricant with lubricant in the mixing container
Afterwards, heat and carry out.The CaS material powders through covering can either be prepared in advance or hot melt can be used in CaS raw material powder
The surface coverage lubricant at end.The step of hot melt, is, first, by lubricant with forming removing for ferrous based powder metallurgical mixed powder
Each powder beyond lubricant is filled into stainless steel together.Then, each powder is heated while being mixed, so
After be cooled to room temperature.Thus, ferrous based powder metallurgical is formed to be covered by lubricant respectively with each powder of mixed powder.
And then as another covering method, will form ferrous based powder metallurgical with removed in each powder of mixed powder lubricant with
Outer whole powder are filled into stainless steel.Thereafter, binding agent is dissolved in what solvent formed by addition in the stainless steel
Binder solution is simultaneously mixed.Then, the solvent for making to be contained in binder solution volatilizees.Finally, can be moistened by adding
Lubrication prescription and by CaS material powders with lubricator and/or binding agent covering.In this case, each powder by lubricant and/or glues respectively
Tie agent covering.The details of the process will be described below.
CaS material powders preferably reached more than 0.01 weight % with the weight rate of the CaS after sintering and 0.1 weight % with
Under mode be comprised in ferrous based powder metallurgical mixed powder.More preferably reach 0.02 with the weight rate of the CaS after sintering
More than weight % mode includes CaS material powders, further preferably reaches 0.03 weight with the weight rate of the CaS after sintering
Amount more than % mode includes CaS material powders.The machinability that CaS sintered body is included with such weight rate is especially excellent
It is different.On the other hand, CaS raw material powder is included preferably in a manner of the weight rate of the CaS after sintering reaches below 0.09 weight %
End, more preferably included in a manner of reaching below 0.08 weight %.By including CaS, Ke Yiti with such weight rate
The intensity of high sintered body.
Here, " weight rate of the CaS after sintering " refers to obtain being sintered ferrous based powder metallurgical with mixed powder
To sintered body in weight rate shared by CaS.The weight rate of the CaS contained by sintered body after the sintering can pass through sintering
The weight rates of preceding contained CaS material powders adjusts.
For the weight rate of the CaS contained by sintered body, it is processed by drilling etc. to sintered body to gather examination
Print, quantitative analysis is carried out to the weight of the Ca contained by the coupons, obtained Ca weight is converted into CaS weight, then
Calculate.The conversion passes through divided by Ca atomic weight (40.078) and is multiplied by CaS molecular weight (72.143) to carry out.Ca is burning
Hardly react and will not disappear during knot, therefore Ca weight is rear constant before sintering, Ca and S are with 1: 1 bonding.
Preferably more than 0.1 μm, more preferably more than 0.5 μm, further preferred 1 μm of the volume average particle size of CaS material powders
More than.In addition, preferably less than 60 μm, more preferably less than 30 μm, further preferred 20 μm of the volume average particle size of CaS material powders
Below.The CaS material powders of such volume average particle size, such as commercially available CaS material powders can be used to known crush
Machine crushes and is classified and obtains.In addition, the CaS material powders being made up of II type dead plasters, such as can be by semi-hydrated gypsum
More than 350 DEG C and less than 900 DEG C heating, keep more than 1 hour and less than 10 hours, then it is crushed and be classified and
Obtain.The volume average particle size of CaS material powders is smaller, then burning can also be improved by being reduced even if the addition of CaS material powders
The machinability of knot body.Above-mentioned volume average particle size be using laser diffraction formula particle size distribution device (day machine dress system
Microtrac " MODEL9320-X100 ") aggregate-value in obtained size distribution be 50% granularity D50Value.
＜ lubricants ＞
Covering CaS material powders lubricant be in order to suppress type III dead plaster, calcium sulphate dihydrate, calcium sulfide and
The hygroscopicity of half-H 2 O calcium sulphate and add.The lubricant also has following function：Make to compress ferrous based powder metallurgical in mould
Formed body easily takes out from mould obtained from mixed powder.That is, lubricated by being added in ferrous based powder metallurgical mixed powder
Agent, come can reduce from mould take out formed body when taking-up pressure (withdrawing pressure), so as to prevent
The damage of the crackle and mould of formed body.In addition, in the case of using hot melt, lubricant plays make alloy powder and graphite
Powder is attached to the function on the surface of iron-based powder, therefore is also prevented from the segregation at iron base powder mixture end.Need what is illustrated
It is that outside the lubricant of covering CaS material powders, can both be added during ferrous based powder metallurgical is made with mixed powder
Lubricant, can also be when ferrous based powder metallurgical be filled into mould with mixed powder, in the surface application of lubricating of mould.
Relative to the weight of ferrous based powder metallurgical mixed powder, lubricant is more excellent preferably by comprising more than 0.01 weight %
Choosing is further preferably included more than 0.2 weight % by comprising more than 0.1 weight %.By making the content of lubricant be 0.01
More than weight %, it is readily obtained and suppresses CaS material powders with outside atmosphere so as to the effect of the stable performance of sintered body.
In addition, relative to the weight of ferrous based powder metallurgical mixed powder, lubricant preferably by comprising below 1.5 weight %, more preferably by
Comprising below 1.2 weight %, further preferably below 1.0 weight % are included.By making the content of lubricant be 1.5 weight %
Hereinafter, densely sintered body is readily obtained, the high sintered body of intensity can be obtained.
Above-mentioned lubricant preferably uses wax base lubricant, and iron-based powder is attached to from alloy powder, powdered graphite etc. is made
From the viewpoint of the segregation at the functional and easy mitigation iron base powder mixture end on surface, more preferably using acid amides base lubricant.
As acid amides base lubricant, stearic acid monoamides, fatty acid amide, amide waxe etc. can be enumerated.As acid amides base lubricant with
Outer lubricant, it can use selected from the group being made up of hydrocarbon system wax, zinc stearate and crosslinking (methyl) acid alkyl ester resin
One or more of.
＜ binding agents ＞
Covering CaS material powders binding agent be in order to suppress type III dead plaster, calcium sulphate dihydrate, calcium sulfide and
The hygroscopicity of half-H 2 O calcium sulphate and prevent iron base powder mixture end segregation and add.Binding agent, which also has, makes alloy powder attached
The function on iron-based powder surface.It should be noted that outside the binding agent of covering CaS material powders, can also make
Make ferrous based powder metallurgical and add binding agent with during mixed powder.
For the step of covering CaS material powders with binding agent, it is organic molten that binding agent is dissolved in such as toluene first
Agent, so as to prepare the organic solvent containing binding agent.Then, the organic solution is mixed with CaS material powders.Finally, make to have
Solvent is volatilized, so that binding agent is covered on CaS material powders.
Binding agent more preferably using be selected from by styrene butadiene ribber, isoprene rubber, butylene based polymer and
One or more of group that metha crylic polymer is formed.As butylene based polymer, preferably use：By the independent structure of butylene
Into 1- chevrons；Or the copolymer of butylene and alkene.As the alkene, preferably light alkene, optimal ethylene or
Propylene.As metha crylic polymer, it can use and be selected from by methyl methacrylate, EMA, methyl
Butyl acrylate, cyclohexyl methacrylate, ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate and
One or more of group that ethyl acrylate is formed.
Relative to the weight of ferrous based powder metallurgical mixed powder, binding agent is more excellent preferably by comprising more than 0.01 weight %
Choosing is included more than 0.05 weight %.By including more than 0.01 weight % binding agent, type III anhydrous slufuric acid can be suppressed
Calcium, calcium sulphate dihydrate, the hygroscopicity of calcium sulfide and half-H 2 O calcium sulphate.In addition, the weight relative to ferrous based powder metallurgical mixed powder
Amount, binding agent is preferably by comprising below 0.5 weight %, more preferably by comprising below 0.4 weight %, further preferably by comprising
Below 0.3 weight %.By the way that the content of binding agent is set to below 0.5 weight %, high density is readily obtained in extrusion molding
Formed body.
3 yuan of ＜ is oxide ＞
In order to improve machinability during sintered body long-time machining, it is oxide that can add 3 yuan.Above-mentioned 3
Member is oxide, and its addition with CaS material powders synergistically, can significantly improve the machinability of sintered body.Here, 3 yuan are
Oxide refers to the composite oxides of 3 kinds of elements, is specifically preferably selected from by Ca, Mg, Al, Si, Co, Ni, Ti, Mn, Fe and Zn structure
Into group in 3 kinds of elements composite oxides, more preferably Ca-Al-Si systems oxide, Ca-Mg-Si systems oxide etc..As
Ca-Al-Si systems oxide, can enumerate 2CaOAl2O3·SiO2Deng.As Ca-Mg-Si systems oxide, can enumerate
2CaO·MgO·2SiO2Deng.Wherein, 2CaOAl is preferably added2O3·SiO2.Above-mentioned 2CaOAl2O3·SiO2With skiver
The TiO contained by coating applied in tool or on cutting element2Reaction, protection epithelium is formed on the surface of cutting element, therefore can
To significantly improve the resistance to abrasion of cutting element.
It is not particularly limited for the shape that 3 yuan are oxide, preferably：It is spherical；Or the circular shape being slightly distorted
Shape, i.e., substantially there is circular shape.
3 yuan be oxide volume average particle size preferably more than 0.1 μm of lower limit, more preferably more than 0.5 μm, further it is excellent
Select more than 1 μm.Volume average particle size is smaller, and more there is a small amount of addition can also improve the tendency of machinability of sintered body.This
Outside, 3 yuan be oxide volume average particle size preferably less than 15 μm of the upper limit, more preferably less than 10 μm, further preferred 9 μm with
Under.In the case where volume average particle size is excessive, it is difficult to improve the machinability of sintered body.3 yuan are that the volume of oxide is averaged
Particle diameter is the value determined by the assay method same with above-mentioned CaS material powders.
3 yuan are the content lower limit of oxide preferably more than 0.01 weight %, further excellent more preferably more than 0.03 weight %
Select more than 0.05 weight %.In addition, 3 yuan are the upper content limit of oxide preferably below 0.25 weight %, more preferably 0.2 weight %
Hereinafter, further preferred below 0.15 weight %.By being included with such weight rate, can not only be suppressed cost but also
The excellent sintered body of machinability in long-term machining.By being that oxide uses with CaS material combinations by 3 yuan, even if 3
Member is that the addition of oxide is few, can also improve the machinability in long-term machining.
It is oxide with for the weight ratio of the CaS after sintering, preferably being included with 1: 9~9: 1 ratio, more with regard to 3 yuan
It is preferred that 3: 7~9: 1, further preferred 4: 6~7: 3.By including two-component with such weight ratio, sintering can be significantly improved
The machinability of body.
2 yuan of ＜ is oxide ＞
In order to improve the machinability for cutting initial stage when machining is carried out to sintered body, it is oxidation that can add 2 yuan
Thing.Here, the composite oxides of 2 yuan of to be oxide refer to two kinds of elements, be specifically preferably selected from by Ca, Mg, Al, Si, Co, Ni,
The composite oxides of two kinds of elements in the group that Ti, Mn, Fe and Zn are formed, more preferably Ca-Al systems oxide, the oxidation of Ca-Si systems
Thing etc..As Ca-Al systems oxide, CaOAl can be enumerated2O3、12CaO·7Al2O3Deng., can as Ca-Si systems oxide
To enumerate 2CaOSiO2Deng.
2 yuan are that shape, volume average particle size, its assay method and the weight rate of oxide is preferably with above-mentioned 3 yuan
Each feature of oxide is identical.
2 yuan of ＜ is oxide and 3 yuan are oxide ＞
The ferrous based powder metallurgical of the present invention is preferably comprised with mixed powder to be calculated as more than 0.02 weight % and 0.3 with total weight
2 yuan of below weight % are oxide and 3 yuan are both oxides.Total weight of above-mentioned oxide preferably 0.05 weight % with
On, more preferably more than 0.1 weight %.From the viewpoint of cost, 2 yuan are oxide and 3 yuan are that the weight rate of oxide is got over
It is few more preferred.In addition, total weight of above-mentioned oxide is preferably below 0.25 weight %, more preferably below 0.2 weight %.Pass through
Total weight of oxide is below 0.25 weight %, it can be ensured that the pressure ring intensity of sintered body is enough.
It is oxide with for the weight ratio of the CaS after sintering, preferably being included with 1: 9~9: 1 ratio, more with regard to 2 yuan
It is preferred that 3: 6~9: 1, further preferred 4: 6~7: 3.By including two-component with such weight ratio, cutting initial stage can be made
The excellent sintered body of machinability.
＜ alloys powder ＞
In order to promote the mutual combination of iron-based powder and improve the intensity of the sintered body after sintering, alloy powder can be added
End.It is overall with mixed powder relative to ferrous based powder metallurgical, preferably comprise more than 0.1 weight % and below the 10 weight % alloy
Use powder.In the case of more than 0.1 weight %, the intensity of sintered body can be improved, in addition, the situation below 10 weight %
Under, it can be ensured that dimensional accuracy when sintered body sinters.
As above-mentioned alloy powder, can enumerate：Copper (Cu) powder, nickel (Ni) powder, Mo powder, Cr powder, V powder, Si powder, Mn powder
Deng nonferrous metal powder；Cuprous oxide powder etc..Can be used alone one of which, can also be applied in combination two of which with
On.
The manufacture method ＞ of ＜ ferrous based powder metallurgical mixed powders
The ferrous based powder metallurgical mixed powder of the present invention, such as can be made by the manufacture method of following (1)~(3)
Make.
(1) surface of CaS material powders is covered using lubricant.Then, by CaS material powders, the iron through covering
The powder of based powders and other compositions is mixed with mechanical agitation type mixer, so as to make ferrous based powder metallurgical mixed powder.
(2) surface of unfavorable with lubricator advance covering CaS material powders, but by whole compositions in closed container
Powder is heated while mixing.Then, the powder surface of whole compositions is with lubricator covered with hot melt, so as to make iron-based
Powder used in metallurgy mixed powder.
(3) will form ferrous based powder metallurgical be added to whole powder in each powder of mixed powder in addition to lubricant it is close
Close in container.Thereafter, organic solution of the addition dissolved with binding agent and mixing in the closed container, then makes above-mentioned organic molten
Agent is volatilized.Finally, lubricant is added in closed container, each powder for forming ferrous based powder metallurgical mixed powder is mixed.By
This is with lubricator and/or binding agent covers the surface of whole powder in addition to lubricant, so as to make ferrous based powder metallurgical
Use mixed powder.The volume average particle size of above-mentioned CaS material powders is preferably more than 0.1 μm and less than 60 μm.
For the heating-up temperature in hot melt, optimum temperature is different according to the fusing point of lubricant, such as preferably 50 DEG C
Above and less than 150 DEG C.In the case where heating-up temperature is set to more than 50 DEG C, the mobility of lubricant is easily improved.Heating
In the case that temperature is set to less than 150 DEG C, the oxidation of iron-based powder can be suppressed in the process that mixed powder makes, and can be with
Reduce the cost required for heating.
The heat time of hot melt is preferably more than 10 minutes and less than 5 hours.Heating-up temperature is more high, can more shorten
Heat time.In the case where the heat time is short, have be difficult to lubricator and/or binding agent covering CaS material powders it is whole
The possibility on surface.
The ferrous based powder metallurgical of the present invention can for example make as follows of mixed powder：, will using mechanical agitation type mixer
Iron-based powder and the mixing of the CaS material powders of above-mentioned making, thus make.In addition to these powder, it can also be properly added
Such as 3 yuan be oxide, alloy powder, powdered graphite, 2 yuan be oxide, binding agent, lubricant various additives.As
Above-mentioned mechanical agitation type blender, such as high-speed mixer, vertical spiral mixers, V-Mixer, biconial can be enumerated and mixed
Clutch etc..For the order by merging of above-mentioned each powder, it is not particularly limited.For mixing temperature, it is not particularly limited, but
It is, from the viewpoint of the oxidation for suppressing iron-based powder from mixed processes, preferably less than 150 DEG C.
The manufacture method ＞ of ＜ sintered bodies
After the ferrous based powder metallurgical of above-mentioned making is filled into mould with mixed powder, apply more than 300MPa and
Below 1200MPa pressure, so as to manufacture press-powder formed body.Preferably more than 25 DEG C and less than 150 DEG C of forming temperature now.
The press-powder formed body of above-mentioned making is sintered using common sintering method, it is hereby achieved that sintered body.Sintering
Condition can be non-oxidizing atmosphere or reducing atmosphere.Above-mentioned press-powder formed body is preferably in nitrogen atmosphere, nitrogen and hydrogen
Carried out more than 5 minutes and 60 minutes more than 1000 DEG C and at less than 1300 DEG C of temperature in the atmosphere such as mixed atmosphere or hydrocarbon
Following sintering.
＜ sintered bodies ＞
As above the sintered body made preferably comprises more than 0.01 weight % and below 0.1 weight % CaS.In sintered body
The CaS upper limit is preferably below 0.09 weight %, more preferably below 0.08 weight %.In addition, the lower limit of the CaS in sintered body is preferred
More than 0.02 weight %, more preferably more than 0.03 weight %.The sintered body can be as needed with the various instruments such as cutting element
Class is processed, so as to be used as the mechanical part of automobile, agricultural machinery and implement, electric tool, household appliances.As to upper
State the cutting element that sintered body is processed, for example, drill bit can be enumerated, slotting cutter, slice processing cutting element, turning add
Work cutting element, reamer, screw tap etc..
According to the ferrous based powder metallurgical mixed powder of above-mentioned embodiment, due to lubricator or binding agent covers vulcanization
The surface of calcium and half-H 2 O calcium sulphate, therefore the hygroscopicity of these compositions can be suppressed, the various stable performances of sintered body can be made
Improve on ground.
Above-mentioned ferrous based powder metallurgical mixed powder, it is selected from due to also including by Ca-Al-Si systems oxide and Ca-Mg-Si systems
3 yuan of one or more of group that oxide is formed is oxide, therefore can improve machinability when cutting for a long time.
Above-mentioned ferrous based powder metallurgical mixed powder, due to the weight rate of the CaS after sintering reach 0.01 weight % with
Upper and below 0.1 weight % mode includes CaS material powders, therefore the machinability of the sintered body after sintering is excellent.
Above-mentioned ferrous based powder metallurgical mixed powder, due to being that the weight ratio of oxide and the CaS after sintering reaches 3 with 3 yuan：
7~9：1 mode is oxide and CaS material powders comprising 3 yuan, therefore machinability when can improve long-term cutting.
Because the volume average particle size of above-mentioned CaS material powders is more than 0.1 μm and less than 60 μm, therefore burning can be improved
The machinability of knot body.
Each stability of characteristics such as the sintered body such as machinability made using above-mentioned ferrous based powder metallurgical of mixed powder and excellent.
In addition, the ferrous based powder metallurgical mixed powder made by above-mentioned manufacture method, because CaS material powders are not easy to absorb moisture,
Thus it is shown that stable performance.
Embodiment
It is exemplified below embodiment and the present invention is described in more detail, but the present invention is not limited by these examples.
(embodiment 1)
First, commercially available vulcanization calcium powder has been carried out point with sieve with -63/+45 μm (54 μm of volume average particle sizes)
Level.By the vulcanization calcium powder after classification, the component that 0.5 weight % is reached according to the weight of the CaS after sintering is added to closed appearance
In device.0.75 weight % acid amides base lubricant (ProductName is with the addition of in the closed container：ACRAWAX C (LONZA companies
System)).Then, 100 DEG C are heated to while mixing 10 minutes, so as to cover vulcanization calcium powder with acid amides base lubricant
Surface.
Then, relative to straight iron powder (ProductName：ATOMEL 300M (Co., Ltd.'s god's Kobe steel is made)) 2 weights of mixing
Measure % copper powders (ProductName：CuATW-250 (Fukuda Metal Foil ＆ POwder Co., Ltd.'s system)), 0.8 weight % graphite powder
(ProductName CPB (Japanese graphite Industrial Co., Ltd system)) and the vulcanization calcium powder with lubricator covered of above-mentioned making, thus
Ferrous based powder metallurgical mixed powder is made.It should be noted that so that the carbon amounts after sintering reaches 0.75 weight % component
And it with the addition of above-mentioned graphite powder.So that the weight of the CaS after sintering reaches 0.5 weight % component and with the addition of above-mentioned through covering
Vulcanization calcium powder.
(embodiment 2)
Will vulcanization calcium powder and acid amides base lubricant (ProductName in embodiment 1：ACRAWAX C (LONZA company systems)) plus
Enter into closed container and be heated to 100 DEG C, and be then to add the powder of the whole compositions used in embodiment 1 in embodiment 2
Enter into closed container, with hot melt be heated to 100 DEG C and mix 30 minutes, so as to acid amides base lubricant cover all into
The surface of the powder divided.Then room temperature is cooled to, has thus made ferrous based powder metallurgical mixed powder.
(embodiment 3)
In embodiment 3, the acid amides base lubricant used in embodiment 2 is substituted for containing styrene butadiene ribber
Toluene solution, each powder same as Example 2 in addition to this is mixed.So that the benzene second after toluene volatilization
The mode that the weight of alkene butadiene rubber reaches 0.1 weight % with the addition of foregoing toluene solution.Then, first is made at 100 DEG C
Benzene is volatilized, thus styrene butadiene ribber is covered in the surface of CaS raw particles.Then, addition in embodiment 1 with making
Acid amides base lubricant used in the embodiment 1 of component equivalent simultaneously mixes, so as to make the iron-based powder of embodiment 3
Metallurgy mixed powder.
(comparative example 1~3)
CaS material powders are not added in comparative example 1, have made ferrous alloy powder similarly to Example 1 in addition to this
Last metallurgy mixed powder.Comparative example 2 and 3 has used the CaS material powders shown in " CaS compositions " column of table 1 but unused profit
Lubrication prescription and binding agent are covered, and have made ferrous based powder metallurgical mixed powder similarly to Example 1 in addition.
Using the ferrous based powder metallurgical of the various embodiments described above and each comparative example two kinds of sintered bodies have been made with mixed powder.It is a kind of
It is to have used the ferrous based powder metallurgical after firm making another kind is with the sintered body (being denoted as below " instant sintered body ") of mixed powder
The ferrous based powder metallurgical from making after 10 days has been used (to be denoted as " sintering after 10 days below with the sintered body of mixed powder
Body ").
The manufacturing step of instant sintered body is as follows：First, the ferrous based powder metallurgical after firm make is filled into mixed powder
In mould, then it is formed, to obtain being in external diameter 64mm, internal diameter 24mm, thickness 20mm annular and shaping density
7.00g/cm3Test film；Then, by the annular test film in 10 volume %H2- N2In atmosphere 30 points are sintered at 1130 DEG C
Clock, sintered body is thus made.On the other hand, except 10 days later ferrous based powder metallurgicals will be placed after making in an atmosphere
It is filled into mixed powder in mould beyond this point difference, the sintered body after having been made in the same manner as instant sintered body 10 days.
Table 1
＜ evaluates ＞
In table 1, shaping volume density, sintered density, pressure ring are described in the form of " sintered body behind instant sintered body/10 day "
The evaluation result of intensity and instrument abrasion amount.Oblique line is clipped in the record, the value on the left of it is the evaluation result of instant sintered body,
Value on the right side of it is the evaluation result of sintered body after 10 days.
Each embodiment and the instant sintered body of each comparative example and after 10 days sintered body shaping volume density and sintered density
Employ the value based on Powder Metallurgy In Japan meeting standard (JPMA M 01) measure.In addition, pressure ring intensity is employed and is based on
Value obtained from JISZ 2507-2000 is measured.Pressure ring intensity is more high, and sintered body is less susceptible to be destroyed, and represents intensity
It is higher.
For the sintered body made in each embodiment and each comparative example, cermet piece (ISO models are used：
SNGN120408 is without chip-breaker (non-breaker)) with peripheral speed 160m/min, cutting-in 0.5mm/pass, feeding 0.1mm/
Rev, dry conditions turning 1150m, the instrument abrasion amount (μm) of now cutting element is determined by tool microscope.Tied
Fruit is shown in " instrument abrasion amount " column of table 1.It should be noted that the value of instrument abrasion amount is smaller, then it represents that the quilt of sintered body
Machinability is more excellent.
Each embodiment and the result of each comparative example as shown in Table 1 is understood：By as each embodiment with lubricator or
Binding agent cover CaS material powders, instant sintered body and after 10 days sintered body various characteristics (sintered density, pressure ring intensity
With instrument abrasion amount) it is almost equal.On the other hand, comparative example 2 with 3 comprising CaS in itself or semi-hydrated gypsum as CaS into
Point, but its surface is not carried out any covering treatment, therefore after 10 days sintered body various characteristics it is notable with instant sintered body compared with
It is deteriorated.
It is believed that in comparative example 2 and 3, it is after 10 days the reason for the quality and degradation of sintered body：By iron
During base powder metallurgy is placed 10 days with mixed powder, ferrous based powder metallurgical is absorbed with the CaS in mixed powder or semi-hydrated gypsum
Moisture.I.e., it is believed that, during comparative example 2 and 3 preserves under the air of 10 days, the CaS sheets in ferrous based powder metallurgical mixed powder
Body or semi-hydrated gypsum absorb moisture, and so as to generate, the density of sintered body declines or pressure ring intensity declines.It should be noted that
Because comparative example 1 is free of CaS compositions, thus immediately sintered body and after 10 days sintered body instrument abrasion amount it is all significantly high, sintering
The machinability of body is significantly low.
Result as shown in Table 1 specify that：By by CaS material powders with lubricator or binding agent cover, immediately sintering
Body and after 10 days sintered body various characteristics (sintered density, pressure ring intensity and instrument abrasion amount) it is almost equal, sintering
The quality and stable performance of body, show the effect of the present invention.
Claims (8)
1. a kind of ferrous based powder metallurgical mixed powder, it is characterised in that include：
Iron-based powder；With
CaS material powders, the CaS material powders contain selected from by type III dead plaster, II types dead plaster, two water
One or more of group that calcium sulfate, calcium sulfide and half-H 2 O calcium sulphate are formed, wherein,
The CaS material powders are covered by any one of lubricant and binding agent or both.
2. ferrous based powder metallurgical mixed powder according to claim 1, it is characterised in that also include and be selected from by Ca-Al-Si
It is that 3 yuan of one or more of group that oxide and Ca-Mg-Si systems oxide are formed is oxide.
3. ferrous based powder metallurgical mixed powder according to claim 1 or 2, it is characterised in that with described 3 yuan be oxide
Reach 3 with the weight ratio of the CaS after sintering：7~9：1 mode is oxide and the CaS material powders comprising described 3 yuan.
4. ferrous based powder metallurgical mixed powder according to claim 1, it is characterised in that with the weight of the CaS after sintering
Ratio reaches more than 0.01 weight % and below 0.1 weight % mode includes the CaS material powders.
5. ferrous based powder metallurgical mixed powder according to claim 1, it is characterised in that the body of the CaS material powders
Product average grain diameter is more than 0.1 μm and less than 60 μm.
6. a kind of sintered body, it is characterised in that made by sintering the ferrous based powder metallurgical described in claim 1 with mixed powder
.
A kind of 7. manufacture method of ferrous based powder metallurgical mixed powder, it is characterised in that including：
By CaS material powders with lubricator with any one of binding agent or both covering the step of, the CaS material powders contain
Have selected from the group being made up of type III dead plaster, II types dead plaster, calcium sulphate dihydrate, calcium sulfide and half-H 2 O calcium sulphate
One or more of；And
The step of CaS material powders through covering and iron-based powder are mixed.
A kind of 8. manufacture method of sintered body, it is characterised in that including：
The ferrous based powder metallurgical mixed powder that sintering is made by the manufacture method described in claim 7, thus obtains sintered body
The step of, wherein,
The sintered body contains weight rate for more than 0.01 weight % and below 0.1 weight % CaS.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-107347 | 2015-05-27 | ||
| JP2015107347A JP6480265B2 (en) | 2015-05-27 | 2015-05-27 | Mixed powder for iron-based powder metallurgy, method for producing the same, sintered body and method for producing the same |
| PCT/JP2016/063169 WO2016190038A1 (en) | 2015-05-27 | 2016-04-27 | Mixed powder for iron-based powder metallurgy, method for producing same, sintered body produced using same, and method for producing sintered body |
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| Publication Number | Publication Date |
|---|---|
| CN107614158A true CN107614158A (en) | 2018-01-19 |
| CN107614158B CN107614158B (en) | 2020-06-09 |
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Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20180141117A1 (en) |
| EP (1) | EP3321000B1 (en) |
| JP (1) | JP6480265B2 (en) |
| KR (1) | KR102102584B1 (en) |
| CN (1) | CN107614158B (en) |
| WO (1) | WO2016190038A1 (en) |
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| JP6480264B2 (en) * | 2015-05-27 | 2019-03-06 | 株式会社神戸製鋼所 | Mixed powder and sintered body for iron-based powder metallurgy |
| JP6480266B2 (en) * | 2015-05-27 | 2019-03-06 | 株式会社神戸製鋼所 | Mixed powder for iron-based powder metallurgy, method for producing the same, and sintered body |
| JP6929259B2 (en) * | 2018-01-25 | 2021-09-01 | 株式会社神戸製鋼所 | Mixed powder for powder metallurgy |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3321000A4 (en) | 2018-08-22 |
| KR102102584B1 (en) | 2020-04-21 |
| EP3321000B1 (en) | 2023-02-15 |
| KR20180008732A (en) | 2018-01-24 |
| US20180141117A1 (en) | 2018-05-24 |
| JP6480265B2 (en) | 2019-03-06 |
| CN107614158B (en) | 2020-06-09 |
| EP3321000A1 (en) | 2018-05-16 |
| WO2016190038A1 (en) | 2016-12-01 |
| JP2016222943A (en) | 2016-12-28 |
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