CN1488006A - Copper-containing ferrous sintered materials - Google Patents
Copper-containing ferrous sintered materials Download PDFInfo
- Publication number
- CN1488006A CN1488006A CNA028039203A CN02803920A CN1488006A CN 1488006 A CN1488006 A CN 1488006A CN A028039203 A CNA028039203 A CN A028039203A CN 02803920 A CN02803920 A CN 02803920A CN 1488006 A CN1488006 A CN 1488006A
- Authority
- CN
- China
- Prior art keywords
- copper
- powder
- iron
- steel powder
- sintering
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for producing a ferrous sintered material with a copper content of 12 to 26 wt.%. The method comprises the following steps: a powder mixture of a desired composition is produced, at least a proportion of the total iron and copper content being provided by an iron powder inseparably associated with copper, such as a prealloyed or diffusion bonded powder, the powder mixture is compacted to form a green compact of the article to be produced, and the green compact is then sintered.
Description
The goods that the present invention relates to sintered ferrous material, make by this material with and manufacture method, the particularly manufacture method of cupric ferrous material.
Powder metallurgy makes the possibility that creates of the metallic substance that can't make with the casting of routine and spindle complete processing.Permeate irony sinter powder metal goods with low melting point metal as plumbous and copper, this method is known.Lead is used for improving the cutting ability of sintered ferrous material, and copper also has this effect, but it also gives the performance of the some other needs of agglomerated material.Avoid now using lead, because it is unfavorable to environment as far as possible.Copper can improve the cutting ability and the heat-conductive characteristic of sintered article.
The copper penetration goods are widely used in automotive industry, as making the valve seat edge circle of IC engine cylinder head.These goods must for example repetitive shock load, edge be lubricated in harsh condition, work under high temperature and the thermal etching gas condition.The irony matrix system is carried out appropriate selection can make parts obtain to stand the performance of above-mentioned condition.This irony matrix usually is a high-alloying, thereby its cutting ability of negative impact.Extremely important the man of engine shop of cutting ability in production of articles, because it can influence productive rate.Can improve cutting ability with copper penetration, and copper itself makes heat-conductive characteristic increase, this can reduce service temperature, and helps to keep mechanical property.
Process of osmosis is following carrying out: the copper alloy powder briquetting is placed on the irony parts be in contact with it, then it is passed through sintering oven in the about 1100 ℃ of scopes of sintering temperature under inertia or reducing atmosphere, sintering and infiltration are taken place simultaneously.Copper alloy powder briquetting fusing in this sintering process, the fused alloy enters in the hole of irony parts by capillary action infiltration and filling.The hole that only is interconnected can be filled in this way, and is isolated and then can not be filled by melt because of the disconnected hole of other reasons.The composition of copper alloy powder briquetting makes that through selecting it can be compatible with ferrous material, and bad reaction and so and erosion of generation do not take place as far as possible.The weight of copper alloy powder briquetting will be selected, makes to fill most of hole, yet, still some residual porosity can be arranged inevitably as mentioned above.
A variant of said process is that the copper alloy powder briquetting is placed above the irony parts of presintering, then it is permeated by sintering oven.
Because comprise more extra production stages, the expense of osmosis process process is bigger.These extra steps are: prepare the copper alloy powder mixture individually; The powder mixture of correct weight is become suitable briquetting; Briquetting is placed on the irony parts, pass through sintering oven then; And after cooling, the goods through sintering and infiltration are rolled in bucket, remove the powder deposits that in sintering process, on goods, forms inevitably.
In the copper penetration ferrous products of routine, copper content is generally in 15-25 weight % scope.In non-entered preparation, in the presuppression powdered mixture, add the copper of maximum 5 weight % usually.This more a spot of relatively copper joins in the non-infiltration ferrous material and helps sintering, because the cause that liquid phase copper exists.
People once attempted in process of osmosis, by add the content that an amount of elemental copper improves copper in initial powdered mixture before compacting and sintering.Yet, since the difference of various factors as: the difference of powder particle granularity, powder density and powder particle form, segregation takes place in copper easily in the treating processes of powdered mixture.This powder segregation meeting causes end article unwelcome variation to occur.At the content of elemental copper powder seldom, under the situation of 5 weight % for example above-mentioned, still segregation can take place, but its influence to end article is very little, can not cause great problem.
The parts of under harsh and unforgiving environments, working, engine valve seat edge circle for example, once be fully by high quality steel for example M3/2 rank steel get.This steel contains chromium, tungsten, molybdenum, vanadium of high level etc.Though the component capabilities that this material makes is superior, long service life, their manufacturing of Yu is very expensive.First reason of their costlinesses is the material cost height, and second reason is the high parts of hard carbide content in the microstructure, its difficult cutting.In the continuous pursuit that reduces cost, done a lot of work and reduced material cost, one of its way is to add the high-purity iron powder of higher proportion in powdered mixture, thereby reduces the hard phase, thereby make final agglomerated material be easy to cutting, thereby reduce the technology cost.Also way is to add to help the phase of cutting, as copper or make smear metal that the phase of rifting be arranged.
These type materials are in the shortcoming aspect performance and work-ing life, for example show as among the GB-A-2 188 062, be that the ferrous powder granules that compresses at first in powdered mixture has soft ferritic phase to keep in the nuclear of sintering and the iron crystal grain that produces together, and this can reduce the wear resistance and the intensity of material.This material comprises the M3/2 material of about 50% high-alloying, the mixture of the carbon that adds of about 50% straight iron powder, trace and mould lubricating wax etc. for example at first.Even behind tight burning, iron crystal grain still remains with ferrite core, and small additions of chromium is arranged, and is diffused into the surf zone of iron crystal grain from the M3/2 zone, may form martensite there behind the sintering.Even permeated when material, perhaps added reach 5 weight % elemental copper in powdered mixture, this structure still exists.
An object of the present invention is to provide a kind of method of making the ferrous material goods, in high copper content in this material and the penetration material quite, and this method not have the shortcoming of the required additional step of those methods previously.
Other advantages will be hereinafter invention more obvious in describing.
According to a first aspect of the invention, it is that basic copper content is the method for the sintered article of 12-26 weight % with iron that a kind of manufacturing is provided, the step of this method is: the powdered mixture for preparing required composition, the wherein all iron and the copper of content have at least a certain proportion of part to be provided by the iron powder that contains inseparable continuous copper; The described powdered mixture of compacting forms the green compact casting die of goods, this green compact casting die of sintering then.
The content of copper mainly is in order to improve the thermal conductivity of resulting product, yet the inventive method is returned goods some other important benefit is provided.Copper content is lower than 12 weight %, and desired heat-conductive characteristic can not get improving, and copper content is higher than 26 weight %, and fused copper can ooze out from material when sintering.The optimum range of copper content is 15-20 weight %.
In process of the present invention, be actually a kind of pre-alloying powder with the inseparable iron powder of copper, wherein one powder particle not only iron content but also cupric, tangible segregation situation just can not take place between iron and the copper like this.The powder particle of iron content and copper can be selected from following two kinds of basic powder stocks: the iron/copper pre-alloying powder; Perhaps, the iron/copper powder of diffusion-bonded.The iron/copper pre-alloying powder can prepare melt water or this known technology of gas atomization then by constitutive material is melted together.The iron/copper powder of diffusion-bonded then is by making earlier the mixture of element iron powder and copper powder, and this mixture just by stove, makes phase mutual diffusion between particle and the technology preparation that combines without compacting then." the material cake " that forms like this becomes through slight crushing operation and comprises the iron that closely links to each other and the particle of copper.This process causes having a little copper to diffuse to each iron particulate external region.
The inventive method has been removed the required several steps of previous those technologies from, in this method, need not to prepare individually copper alloy powder mixture and briquetting afterwards thereof, need not this briquetting is placed on the ferrous material briquetting, final sintered component also need not to resemble to be handled to remove the settling of attachment removal the previous osmosis process.
Special advantage of the inventive method relates to the processing of the iron-bearing materials of the powdered mixture that contains alloying comminuted steel shot and low-alloy iron powder or straight iron powder.People have known this mixture that carbon dust is arranged that adds of use, make goods such as similar engine valve seat edge circle by compacting, sintering and sintering postheat treatment.The material of this previous technology may or may not permeate with copper alloy by one of above-mentioned common process method.This material illustration in GB-A-2 188 062 and EP-A-0 312 161 described materials and manufacture method is come out.These materials may contain certain proportion, for example, and about 50 weight % high-alloying comminuted steel shots and the pure substantially iron powder of 50 weight %.This alloying comminuted steel shot contains chromium usually, chromium is under common about 1100 ℃ of sintering conditions, be one of element atom that reactivity is the strongest aspect rate of diffusion outside the de-carbon, it still is that those promote to form one of martensitic alloying element in the goods sintering postcooling process.The carbon atom reactivity is the strongest, and it can enter in the iron atom gap in the crystalline structure.Yet because the size of chromium atom and iron atom and quality are close, it can substitute iron atom, therefore presents under common sintering condition and reactivity like the iron phase.The existence of chromium has promoted that those have spread the interior martensitic formation in zone of chromium in the agglomerated material, and martensite forms when sintering finishes material cooled.The sintering of this goods normally carries out in stove, and the device that moves through stove is continuously arranged in the stove, and for example the travelling belt or the formula mechanism of coming into transmit goods, and goods generally are placed on the pallet.In general, the first part of kiln rises to sintering temperature with temperature of articles; Second section makes the goods insulation in sintering temperature; Third part makes goods be cooled to prevent that from sintering temperature goods from the temperature of obvious oxidation taking place in the sintering oven outlet.Goods usually continuously by whole stove protective atmosphere in sintering, this atmosphere is neutrality or reductibility, can also excluding air (oxygen) enter.Furnace pressure is malleation, and is bigger slightly than normal atmosphere, can prevent air admission like this.Contain the position of the iron powder in a great deal of initial mixture at agglomerated material, often can find, in the nucleus of the non-tool steel of rich iron, the iron crystal grain that has some to produce by compacted iron powder particles sintering, they have from the ferrite to the perlite and the microstructure of this two-phase mixture, decide according to the content of carbon.Usually contain the martensite that in sintering process, spreads generation by chromium in the external region of iron crystal grain, and nucleus still remains ferrite or pearl layer iron or both mixtures, decides on added carbon content.At the state that has just sintered into, in the centre of crystal grain, non-tool steel phase of Fu Tie or crystalline-granular texture mainly contain pearl layer iron, some ferrites may also be arranged, and the crystal grain external region are the mixtures of martensite/bainite.If also have some residual austenites in sintered article, then it normally changes during the subzero treatment behind sintering and to form.In the drawing process after subzero treatment, part takes place and decomposes in pearl layer iron phase, causes forming ferrite in rich iron crystal grain and rich iron phase.Because ferritic existence, make material wear-resistant performance variation, intensity also decreases.Thermal treatment behind the sintering, comprise and make any residual γ phase (austenite) be transformed into martensitic subzero treatment, the temper of following later is for hardness that reduces martensitic phase and fragility, rather than in order to cause the decomposition of pearl layer iron, this is the side reaction that produces in the drawing process.Because temper is carried out being higher than under the goods expections working temperature, so (for example, the edge of the valve seat in combustion chambers of internal combustion engines circle) can guarantee the dimensional stability of goods in its Working environment.Yet, this thermal treatment can not influence the existing of ferritic phase (except producing a certain proportion of ferrite) with and relatively poor wear resisting property and the cutting ability of inherent.
It is found that, utilize the inventive method, copper (no matter being with the diffusion-bonded form or with prealloy form and iron bonded) and chromium can occur is promoting separately to having synergy aspect the diffusion of iron crystal grain central authorities, and the core of finding iron crystal grain can be transformed into martensite in normal furnace cooling process, rather than still remains ferrite or pearl layer iron or the two mixture.According to the inventive method, the sintered ferrous material made from the iron/copper powder of pre-alloyed iron/copper or diffusion-bonded, be presented in the rich iron crystal grain core and have martensite, this is because chromium or other Elements Diffusion that can promote martensite to form enter the cause in the iron crystal grain.Martensite forms in austenitic process of cooling, and in any residual subzero treatment of austenite behind sintering transformation has taken place all.The process of cooling that begins from sintering temperature, some austenite can be transformed into bainite.Martensite is tempered may to form a kind of tempered martensite structure, and this structure is easy to processing.Yet, importantly, according to the inventive method, the soft ferritic/pearl layer iron core of previous iron crystal grain, the material that comprises now is harder, and intensity is bigger, also more resistance to wears.Can think, be used for forming process pre-alloyed and the material iron/copper diffusion-bonded, make that some copper diffuses in the iron composition mutually at least, and this of copper has in the iron crystal grain that helps form when chromium and other Elements Diffusion that can promote martensite to form enter sintering, so just promoted martensitic formation.
Prepare material according to the inventive method, and adopt processing parameter substantially the same such as pressure and sintering temperature to wait with previous osmose process to prepare substantially the same material with the former, these two kinds of tests show, use the powder of aforesaid iron/copper prealloy or diffusion-bonded can produce useful effect.Made except copper content, formed identical materials substantially, adopted three kinds of methods: by 1) the inventive method; 2) while sintering and permeating method; 3) the elemental copper powder of adding 13 weight %, sintering (, also not adding the iron/copper pre-alloying powder) then in initial powdered mixture promptly without infiltration.
Under the same process condition, the material for preparing with conventional osmose process forms martensitic beneficial effect in iron crystal grain core.Scanning electron microscope analysis shows have chromium to exist in the material grains core with the inventive method manufacturing.It is emphasized that the processing condition that adopt in simultaneous test are identical with the condition of previous proprietary concentrate manufacturing, promptly is the present optimised process level that all factors are taken into account therefore.
Also to carry out thermal treatment behind the sintering according to the material of the inventive method manufacturing,, make any residual austenite be transformed into martensite mutually as-120 ℃ or the lower subzero treatment of carrying out, and then tempering, make martensite softer, size is more stable, thus easy machining.
Like this, characteristics according to an embodiment of the invention, powdered mixture comprises: relatively not the iron powder of alloying, contain some chromium at least or other promote the comminuted steel shot of the alloying element that martensite forms, also have powder pre-alloyed or the iron/copper diffusion-bonded.In addition, powdered mixture may contain the element that can promote martensite formation of extra adding, for example molybdenum and/or nickel.Described the example that adopts M3/2 rapid steel powder herein, yet the powder of other any proper tools steel or rapid steel such as chrome-bearing steel can adopt also, see with the purposes of the goods of this material manufacturing and decide.
An example of available steel is 316 steel, and it is a kind of stainless steel, and its composition weight % content is: 17Cr/2Mo/13Ni/ surplus Fe is substantially free of carbon.
Like this, it seems the mode of copper being introduced sintered ferrous material, promptly make copper and iron phase connect (previous processing causes mutual reaction at this position), helping chromium or other Elements Diffusion that promotes martensite to form that unexpected synergy is arranged aspect matrix, to martensitic transformation, or realize the transformation of retained austenite by subzero treatment when helping the cooling behind sintering.
The composition of the material of the pre-alloyed or diffusion-bonded of iron/copper can be any needed, for example, and Fe-20Cu.Each used raw material of powdered mixture can be: iron; Iron/copper; Prealloy comminuted steel shot and carbon dust.The quantity of iron/copper pre-alloying powder will be decided on the final required copper content and the original composition of iron/copper pre-alloying powder in the goods.
In powdered mixture, add some element copper powders in the material of and/or diffusion-bonded pre-alloyed and also be fine, and, may be useful in some cases at iron/copper.And pre-alloyed and the powder iron/copper diffusion-bonded, these two kinds of powder also can be used in the powdered mixture.
The pre-alloyed material of iron/copper aspect the martensitic formation, seems more effective than the material of iron/copper diffusion-bonded in promoting iron crystal grain.Therefore, use pre-alloyed material better, yet, can point out that the material of diffusion-bonded can produce martensite after oversintering and subsequent technical steps, still, previous penetration material can not produce martensite in iron crystal grain core, and this core only contains pearl layer iron and ferritic mixture.
According to a second aspect of the invention, provide the sintered article that utilizes first aspect of the present invention to make.
For the present invention is more fully understood, for some embodiment it is described below in conjunction with accompanying drawing.
The histogram of Fig. 1 is presented at the wearing and tearing of valve seat edge circle in the testing of engine, and this edge circle is made with material of the present invention;
That Fig. 2 shows is the part count figure of tool wear and machining, and parts adopt the material of material of the present invention and previous technology respectively.
Valve seat edge loop material-embodiment 1
The manufacturing of valve seat edge circle in the combustion engine, the iron mixture that the typical case of employing forms prepares with different methods.The definite content of each powder composition of powdered mixture is listed in the table below in 1:
Table 1
| Composition weight % | ???M3/2 | Graphite | ????MoS 2 | Element Cu | The Fe-Cu powder | Lubricating wax | The Fe powder |
| Embodiment 1 | ???45 | ????0.55 | ????1 | ????6 | ???47.47 | ???0.75 | ????- |
| Embodiment 1a | ???42.9 | ????0.42 | ????0.87 | ????13 | ???- | ???0.75 | ????42.9 |
| Embodiment 1b | ???49.75 | ????0.5 | ????- | Infiltration | ???- | ???0.75 | ????49.75 |
Embodiment 1 is a material prepared according to the methods of the invention, and wherein all iron and a certain proportion of copper add as the Fe-20Cu pre-alloying powder.Copper in the pre-alloying powder accounts for 9.5 weight % of final material greatly.The elemental copper powder of other 6 weight % adds in the initial powdered mixture, and the total content of copper just is increased to 15 weight % like this.The steel pre-alloying powder is that a kind of water spray method is made the M3/2 powder, and its nominal composition is: 1C; 4Cr; 5Mo; 3V; 5W.Because only added the elemental copper powder of 6 weight %, so that segregation phenomena reduces to is minimum.
Embodiment 1a is a powdered mixture, and wherein the iron powder of all content all is a straight iron powder, and copper is then provided by the element copper powder of 13 weight %.Though this material can not normally prepare with high-load element copper powder like this, reason is as above-mentioned, and this material is to be used for determining that copper content enters the influence of iron diffusion of components characteristic for chromium.
Embodiment 1b is the material according to the preparation of technological process previous among the GB-A-2 188 062, and wherein copper is that step by while sintering and infiltration provides.
All powder are the principle blended according to the Y-cone-type mixer.For each situation, pressing pressure all in the 650-800MPa scope, sintering in about 1100 ℃ conveyor furnace then, all samples are sintering under identical condition.Behind the sintering, all samples carry out subzero treatment under-120 ℃, and austenite residual in the structure (γ-phase) is changed, and make martensite softening in 2 hours 600 ℃ of following tempering then, make sample size more stable, and strengthen its cutting ability.
The actual composition that constitutes element representation with each, density of sintered material that subzero treatment behind sintering and temper are later and final hardness have been listed in the following table 2.
Table 2
| Composition weight % | ??C | ??Cr | ???Cu | ??Mo | ??S | ??V | ??W | ??Fe | Density Mgm -3 | Hardness HRA |
| Embodiment 1 | ??1 | ??1.8 | ???15.5 | ??2.9 | ??0.4 | ??1.4 | ??2.3 | Surplus | ????7.2 | ??64-67 |
| Embodiment 1a | ??0.9 | ??1.7 | ???13 | ??2.7 | ??0.3 | ??1.3 | ??2.1 | Surplus | ????7.0 | ??59-64 |
| Embodiment 1b | ??0.9 | ??2.0 | ???15 | ??2.5 | ??1.5 | ??2.5 | Surplus | ????7.95 | ??67-71 |
The microstructure of the sample of embodiment 1 preparation has shown the structure of tempered martensite in the iron crystal grain core.Martensite forms the process of cooling that begins from sintering temperature.Subzero treatment is used for the retained austenite of M3/2 in the material in mutually is transformed into martensite.Can not see easily at microscopically to martensitic transformation that from austenite this variation can embody from the increase of the hardness that caused to martensitic transformation by austenite.
The sample of embodiment 1a has shown contained the martensite that forms and residual austenitic microtexture from the process of cooling that sintering temperature begins.After subzero treatment, in the M3/2 zone, residual austenitic transformation becomes martensite, and iron crystal grain mainly contains pearl layer iron (contain ferrite with cementite stratiform structure mutually) and some ferrites.Pearl layer iron is to form from the carbon dust that the graphite form adds, yet, owing to do not have chromium in the iron crystal grain nuclear, can not form martensite.When tempering, the decomposition of a large amount of pearl layer iron has taken place, so the state of ferritic volume fraction after than firm sintering increases to some extent.Therefore, the wear resistance of material and mechanical property among the embodiment 1a, hardness data as shown in Table, also relatively poor.
Structure and the performance of the sample of embodiment 1b and embodiment 1a are very nearly the same.This material is according to the preparation of the currently known methods of GB-A-2188 062.The hardness of embodiment 1b is big slightly than the hardness of embodiment 1a, and this is because the former density of material behind copper penetration is bigger.Yet the material of embodiment 1b shows, after the tempering on intensity intrinsic relatively poor ferrite zone quantity a lot, rather than as among the inventive method embodiment 1 required tempered martensite structure.
Fig. 1 has shown by embodiment 1 material made, at 1.8l, 4-cylinder, the histogram of the edge circle wear resistance of the valve seat edge circle of the exhaust position of 16-air valve engine, this engine is to move 180 hours with white gasoline with 6000 rev/mins speed, and its adopts the valve of Si Tailite alloy inserted faces.The standard of this test is that the wearing and tearing of valve seat edge circle must not surpass 100 μ m.As seen from Figure 1, maximum wearing and tearing are 60m in valve seat position 4, and every other edge circle wearing and tearing are all about 30m.
Like this, from embodiment 1,1a and 1b can find out obviously that main difference is copper is introduced the mode of agglomerated material in the manufacturing.Have reason to believe that directly owing to the use of the pre-alloyed material of iron/copper, having a certain proportion of copper and iron in this material at least is to link to each other inseparably for improved structure and performance, also owing to the caused diffusion enhancing of pre-alloyed material thus.
Embodiment 2
It is M3/2 instrument comminuted steel shot/0.55C/1MoS of 45 that preparation comprises weight percentage
2The powdered mixture of/6Cu/47.45FeCu20 (powder of diffusion-bonded)/0.75 lubricating wax.This mixture is at 770MPa compacting green compact casting die, and green density is 7.1Mgm
-3, then under about 1100 ℃ in the conveyor furnace that is connected with nitrogen/hydrogen continuously sintering.Sintered article carries out subzero treatment-120 ℃ or lower temperature, residual austenitic transformation is become martensite, at last 600 ℃ of tempering.The density of agglomerated material is 7.0Mgm
-3The hardness of sintering state material is 61HRA; Material hardness after the subzero treatment is 65HRA; Material hardness after subzero treatment and the tempering is 62-65HRA.
Microstructure after embodiment 2 materials (with the powder of the iron/copper diffusion-bonded) tempering (what carry out after sintering and the subzero treatment), being presented at the non-tool steel of Fu Tie has some little occurrent ferrite zones in mutually.Yet this richness iron phase only contains pearl layer iron basically, and does not contain the ferrite of the bulk zone that can occur in those materials of useful previous osmose process preparation.
Embodiment 3
Prepare a kind of powdered mixture, its composition (weight %) is: the pre-alloyed powder of 75%Fe-20Cu/23%316 Stainless Steel Powders/0.75%MoS
2Powder/1% carbon dust, this material number are N1.316 stainless steels are 17Cr/2Mo/13Ni/ surplus Fe.The Comparative Examples mixture that another kind is numbered N is formed (weight %) and is: the 70.9% iron powder/27%316 Stainless Steel Powders/0.9%MoS that undopes
2Powder/1.2% carbon dust.These two kinds of materials are all suppressed under 770MPa.Yet according to the previous technology that people understand, the N1 material only carries out sintering (because about 15% copper is provided by the Fe-Cu prealloy), and the N material carries out sintering and infiltration simultaneously.The final theory of N1 material and N material is formed (weight %) and all is: 1C/3.9Cr/15Cu0.9Mo/3Ni/0.3S/ surplus Fe.Sintering/infiltration in nitrogen/hydrogen atmosphere 1100 ℃ carry out.These two kinds of materials have all carried out subzero treatment and tempering behind sintering.
Do not find ferrite in the N1 material microstructure, even in the crystal grain core that is iron basically, be like this yet.This material structure is the tempered martensite structure basically.Even and if the carbon content of N material is high slightly, be 1.2%, but its ubiquity ferrite in iron crystal grain core, the transitional region between original iron crystal grain and 316 stainless steel particles is a pearl layer iron construction.Like this, in the final structure after technological process, another has shown the effect of the copper that links to each other inseparably with iron.
Embodiment 4
According to the inventive method, made the material that is called FMCA and FMCD again.The various one-tenth that table 3 has been listed powdered mixture are grouped into:
Table 3
| ????FMCA | ????FMCD | |
| Fe-20 Cu (pre-alloyed) | ????75 | ????75 |
| ?C | ????1.35 | ????1.35 |
| ?Mo | ????0.5 | |
| ?MoS 2 | ????1 | |
| The Fe of alloying not | ????23.15 | ????22.65 |
| Lubricating wax | ????0.75 | ????0.75 |
Material is suppressed under 770MPa, and is the same with some examples of implementation of front, 1100 ℃ of sintering in successive shielding gas atmosphere.The final density and hardness of agglomerated material is listed in table 4.Concerning these materials, do not carry out the thermal treatment behind the sintering.
Table 4
| ????FMCA | ????FMCD | |
| Give birth to density, Mgm -3 | ????7.05 | ????7.05 |
| Sintered density, Mgm -3 | ????7.35-7.40 | ????7.15-7.20 |
| Hardness, HRB | ????99-101 | ????95-98 |
According to the FMCA material that the inventive method is made, adopted the elements Mo powder of Fe-Cu pre-alloying powder and 0.5% in its initial powdered mixture.The FMCA material shows more rich Mo district and these zones also are connected with martensitic regions and bainite district.The FMCA material also shows the intergranular carbide.A bit (with alloying iron powder not, material 1.35%C/0.5%Mo), its copper content is provided by while sintering and process of osmosis by previous technology the microstructure of FMCA material similar in appearance to being called as FMC.Except process of osmosis, the sintering condition of FMC is the same with the condition of FMCA and FMCD material.Have the intergranular carbide in the FMC material, matrix is a pearl layer iron, also has the rich Mo district relevant with the Mo particle, but compares with the FMCA material, and this zone is very little.
In sintering process, the MoS in the FMCD material
2Part is decomposed, and free Mo is discharged in the structure, and this structure can produce the localization martensite/bainite structure relevant with rich Mo district.MoS
2In some S of decompositing and iron and copper reaction, form metallic sulfide, these sulfide can improve the cutting ability of material.In the FMCD material, do not see the carbide network, matrix is a pearl layer iron.
Fig. 2 shows is the number graphic representation that tool wear and FMC, FMCA and FMCD material are cut the parts of processing.As seen from the figure, adopt the material of the Fe-Cu pre-alloying powder that has enlarged martensite/bainite range, although its intensity is bigger, more resistance to wear, its machining property is unaffected.In fact, the cutting ability of FMCA material and FMCD material all surpasses the FMC material with previous prepared.
Claims (21)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0101770.6 | 2001-01-24 | ||
| GB0101770A GB0101770D0 (en) | 2001-01-24 | 2001-01-24 | Sintered ferrous material |
| GB0120401A GB0120401D0 (en) | 2001-08-22 | 2001-08-22 | Sintered Ferrous Material |
| GB0120401.5 | 2001-08-22 | ||
| PCT/GB2002/000176 WO2002059388A1 (en) | 2001-01-24 | 2002-01-17 | Sintered ferrous material containing copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488006A true CN1488006A (en) | 2004-04-07 |
| CN1314824C CN1314824C (en) | 2007-05-09 |
Family
ID=26245610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028039203A Expired - Fee Related CN1314824C (en) | 2001-01-24 | 2002-01-17 | Sintered ferrous material containing copper |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US20040112173A1 (en) |
| EP (1) | EP1370704B1 (en) |
| JP (1) | JP2004520486A (en) |
| KR (1) | KR20030070116A (en) |
| CN (1) | CN1314824C (en) |
| AT (1) | ATE294255T1 (en) |
| BR (1) | BR0206677A (en) |
| DE (1) | DE60203893T2 (en) |
| ES (1) | ES2237669T3 (en) |
| GB (1) | GB2386908B (en) |
| PL (1) | PL200915B1 (en) |
| RU (1) | RU2280706C2 (en) |
| WO (1) | WO2002059388A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102528020A (en) * | 2010-12-16 | 2012-07-04 | 杰富意钢铁株式会社 | Alloy steel powder for powder metallurgy, iron-based sintering material and manufacturing method thereof |
| CN103758746A (en) * | 2014-01-17 | 2014-04-30 | 钢铁研究总院 | Steel-steel double-metal rotor and manufacturing method thereof |
| CN104067358A (en) * | 2012-01-18 | 2014-09-24 | 日立金属株式会社 | Dust core, coil component, and method for producing dust core |
| CN106222566A (en) * | 2016-08-23 | 2016-12-14 | 秦皇岛市雅豪新材料科技有限公司 | A kind of superhard material products rare earth special regulation water atomization Fe Cu pre-alloyed powder and preparation method thereof |
| CN106636856A (en) * | 2016-12-15 | 2017-05-10 | 江门市佳久新材料科技有限公司 | High density stainless steel alloy material for powder metallurgy |
| CN106694885A (en) * | 2016-12-15 | 2017-05-24 | 江门市佳久新材料科技有限公司 | Powder metallurgy stainless steel alloy balance weight for scroll compressor |
| CN107052350A (en) * | 2017-06-16 | 2017-08-18 | 大连理工大学 | A kind of method for connecting tungsten material and copper material |
| CN110914009A (en) * | 2017-10-30 | 2020-03-24 | 帝伯爱尔株式会社 | Valve guide tube made of iron-based sintered alloy and method for producing same |
| CN111527221A (en) * | 2017-11-30 | 2020-08-11 | Gkn烧结金属有限公司 | Powder metal alloy composition for sintered powder metal inserts for aluminum castings |
| CN112756608A (en) * | 2020-12-14 | 2021-05-07 | 北京有研粉末新材料研究院有限公司 | Preparation method for in-situ generation of liquid absorbent core material of copper-clad iron heat pipe |
| CN114425617A (en) * | 2020-10-29 | 2022-05-03 | 马勒国际有限公司 | Wear-resistant high-thermal-conductivity sintered alloy especially suitable for bearing and valve seat ring |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE0203135D0 (en) * | 2002-10-23 | 2002-10-23 | Hoeganaes Ab | Dimensional control |
| GB2429464B (en) * | 2005-08-23 | 2009-04-15 | Federal Mogul Sintered Prod | Manufacture of a ferrous article |
| EP2051826B1 (en) * | 2006-07-21 | 2011-09-21 | Höganäs Aktiebolag | Iron-based powder |
| RU2353694C1 (en) * | 2007-10-02 | 2009-04-27 | Юлия Алексеевна Щепочкина | Sintered alloy on basis of iron |
| JP5384079B2 (en) * | 2008-10-29 | 2014-01-08 | Ｎｔｎ株式会社 | Sintered bearing |
| CN103038025B (en) * | 2010-03-01 | 2014-10-15 | 俄罗斯联邦政府预算机构《联邦军事、特殊及双用途智力活动成果权利保护机构》 | Copper-Based Bonds for Diamond Tool Manufacturing |
| BR112012026851B1 (en) * | 2010-05-19 | 2018-03-06 | Hoeganaes Corporation | Powder metallurgical composition and sintered powder metallurgical piece |
| AT509868B1 (en) * | 2010-06-10 | 2011-12-15 | Miba Sinter Austria Gmbh | CONSTRUCTION ELEMENT WITH REDUCED METAL HINGING |
| DE102012013226A1 (en) | 2012-07-04 | 2014-01-09 | Bleistahl-Produktions Gmbh & Co Kg | High heat conducting valve seat ring |
| JP5859395B2 (en) * | 2012-07-27 | 2016-02-10 | 日立オートモティブシステムズ株式会社 | Piston for internal combustion engine and method for manufacturing the piston |
| CN103131930A (en) * | 2013-03-07 | 2013-06-05 | 江苏大学 | Method for preparing powdery high-speed steel piece |
| JP6213809B2 (en) * | 2013-03-12 | 2017-10-18 | 日立金属株式会社 | Powder magnetic core, coil component using the same, and method for manufacturing powder magnetic core |
| JP6194613B2 (en) * | 2013-03-29 | 2017-09-13 | 日立化成株式会社 | Iron-based sintered alloy for sliding member and manufacturing method thereof |
| EP3024000B1 (en) * | 2013-07-17 | 2018-12-19 | Hitachi Metals, Ltd. | Dust core, coil component using same and process for producing dust core |
| JP6146548B1 (en) * | 2015-09-11 | 2017-06-14 | Ｊｆｅスチール株式会社 | Method for producing mixed powder for powder metallurgy, method for producing sintered body, and sintered body |
| CA2992092C (en) | 2015-09-18 | 2020-04-07 | Jfe Steel Corporation | Mixed powder for powder metallurgy, sintered body, and method of manufacturing sintered body |
| ITUA20165254A1 (en) * | 2016-06-28 | 2017-12-28 | Antonino Rinella | CRIOTEMPRATI METALLIC MATERIALS, EQUIPPED WITH A HIGH ABILITY TO ABSORB ENERGY OF ELASTIC DEFORMATION, INTENDED FOR THE CONSTRUCTION OF PROTECTIVE REINFORCEMENT FOR PERFORATING RESISTANT TIRES AND LACERATIONS. |
| US10780491B2 (en) | 2018-01-11 | 2020-09-22 | Ford Global Technologies, Llc | Aluminum casting design with alloy set cores for improved intermetallic bond strength |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH275201A (en) * | 1948-07-08 | 1951-05-15 | Plansee Metallwerk | Alloy sintered steel. |
| US3583864A (en) * | 1969-05-05 | 1971-06-08 | Pfizer & Co C | Chemical process of producing an iron-copper alloy powder |
| GB1339132A (en) * | 1970-05-28 | 1973-11-28 | Brico Eng | Ferrous alloys |
| US3752712A (en) * | 1971-06-07 | 1973-08-14 | Domtar Ltd | Iron copper prealloys |
| BE793539A (en) * | 1971-12-30 | 1973-06-29 | Int Nickel Ltd | IMPROVEMENTS RELATED TO POWDER COMPRESSION |
| US3860457A (en) * | 1972-07-12 | 1975-01-14 | Kymin Oy Kymmene Ab | A ductile iron and method of making it |
| US4064914A (en) * | 1974-05-08 | 1977-12-27 | Union Carbide Corporation | Porous metallic layer and formation |
| SU955726A1 (en) * | 1980-12-30 | 1990-08-30 | Предприятие П/Я Р-6543 | Charge for making iron-base sintered articles |
| US4678510A (en) * | 1985-12-24 | 1987-07-07 | General Motors Corporation | Wear resistant iron powder article |
| CA1337468C (en) * | 1987-08-01 | 1995-10-31 | Kuniaki Ogura | Alloyed steel powder for powder metallurgy |
| GB8723818D0 (en) * | 1987-10-10 | 1987-11-11 | Brico Eng | Sintered materials |
| SU1637141A1 (en) * | 1989-08-18 | 1995-11-10 | Белорусское республиканское научно-производственное объединение порошковой металлургии | Method for manufacture of products from iron-base alloy |
| GB8921260D0 (en) * | 1989-09-20 | 1989-11-08 | Brico Engineering Company | Sintered materials |
| RU2023737C1 (en) * | 1992-04-28 | 1994-11-30 | Тамара Федоровна Волынова | Iron-based antifriction alloy having martensite structure and antifriction product |
| RU2043868C1 (en) * | 1993-07-06 | 1995-09-20 | Тамара Ароновна Пумпянская | Method to produce sintered pieces from diffusion alloyed iron powders |
| US5529604A (en) * | 1995-03-28 | 1996-06-25 | Ametek, Specialty Metal Products Division | Modified stainless steel powder composition |
-
2002
- 2002-01-17 JP JP2002559869A patent/JP2004520486A/en active Pending
- 2002-01-17 EP EP02715503A patent/EP1370704B1/en not_active Expired - Lifetime
- 2002-01-17 AT AT02715503T patent/ATE294255T1/en not_active IP Right Cessation
- 2002-01-17 DE DE60203893T patent/DE60203893T2/en not_active Expired - Fee Related
- 2002-01-17 RU RU2003125845/02A patent/RU2280706C2/en not_active IP Right Cessation
- 2002-01-17 PL PL362787A patent/PL200915B1/en not_active IP Right Cessation
- 2002-01-17 KR KR10-2003-7009507A patent/KR20030070116A/en not_active Ceased
- 2002-01-17 BR BR0206677-7A patent/BR0206677A/en not_active Application Discontinuation
- 2002-01-17 ES ES02715503T patent/ES2237669T3/en not_active Expired - Lifetime
- 2002-01-17 US US10/470,144 patent/US20040112173A1/en not_active Abandoned
- 2002-01-17 GB GB0315414A patent/GB2386908B/en not_active Expired - Fee Related
- 2002-01-17 CN CNB028039203A patent/CN1314824C/en not_active Expired - Fee Related
- 2002-01-17 WO PCT/GB2002/000176 patent/WO2002059388A1/en not_active Ceased
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102528020B (en) * | 2010-12-16 | 2015-10-07 | 杰富意钢铁株式会社 | Alloy steel powder for powder metallurgy and iron based material and manufacture method thereof |
| CN102528020A (en) * | 2010-12-16 | 2012-07-04 | 杰富意钢铁株式会社 | Alloy steel powder for powder metallurgy, iron-based sintering material and manufacturing method thereof |
| CN104067358A (en) * | 2012-01-18 | 2014-09-24 | 日立金属株式会社 | Dust core, coil component, and method for producing dust core |
| CN103758746A (en) * | 2014-01-17 | 2014-04-30 | 钢铁研究总院 | Steel-steel double-metal rotor and manufacturing method thereof |
| CN103758746B (en) * | 2014-01-17 | 2015-10-28 | 钢铁研究总院 | A kind of steel-bimetal copper-steel rotor and manufacture method thereof |
| CN106222566A (en) * | 2016-08-23 | 2016-12-14 | 秦皇岛市雅豪新材料科技有限公司 | A kind of superhard material products rare earth special regulation water atomization Fe Cu pre-alloyed powder and preparation method thereof |
| CN106222566B (en) * | 2016-08-23 | 2018-10-09 | 秦皇岛市雅豪新材料科技有限公司 | A kind of superhard material products rare earth special adjusts water atomization Fe-Cu pre-alloyed powders and preparation method thereof |
| CN106694885B (en) * | 2016-12-15 | 2018-12-28 | 江门市佳久新材料科技有限公司 | A kind of screw compressor powder metallurgical stainless steel alloy balance weight |
| CN106636856A (en) * | 2016-12-15 | 2017-05-10 | 江门市佳久新材料科技有限公司 | High density stainless steel alloy material for powder metallurgy |
| CN106694885A (en) * | 2016-12-15 | 2017-05-24 | 江门市佳久新材料科技有限公司 | Powder metallurgy stainless steel alloy balance weight for scroll compressor |
| CN107052350A (en) * | 2017-06-16 | 2017-08-18 | 大连理工大学 | A kind of method for connecting tungsten material and copper material |
| CN110914009A (en) * | 2017-10-30 | 2020-03-24 | 帝伯爱尔株式会社 | Valve guide tube made of iron-based sintered alloy and method for producing same |
| US11951547B2 (en) | 2017-10-30 | 2024-04-09 | Tpr Co., Ltd. | Valve guide made of iron-based sintered alloy and method of producing same |
| CN111527221A (en) * | 2017-11-30 | 2020-08-11 | Gkn烧结金属有限公司 | Powder metal alloy composition for sintered powder metal inserts for aluminum castings |
| CN114425617A (en) * | 2020-10-29 | 2022-05-03 | 马勒国际有限公司 | Wear-resistant high-thermal-conductivity sintered alloy especially suitable for bearing and valve seat ring |
| CN112756608A (en) * | 2020-12-14 | 2021-05-07 | 北京有研粉末新材料研究院有限公司 | Preparation method for in-situ generation of liquid absorbent core material of copper-clad iron heat pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1314824C (en) | 2007-05-09 |
| WO2002059388A1 (en) | 2002-08-01 |
| DE60203893T2 (en) | 2006-01-19 |
| GB2386908B (en) | 2004-09-29 |
| EP1370704B1 (en) | 2005-04-27 |
| GB0315414D0 (en) | 2003-08-06 |
| BR0206677A (en) | 2004-01-13 |
| GB2386908A (en) | 2003-10-01 |
| DE60203893D1 (en) | 2005-06-02 |
| PL200915B1 (en) | 2009-02-27 |
| KR20030070116A (en) | 2003-08-27 |
| ES2237669T3 (en) | 2005-08-01 |
| EP1370704A1 (en) | 2003-12-17 |
| JP2004520486A (en) | 2004-07-08 |
| RU2280706C2 (en) | 2006-07-27 |
| ATE294255T1 (en) | 2005-05-15 |
| PL362787A1 (en) | 2004-11-02 |
| US20040112173A1 (en) | 2004-06-17 |
| RU2003125845A (en) | 2005-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1488006A (en) | Copper-containing ferrous sintered materials | |
| Narasimhan | Sintering of powder mixtures and the growth of ferrous powder metallurgy | |
| CA1337748C (en) | Sintered materials | |
| EP0339436B1 (en) | A hard alloy particle dispersion type wear resisting sintered ferro alloy and method of forming the same | |
| US5188659A (en) | Sintered materials and method thereof | |
| TWI482865B (en) | High strength low alloyed sintered steel | |
| CA2725652C (en) | Iron-based pre-alloyed powder | |
| US5308702A (en) | Iron-based powder composition for use in powder metallurgy, process for its production and process for producing iron-base sintered material | |
| GB2104551A (en) | A method for manufacturing a cam-cam shaft assembly | |
| US6783568B1 (en) | Sintered steel material | |
| EP0711845A1 (en) | Wear-resistant sintered ferrous alloy for valve seat | |
| CN100449024C (en) | Alloy steel powder for powder metallurgy | |
| JP4839275B2 (en) | Mixed powder for powder metallurgy and sintered iron powder | |
| WO2002072904A1 (en) | Sintered ferrous materials | |
| JPH0959740A (en) | Powder mixture for powder metallurgy and its sintered compact | |
| Fodor et al. | Effect of carbon on microstructure of mixed powder system cooled at moderate rates after sintering | |
| Hanejko | Advances in P/M gear materials | |
| EP1066128B1 (en) | Metal powders obtained from residue of material removal processes on iron parts produced by chill casting | |
| JP2006037138A (en) | Valve seat made of iron based sintered alloy | |
| WO2024154811A1 (en) | Valve seat formed of iron-based sintered alloy for internal combustion engines and method for producing same | |
| James et al. | Sintered Steels I-Composition: Lean Hybrid Low-Alloy PM Molybdenum Steels | |
| Davala et al. | Productivity enhancement through improved machinability materials | |
| Unami et al. | Sintered Steels: Low Alloy Steels: Properties of Sintered Compacts Made of Ni-Free Pre-Mixed Powder Based on Low Mo Prealloyed Steel Powder | |
| JPS6152301A (en) | Iron-based alloy powder for wear-resistant sintered parts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070509 Termination date: 20100220 |