CN110102771A - A kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder - Google Patents

A kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder Download PDF

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CN110102771A
CN110102771A CN201910226936.9A CN201910226936A CN110102771A CN 110102771 A CN110102771 A CN 110102771A CN 201910226936 A CN201910226936 A CN 201910226936A CN 110102771 A CN110102771 A CN 110102771A
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powder
copper
atomization
copper powder
green compact
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CN110102771B (en
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胡柏明
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Anhui Xinjia Copper Industry Co Ltd
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Anhui Xinjia Copper Industry Co Ltd
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    • 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
    • B22F1/14—Treatment of metallic powder
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
    • 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
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
    • 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
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/088—Fluid nozzles, e.g. angle, distance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder, a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder is the following steps are included: (1) raw material is chosen: it is spare to choose the secondary resources such as high-purity copper, zinc and the copper-tin alloy leftover pieces of certain mass number；(2) low pine is than the formation of prealloy powder: high-purity copper powder of low apparent density and Albaloy powder is prepared by using water atomization, by the parameter for adjusting atomization process.Pass through the innovation to production technology, formula technique, equipment development etc. in the present invention, Gu admittedly diffusion type tin zinc-copper powder technology of preparing, its product stability is high, compared with conventional diffusion technique (copper powder, glass putty, zinc powder mixing diffusion), uniformity is good, basic segregation-free, production cost is low (glass putty, zinc powder are at high price), meanwhile the present invention substantially increases product production capacity and production efficiency, considerably reduces equipment investment and energy consumption.

Description

A kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder
Technical field
The present invention relates to technical field of metal material, specially a kind of high green compact high stability environmental protection diffusion type tin zinc-copper powder Preparation method.
Background technique
Thermal diffusion type tin zinc-copper powder (CuSn6Zn6) is the Pb-free copper-alloy powder that developed recently gets up, and has excellent molding Property, the features such as high green, the variation of stable sintered dimensions, wide market, domestic and international copper powder manufacturing enterprise is by it Object is developed as emphasis, such as Japanese Fukuda Metal Foil & POwder Co., Ltd., U.S. ACuPowder International Have levigation end new material Co., Ltd etc. with China, but existing product apparent density is higher, homogeneity of ingredients and stablize it is bad, sternly Recasting about properties of product, for this purpose, it is proposed that a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder, with It solves the problems, such as to propose in background technique.
To achieve the above object, the invention provides the following technical scheme: a kind of high green compact high stability environmental protection diffusion type tin The preparation method of zinc-copper powder, a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder includes following step It is rapid:
(1) raw material is chosen: it is spare to choose the secondary resources such as high-purity copper, zinc and the copper-tin alloy leftover pieces of certain mass number；
(2) low pine is than the formation of prealloy powder: high-purity copper powder of low apparent density and Albaloy powder are prepared by using water atomization, Parameter by adjusting atomization process improves the hollowness of particle so that granule-morphology is irregular, and the regular shape of generation is porous Shape, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
(3) high green is realized: by the way that suitable extraordinary lubricant is added in " solid-solid " two-phase thermal diffusion process, to improve The green compact performance of product, by being tin zinc to the phase transition mechanism and the expansion research of interfacial reaction process in thermal diffusion process The optimization of copper powder Integration ofTechnology and demonstration, using the alloyed powder of special lubricant processing, its green compact typed pressure can achieve 12MPa More than；
(4) degree of segregation improving performance is reduced: by the microsegregation performance and gravity segregation performance during change powder compacting Two key factors reduce segregation performance, and Main is to change crystal grain atom using dynamics+Thermodynamic Mechanism principle Spacing is spread to reduce microsegregation degree；Using reverse order freezing method, changes mother liquor and match the solidification sequence reduction material of liquid The gravity segregation of material.
Preferably, low pine is expanded than prealloy powder using solid in the high green compact high stability environmental protection diffusion type tin zinc-copper powder The tin zinc-copper powder of the technology of dissipating production combines shape in the selection of material, using CuSnZn alloyed powder+CuSn alloyed powder+Cu powder Formula is basic material, and the parameter by adjusting atomization process improves the hollowness of particle so that granule-morphology is irregular, generates Regular shape it is cavernous, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
It is described it is low pine than prealloy powder production in Countermeasures the following steps are included:
(1) degree of superheat of metal bath: the degree of superheat is bigger, and molten metal surface tension is small, the easier formation of first time drop, generates Particle it is thin, but the time of cooling requirement is long, and the degree of irregularity of metal reduces, Song Bigao；
(2) chilled water: chilled water is low, the distance that particle flies in the sky, and degree of irregularity reduces, when lower overheat When degree, atomizing medium flow are big, influence less, as long as it is as high as possible not influence atomization process chilled water；
(3) structure of nozzle is to relevant size: under other identical conditions, the structure type of nozzle is different, pyrosol The situation of atomizing medium and metal bath is entirely different when change, directly affects atomizing effect, for free fall type nozzle, generally There are the structure types such as board-like " V " shape, taper, annular distance, circumferential weld, using " V " shape plate nozzle, cannot be formed in atomization closed Nebulization region is in wavy band before metal bath atomization, and granularity is big after atomization, and ingredient rate is low.Circumferential weld nozzle processing difficulties, combination mill Lamps structure requires height during installation, and concentricity is too low, causes atomizing medium to be unevenly distributed, out-focus, not can be carried out effective atomization, Thus ring pore structures are relatively reasonable, and to reach technique purpose, ring pore structures will meet claimed below: the aperture A is small, pore size distribution is equal Even, hole sufficiently focuses, and can form closed nebulization region；B nozzle annular distance resistance is small, and under identical atomizing pressure, nozzle goes out Mouth atomizing medium speed improves, and subdivision rate is high, and atomization is abundant；C atomization item angle is reasonable, and atomization apex angle is big, and stream distance is small, does not advise Then degree reduces, and granularity variation is unobvious, high-efficient, and it is excessive to be atomized apex angle, easy plug nozzle；
(4) atomizing pressure: i.e. water jet speed.When atomizing pressure is less than 7MPa, pressure is bigger, and granularity is smaller, works as pressure When being 7MPa, influence of the pressure to granularity is little.But when the degree of superheat is smaller, atomizing pressure has granularity and degree of irregularity It influences, atomizing pressure is big, fine size, irregular raising.Water jet speed is improved, atomizing pressure, another party are on the one hand improved Nozzle resistance is reduced in face, by reducing the draw ratio of nozzle, improves inner nozzle surface finish and realizes；
(5) water flow: although the energy for being actually used in the powder particle of production dispersion is one of consumed energy in atomization process Fraction, biggish water flow can preferably reduce the humidity of crushed powder, slow down nodularization, loose ratio be reduced, to particle size influences Less.
Preferably, in the high green compact high stability environmental protection diffusion type tin zinc-copper powder high green alloyed powder realization side Method the following steps are included:
(1) using secondary resources such as high-purity copper, zinc and copper-tin alloy leftover pieces as raw material, fusing obtains metal in electric induction furnace Solution is carried out degasification deslagging to metallic solution, is then allowed to stand slag hitting, keeps impurity content in melt small by furnace bottom gon technics In 0.2%, then metallic solution passes through special nozzle, prepares copper powder and Albaloy powder using water atomization；
(2) there are small amounts on water atomization copper or copper alloy powder, surface, so using oxidation --- and reducing process is to water atomization Copper powder and Albaloy powder are modified, and are further improved its performance.Use oxidationreduction technique: wherein oxidizing temperature for It 300-500 DEG C, oxidization time 2-4h, according in oxidation process, wherein in oxidation process, after oxidation, is gone back in hydrogen Original, reduction temperature are 400-600 DEG C, chemical reaction equation:
Oxidation reaction: 2M (metal)+O2=2MO
Reduction reaction: MO+H2=M+H2O
Wherein oxidation-reduction process meets thermodynamics theorem, according to thermodynamic temperature map, can consult, wherein the preferential oxygen of copper Change, in copper alloy, wherein the volume of oxygen occupies certain position in the grain, leads to growing up for particle after due to oxidation.So After passing through reduction afterwards, a kind of porous structure is formed, by the way that suitable extraordinary lubrication is added in " solid-solid " two-phase thermal diffusion process Agent, to improve the green compact performance of product.For affecting laws of the technological parameter to powder characteristic during this, thermal diffusion process In phase transition mechanism and interfacial reaction process expansion study, for tin zinc-copper powder Integration ofTechnology optimize and demonstrate.Using spy Its green compact typed pressure of the alloyed powder of different lubricant processing can achieve 12MPa or more.
Preferably, the realization of degree of segregation improving performance is reduced in the high green compact high stability environmental protection diffusion type tin zinc-copper powder Method is that gravity segregation degree reduces method: change traditional solidification atomization process, using top-down solidification atomization technique, By parameters such as the temperature of adjusting atomizer, angles, Inversion is carried out to the built-up sequence of nascent crystalline substance, is first solidified low-melting Tin, zinc, it is rear to solidify the high copper of fusing point, the crystal grain fusion of different metal material is generated in fusion, passes through thermodynamics+dynamics Mechanism principle, realize secondary fusion reduction gravity segregation.
By the innovation to production technology, formula technique, equipment development etc. in the present invention, admittedly diffusion type tin zinc-copper admittedly Powder technology of preparing, product stability is high, compared with conventional diffusion technique (copper powder, glass putty, zinc powder mixing diffusion), uniformity Good, basic segregation-free, production cost is low (glass putty, zinc powder are at high price), meanwhile, the present invention substantially increases product production capacity and life Efficiency is produced, equipment investment and energy consumption are considerably reduced.
Specific embodiment
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only It is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Embodiment one:
A kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder, a kind of high green compact high stability environmental protection The preparation method of diffusion type tin zinc-copper powder the following steps are included:
(1) raw material is chosen: it is spare to choose the secondary resources such as high-purity copper, zinc and the copper-tin alloy leftover pieces of certain mass number；
(2) low pine is than the formation of prealloy powder: high-purity copper powder of low apparent density and Albaloy powder are prepared by using water atomization, Parameter by adjusting atomization process improves the hollowness of particle so that granule-morphology is irregular, and the regular shape of generation is porous Shape, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
(3) high green is realized: by the way that suitable extraordinary lubricant is added in " solid-solid " two-phase thermal diffusion process, to improve The green compact performance of product, by being tin zinc to the phase transition mechanism and the expansion research of interfacial reaction process in thermal diffusion process The optimization of copper powder Integration ofTechnology and demonstration, using the alloyed powder of special lubricant processing, its green compact typed pressure can achieve 12MPa More than；
(4) degree of segregation improving performance is reduced: by the microsegregation performance and gravity segregation performance during change powder compacting Two key factors reduce segregation performance, and Main is to change crystal grain atom using dynamics+Thermodynamic Mechanism principle Spacing is spread to reduce microsegregation degree；Using reverse order freezing method, changes mother liquor and match the solidification sequence reduction material of liquid The gravity segregation of material.
Embodiment two:
Low pine is produced than prealloy powder using diffusion technique is consolidated in the high green compact high stability environmental protection diffusion type tin zinc-copper powder Tin zinc-copper powder in the selection of material, the use of CuSnZn alloyed powder+CuSn alloyed powder+Cu powder combining form is basic material Material, the parameter by adjusting atomization process improve the hollowness of particle, the regular shape of generation so that granule-morphology is irregular Cavernous, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
It is described it is low pine than prealloy powder production in Countermeasures the following steps are included:
(1) degree of superheat of metal bath: the degree of superheat is bigger, and molten metal surface tension is small, the easier formation of first time drop, generates Particle it is thin, but the time of cooling requirement is long, and the degree of irregularity of metal reduces, Song Bigao；
(2) chilled water: chilled water is low, the distance that particle flies in the sky, and degree of irregularity reduces, when lower overheat When degree, atomizing medium flow are big, influence less, as long as it is as high as possible not influence atomization process chilled water；
(3) structure of nozzle is to relevant size: under other identical conditions, the structure type of nozzle is different, pyrosol The situation of atomizing medium and metal bath is entirely different when change, directly affects atomizing effect, for free fall type nozzle, generally There are the structure types such as board-like " V " shape, taper, annular distance, circumferential weld, using " V " shape plate nozzle, cannot be formed in atomization closed Nebulization region is in wavy band before metal bath atomization, and granularity is big after atomization, and ingredient rate is low.Circumferential weld nozzle processing difficulties, combination mill Lamps structure requires height during installation, and concentricity is too low, causes atomizing medium to be unevenly distributed, out-focus, not can be carried out effective atomization, Thus ring pore structures are relatively reasonable, and to reach technique purpose, ring pore structures will meet claimed below: the aperture A is small, pore size distribution is equal Even, hole sufficiently focuses, and can form closed nebulization region；B nozzle annular distance resistance is small, and under identical atomizing pressure, nozzle goes out Mouth atomizing medium speed improves, and subdivision rate is high, and atomization is abundant；C atomization item angle is reasonable, and atomization apex angle is big, and stream distance is small, does not advise Then degree reduces, and granularity variation is unobvious, high-efficient, and it is excessive to be atomized apex angle, easy plug nozzle；
(4) atomizing pressure: i.e. water jet speed.When atomizing pressure is less than 7MPa, pressure is bigger, and granularity is smaller, works as pressure When being 7MPa, influence of the pressure to granularity is little.But when the degree of superheat is smaller, atomizing pressure has granularity and degree of irregularity It influences, atomizing pressure is big, fine size, irregular raising.Water jet speed is improved, atomizing pressure, another party are on the one hand improved Nozzle resistance is reduced in face, by reducing the draw ratio of nozzle, improves inner nozzle surface finish and realizes；
(5) water flow: although the energy for being actually used in the powder particle of production dispersion is one of consumed energy in atomization process Fraction, biggish water flow can preferably reduce the humidity of crushed powder, slow down nodularization, loose ratio be reduced, to particle size influences Less.
Embodiment three:
The implementation method of high green alloyed powder includes following in the high green compact high stability environmental protection diffusion type tin zinc-copper powder Step:
(1) using secondary resources such as high-purity copper, zinc and copper-tin alloy leftover pieces as raw material, fusing obtains metal in electric induction furnace Solution is carried out degasification deslagging to metallic solution, is then allowed to stand slag hitting, keeps impurity content in melt small by furnace bottom gon technics In 0.2%, then metallic solution passes through special nozzle, prepares copper powder and Albaloy powder using water atomization；
(2) there are small amounts on water atomization copper or copper alloy powder, surface, so using oxidation --- and reducing process is to water atomization Copper powder and Albaloy powder are modified, and are further improved its performance.Use oxidationreduction technique: wherein oxidizing temperature for It 300-500 DEG C, oxidization time 2-4h, according in oxidation process, wherein in oxidation process, after oxidation, is gone back in hydrogen Original, reduction temperature are 400-600 DEG C, chemical reaction equation:
Oxidation reaction: 2M (metal)+O2=2MO
Reduction reaction: MO+H2=M+H2O
Wherein oxidation-reduction process meets thermodynamics theorem, according to thermodynamic temperature map, can consult, wherein the preferential oxygen of copper Change, in copper alloy, wherein the volume of oxygen occupies certain position in the grain, leads to growing up for particle after due to oxidation.So After passing through reduction afterwards, a kind of porous structure is formed, by the way that suitable extraordinary lubrication is added in " solid-solid " two-phase thermal diffusion process Agent, to improve the green compact performance of product.For affecting laws of the technological parameter to powder characteristic during this, thermal diffusion process In phase transition mechanism and interfacial reaction process expansion study, for tin zinc-copper powder Integration ofTechnology optimize and demonstrate.Using spy Its green compact typed pressure of the alloyed powder of different lubricant processing can achieve 12MPa or more.
Example IV:
The implementation method that degree of segregation improving performance is reduced in the high green compact high stability environmental protection diffusion type tin zinc-copper powder is specific gravity Degree of segregation reduces method: changing traditional solidification atomization process, using top-down solidification atomization technique, by adjusting mist Change the parameters such as temperature, the angle of device, Inversion is carried out to the built-up sequence of nascent crystalline substance, first solidifies low-melting tin, zinc, it is rear solidifying Gu the high copper of fusing point generates the crystal grain fusion of different metal material in fusion, passes through thermodynamics+dynamic (dynamical) Mechanism Primary Reason realizes that secondary fusion reduces gravity segregation.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (4)

1. a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder, it is characterised in that: a kind of Gao Sheng The preparation method of base high stability environmental protection diffusion type tin zinc-copper powder the following steps are included:
(1) raw material is chosen: it is spare to choose the secondary resources such as high-purity copper, zinc and the copper-tin alloy leftover pieces of certain mass number；
(2) low pine is than the formation of prealloy powder: high-purity copper powder of low apparent density and Albaloy powder are prepared by using water atomization, Parameter by adjusting atomization process improves the hollowness of particle so that granule-morphology is irregular, and the regular shape of generation is porous Shape, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
(3) high green is realized: by the way that suitable extraordinary lubricant is added in " solid-solid " two-phase thermal diffusion process, to improve The green compact performance of product, by being tin zinc to the phase transition mechanism and the expansion research of interfacial reaction process in thermal diffusion process The optimization of copper powder Integration ofTechnology and demonstration, using the alloyed powder of special lubricant processing, its green compact typed pressure can achieve 12MPa More than；
(4) degree of segregation improving performance is reduced: by the microsegregation performance and gravity segregation performance during change powder compacting Two key factors reduce segregation performance, and Main is to change crystal grain atom using dynamics+Thermodynamic Mechanism principle Spacing is spread to reduce microsegregation degree；Using reverse order freezing method, changes mother liquor and match the solidification sequence reduction material of liquid The gravity segregation of material.
2. a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder according to claim 1, special Sign is: low pine is more raw using diffusion technique is consolidated than prealloy powder in the high green compact high stability environmental protection diffusion type tin zinc-copper powder The tin zinc-copper powder of production is in the selection of material, based on CuSnZn alloyed powder+CuSn alloyed powder+Cu powder combining form Material, so that granule-morphology is irregular, improves the hollowness of particle, the shape rule of generation by adjusting the parameter of atomization process Then cavernous, the loose specific density of Multihollow degree is lower than the pre-alloyed powder of 2.0g/cm3；
It is described it is low pine than prealloy powder production in Countermeasures the following steps are included:
The degree of superheat of metal bath: the degree of superheat is bigger, and molten metal surface tension is small, the easier formation of first time drop, generation Particle is thin, but the time of cooling requirement is long, and the degree of irregularity of metal reduces, Song Bigao；
Chilled water: chilled water is low, the distance that particle flies in the sky, and degree of irregularity reduces, when the lower degree of superheat, mist When change rate-of flow is big, influence less, as long as it is as high as possible not influence atomization process chilled water；
The structure of nozzle is to relevant size: under other identical conditions, the structure type of nozzle is different, when metal atomization The situation of atomizing medium and metal bath is entirely different, directly affects atomizing effect, for free fall type nozzle, generally has The structure types such as " V " shape is board-like, taper, annular distance, circumferential weld cannot form closed mist in atomization using " V " shape plate nozzle Change region, is in wavy band before metal bath atomization, granularity is big after atomization, and ingredient rate is low；
Circumferential weld nozzle processing difficulties, combination abrasive structure require height during installation, and concentricity is too low, cause atomizing medium distribution not , out-focus not can be carried out effective atomization, thus ring pore structures are relatively reasonable, to reach technique purpose, and ring pore structures will meet Claimed below: the aperture A is small, pore size distribution is uniform, hole sufficiently focuses, and can form closed nebulization region；B nozzle annular distance resistance is small, Under identical atomizing pressure, jet expansion atomizing medium speed is improved, and subdivision rate is high, and atomization is abundant；C atomization item angle is reasonable, It is atomized that apex angle is big, and stream distance is small, degree of irregularity reduces, and granularity variation is unobvious, and it is high-efficient, and it is excessive to be atomized apex angle, easily Plug nozzle；
Atomizing pressure: i.e. water jet speed；
When atomizing pressure is less than 7MPa, pressure is bigger, and granularity is smaller, when pressure is 7MPa, shadow of the pressure to granularity It rings little；
But when the degree of superheat is smaller, atomizing pressure all has an impact to granularity and degree of irregularity, and atomizing pressure is big, fine size, irregular It improves；
Water jet speed is improved, atomizing pressure is on the one hand improved, on the other hand reduces nozzle resistance, by the length for reducing nozzle Diameter ratio improves inner nozzle surface finish and realizes；
Water flow: although the energy for being actually used in the powder particle of production dispersion is a small portion of consumed energy in atomization process Point, biggish water flow can preferably reduce the humidity of crushed powder, slow down nodularization, reduce loose ratio, little to particle size influences.
3. a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder according to claim 1, special Sign is: in the high green compact high stability environmental protection diffusion type tin zinc-copper powder implementation method of high green alloyed powder include with Lower step:
(1) using secondary resources such as high-purity copper, zinc and copper-tin alloy leftover pieces as raw material, fusing obtains metal in electric induction furnace Solution is carried out degasification deslagging to metallic solution, is then allowed to stand slag hitting, keeps impurity content in melt small by furnace bottom gon technics In 0.2%, then metallic solution passes through special nozzle, prepares copper powder and Albaloy powder using water atomization；
(2) there are small amounts on water atomization copper or copper alloy powder, surface, so using oxidation --- and reducing process is to water atomization Copper powder and Albaloy powder are modified, and are further improved its performance；
Use oxidationreduction technique: wherein oxidizing temperature is 300-500 DEG C, oxidization time 2-4h, according to oxidation process In, it wherein in oxidation process, after oxidation, is restored in hydrogen, reduction temperature is 400-600 DEG C, chemical reaction side Journey:
Oxidation reaction: 2M (metal)+O2=2MO
Reduction reaction: MO+H2=M+H2O
Wherein oxidation-reduction process meets thermodynamics theorem, according to thermodynamic temperature map, can consult, wherein the preferential oxygen of copper Change, in copper alloy, wherein the volume of oxygen occupies certain position in the grain, leads to growing up for particle after due to oxidation；
Then after passing through reduction, a kind of porous structure is formed, by the way that suitable spy is added in " solid-solid " two-phase thermal diffusion process Kind lubricant, to improve the green compact performance of product；
Phase transition mechanism and boundary for technological parameter during this to the affecting laws of powder characteristic, in thermal diffusion process The expansion research of face reaction process, optimizes and is demonstrated for tin zinc-copper powder Integration ofTechnology；
Using the alloyed powder of special lubricant processing, its green compact typed pressure can achieve 12MPa or more.
4. a kind of preparation method of high green compact high stability environmental protection diffusion type tin zinc-copper powder according to claim 1, special Sign is: in the high green compact high stability environmental protection diffusion type tin zinc-copper powder reduce degree of segregation improving performance implementation method be than Weight degree of segregation reduces method: changing traditional solidification atomization process, using top-down solidification atomization technique, by adjusting mist Change the parameters such as temperature, the angle of device, Inversion is carried out to the built-up sequence of nascent crystalline substance, first solidifies low-melting tin, zinc, it is rear solidifying Gu the high copper of fusing point generates the crystal grain fusion of different metal material in fusion, passes through thermodynamics+dynamic (dynamical) Mechanism Primary Reason realizes that secondary fusion reduces gravity segregation.
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* Cited by examiner, † Cited by third party
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CN110480022A (en) * 2019-09-04 2019-11-22 泉州天智合金材料科技有限公司 A kind of FeNiCuSn pre-alloyed powder, preparation method and application

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CN103394700A (en) * 2013-08-21 2013-11-20 铜陵卓成金属粉体新材料科技有限公司 Pre-alloyed diffusion method for producing tin bronze powder

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GB2067221A (en) * 1979-12-22 1981-07-22 Tokyo Oilless Metal Ind Sintered Alloys
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