WO2009136552A1 - 黄銅合金粉末、黄銅合金押出材およびその製造方法 - Google Patents

黄銅合金粉末、黄銅合金押出材およびその製造方法 Download PDF

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WO2009136552A1
WO2009136552A1 PCT/JP2009/058142 JP2009058142W WO2009136552A1 WO 2009136552 A1 WO2009136552 A1 WO 2009136552A1 JP 2009058142 W JP2009058142 W JP 2009058142W WO 2009136552 A1 WO2009136552 A1 WO 2009136552A1
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brass
brass alloy
chromium
powder
phase
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PCT/JP2009/058142
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English (en)
French (fr)
Japanese (ja)
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勝義 近藤
元 片野
久志 今井
美治 上坂
明倫 小島
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独立行政法人科学技術振興機構
国立大学法人大阪大学
サンエツ金属株式会社
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Application filed by 独立行政法人科学技術振興機構, 国立大学法人大阪大学, サンエツ金属株式会社 filed Critical 独立行政法人科学技術振興機構
Priority to EP09742676.1A priority Critical patent/EP2275582A4/en
Priority to US12/991,259 priority patent/US20110056591A1/en
Priority to CN200980116310.7A priority patent/CN102016089B/zh
Priority to JP2010511043A priority patent/JP5376604B2/ja
Publication of WO2009136552A1 publication Critical patent/WO2009136552A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • 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
    • C22C1/0425—Copper-based alloys
    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • 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

Definitions

  • the present invention relates to a high-strength brass alloy, and more particularly to a lead-free brass alloy powder and a brass alloy extruded material which are harmful to the environment and the human body.
  • 6/4 brass has moderate strength, good mechanical properties, and is nonmagnetic, so it is not only used as a mechanical part, but also widely used in gas piping, water piping, valves, etc. It is done.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-309835
  • Patent Document 2 International Publication WO 98/10106
  • the low melting point metal evaporates rapidly during melting because the vapor pressure of the low melting point metal is high, and the desired alloy composition is obtained. So difficult to control.
  • Brass is an alloy of copper and zinc. If a high melting point metal is added to this brass, there is a possibility that an improvement in strength can be expected. However, the boiling point of zinc is as low as 907 ° C., and it is not easy to add chromium having a melting point of 1907 ° C., vanadium having a melting point of 1902 ° C., and the like. If the temperature of brass in liquid phase is increased, the amount of evaporation of zinc inevitably increases, and the alloy composition rapidly changes in the copper-rich direction.
  • a melting method of the high melting point metal there are an electron beam melting method, a hydrogen plasma arc melting method and the like, but these methods are not suitable for mass production, but are used for small batch processing of rare metals. Moreover, these methods can not prevent evaporation of the low melting point metal.
  • Patent Document 3 discloses a method of adding an alloy component to zinc.
  • the mother alloy is used for the addition of chromium
  • Zn 17 Cr or Zn 13 Cr as a compound is dispersed in the zinc matrix.
  • this master alloy is added to zinc, the change in the chromium compound does not occur only by increasing the proportion of the zinc component.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 11-209835
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2006-124835
  • the methods disclosed in these publications involve the inclusion of chromium, zirconium, tellurium, sulfur, iron, silicon, titanium or phosphorus in copper. Both are precipitation-type copper alloys, and precipitation of copper / zirconium compounds etc. is performed as a strengthening phase, but unlike zinc-containing alloys, they can be alloyed even at high temperatures, so the preparation of these materials is easy. I have to.
  • the inventors of the present invention have been working on the development of graphite-added brass as a part of the development of leadless brass alloys.
  • the graphite particle dispersion type lead-free machinable brass alloy has the same strength as that of lead-containing machinable brass alloy, and the strength is not improved dramatically.
  • An object of the present invention is to provide a brass alloy powder which contributes to the improvement of the strength of a brass alloy member.
  • Another object of the present invention is to provide a brass alloy extruded material having excellent mechanical strength.
  • Still another object of the present invention is to provide a brass alloy member having excellent mechanical strength.
  • Still another object of the present invention is to provide a method for producing a brass alloy extruded material having excellent mechanical strength.
  • the brass alloy powder according to the present invention has a brass composition consisting of a mixed phase of ⁇ phase and ⁇ phase, and contains 0.5 to 5.0% by mass of chromium.
  • the chromium contains a component dissolved in the matrix of brass and a component precipitated in grain boundaries.
  • the content of chromium needs to be 0.5% by mass or more.
  • the chromium content in the brass alloy powder may be increased, but the limit is 5.0 mass% from the viewpoint of production at the present time is there.
  • the more preferable content of chromium is 1.0 to 2.4% by mass.
  • the chromium component forcibly dissolved in the matrix of brass suppresses the dislocation motion in the crystal and contributes to the improvement of the proof stress value.
  • the chromium component precipitated at the grain boundaries suppresses grain boundary sliding to cause extreme work hardening and contributes to the improvement of tensile strength.
  • the component dissolved in the matrix of brass includes a component dispersed and dispersed in the matrix and a component dispersed as a precipitate in the matrix.
  • the brass alloy powder may contain at least one element selected from the group consisting of nickel, manganese, zirconium, vanadium, titanium, silicon, aluminum and tin.
  • the above-mentioned brass alloy powder is a rapidly solidified powder, more preferably a rapidly solidified powder by a water atomizing method.
  • the extruded brass alloy according to the present invention has a brass composition consisting of a mixed phase of ⁇ phase and ⁇ phase, contains 0.5 to 5.0% by mass of chromium, and the above chromium is in the matrix phase of brass. It is obtained by extruding an assembly of a brass alloy powder containing a component to be solid-solved and a component to be precipitated at grain boundaries.
  • the 0.2% proof stress value of the brass alloy extruded material is 300 MPa or more. Moreover, tensile strength is 500 MPa or more.
  • the brass alloy extruded material is added after 0.2 to 2.0% by weight of graphite particles are added to and mixed with the brass alloy powder. Obtained by extruding this mixed powder aggregate.
  • the particle size of the graphite particles to be added is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • a brass alloy member according to the present invention has a brass composition consisting of a mixed phase of ⁇ phase and ⁇ phase, contains 0.5 to 5.0% by mass of chromium, and further, nickel, manganese, zirconium, vanadium, titanium , At least one element selected from the group consisting of silicon, aluminum and tin. Chromium contains a component dissolved in the matrix of brass and a component precipitated in grain boundaries.
  • the brass alloy member further includes graphite particles to improve the machinability of the brass alloy member.
  • the method for producing a brass alloy extruded material according to the present invention has a brass composition comprising a mixed phase of ⁇ phase and ⁇ phase, and rapidly solidifies a brass alloy powder containing 0.5 to 5.0% by mass of chromium. And extruding the assembly of the rapidly solidified brass alloy powder described above.
  • the rapid solidification method is a water atomization method.
  • the heating temperature at the time of extrusion processing is preferably 650 ° C. or less.
  • the manufacturing method in one embodiment includes the step of adding and mixing 0.2 to 2.0% by weight of graphite particles with respect to the brass alloy powder prior to extrusion processing.
  • Novel brass alloy powder preparation method The inventors of the present invention examined a method for producing an unprecedented high strength free-cutting brass member by increasing the strength of brass itself as a base material.
  • a method of increasing the strength of brass generally, a method of adding various additives is employed.
  • high-strength brass is obtained by adding iron, aluminum, manganese or the like to a copper-zinc alloy and has a high tensile strength of 460 MPa and good corrosion resistance, and thus is applied to propellers for ships and the like.
  • this high strength brass is only guaranteed to have an elongation of about 15%, and it can not be said that the workability is never good.
  • the water atomization method which is a type of rapid solidification method
  • the molten metal is rapidly solidified at a very high speed to produce a powder
  • not only non-equilibrium phase appears in the powder but also fine crystal grains
  • the inventors of the present invention have newly proposed a powder having a property different from that of a conventional brass powder by adding a small amount of chromium (Cr) as a third element to a brass alloy composed of a mixed phase of ⁇ phase and ⁇ phase.
  • Cr chromium
  • the present inventors propose a new method for adding chromium, which is a refractory metal, to 6/4 brass.
  • chromium which is a refractory metal
  • the molten metal must be heated to the melting point of chromium, but such heating temperature exceeds the boiling point of zinc. Therefore, practically, it can be said that it is impossible to heat liquid brass to the melting point of chromium in consideration of the high vapor pressure of zinc.
  • the present inventors developed a brass alloy production method using a commercially available Cu-10% Cr master alloy.
  • chromium is dispersed as grains of about 10 to 50 ⁇ m in size and is not necessarily in solid solution in copper.
  • This mother alloy is first melted at about 1200 ° C. At this temperature, the chromium contained in the master alloy does not dissolve, and therefore, it floats in the liquid phase of copper as it is in solid phase. In this state, add copper and adjust the concentration of chromium to be thin. Then, when the chromium concentration reaches about 4%, the solid-liquid phase line in the phase diagram is crossed to be in the one-phase state of the liquid phase.
  • chromium which is a high melting point metal, could be made into a mixed liquid phase with copper.
  • a predetermined amount of zinc was added, and when it was quenched and solidified by a water atomizing method, it was possible to obtain a powder having a non-equilibrium phase in which chromium was forcibly dissolved in brass.
  • the above-mentioned powder production method developed by the present inventors is an advantageous method for adding a high melting point metal to brass also from the viewpoint of composition control of brass alloy.
  • the addition of relatively low melting point nickel and manganese increases the utility value as a powder which can further improve strength.
  • graphite added to the brass alloy powder thus obtained and extruding it, a lead-less machinable brass alloy excellent in strength and machinability can be obtained.
  • the conventional method of grain refinement has been to repeat the plastic working and heat treatment on the member repeatedly, but if powder metallurgy is used as in the present invention, it is already refined as a starting material Since a powder having a crystalline structure is prepared, no special process for micronization is required. In addition, since the material composition is already determined in the powder state, the composition of the final product can be grasped at this stage. In addition to such production advantages, the material according to the invention has several excellent features as described below.
  • chromium hardly dissolves in brass.
  • a rapid solidification method such as a water atomization method
  • chromium dissolved in a liquid phase is forcibly dissolved in a matrix of brass by a certain amount.
  • the component dissolved in the matrix of brass includes a component dispersed and dispersed in the matrix and a component dispersed as a precipitate in the matrix.
  • the chromium component forcibly dissolved in the matrix and the chromium component precipitated at the grain boundaries exhibit different effects on the applied stress.
  • the chromium component forced to form a solid solution in the matrix suppresses the dislocation movement in the crystal and contributes to the improvement of the proof stress value of the brass alloy member.
  • the chromium component precipitated at the grain boundaries suppresses grain boundary sliding to cause extreme work hardening, which greatly contributes to the improvement of tensile strength.
  • manganese unlike chromium, basically dissolves in brass. Therefore, manganese does not form intergranular precipitates and does not cause extreme work hardening, but acts to improve both the load resistance value and the tensile strength in a well-balanced manner. The reason is believed to be that manganese in solid solution in the matrix phase pinpoints dislocations.
  • Nickel also forms a solid solution completely in brass, but promotes the transformation from ⁇ phase to ⁇ phase in the process of hot extrusion of brass alloy, and forms a fine ⁇ phase in the crystal to greatly contribute to the improvement of proof stress .
  • nickel does not contribute to work hardening, the maximum tensile stress is almost the same as that of a powder extruded material to which no nickel is added.
  • Chromium, manganese and nickel are transition elements that appear in the fourth period of the periodic table, but as described above, their effects when added to brass are different from one another, and they exhibit completely different behavior. The reason is that each transition element strengthens brass by a different mechanism. Therefore, if two or more elements are added, it is considered that the respective effects are exhibited.
  • Vanadium a transition element of the fourth period of the periodic table, has an equilibrium diagram similar to chromium. Therefore, if vanadium is added by the same method as the addition of chromium to make atomized powder, the vanadium component which is forced to form a solid solution in the matrix and the vanadium component which precipitates in grain boundaries appear, and the same reinforcement as chromium The mechanism can improve the performance of brass.
  • titanium, silicon, aluminum, tin, etc. which are generally known as reinforcement elements for brass, are also expected to work effectively for strengthening chromium-added brass as an additional additive element.
  • phase transformation should be a mixed phase of ⁇ phase and ⁇ phase, but this phase transformation hardly occurs because of high quenching degree.
  • phase transformation from the ⁇ phase to the ⁇ phase occurs to become a mixed phase.
  • Chromium and manganese were found to have the effect of delaying the transformation to the alpha phase. This is an effect of suppressing atomic diffusion in crystal grains, and is considered to be highly effective in maintaining the non-equilibrium phase formed by rapid solidification.
  • the work-hardening phenomenon is manifested remarkably by the grain boundary precipitates in the solidification process suppressing the grain boundary sliding.
  • the size of grain boundary precipitates is controlled to a size (maximum length) of about 100 nm to 500 nm.
  • the dispersion state of the precipitates is also an important factor, and it is desirable that the raw material powder be homogeneous since it is ideal that the precipitates be uniformly dispersed in the structure. If it is an atomizing method as a powder production method, control of the solidification speed and the powder particle size accompanying it is easy.
  • the extrusion temperature is a very important factor in improving the strength of the brass alloy extruded material.
  • the extrusion temperature is preferably as low as possible. In order to extrude the powder assembly, the powder needs to be heated. The higher the heating temperature, the faster the atomic diffusion, and the non-equilibrium phase produced by rapid solidification approaches the thermal equilibrium state. Therefore, it is important to extrude the brass alloy powder assembly at the lowest temperature that allows extrusion.
  • the preferred extrusion temperature is 650 ° C. or less. It is difficult to determine the lower limit of the extrusion temperature. This is because the lower limit temperature is determined by the size of the extruded billet, the extrusion ratio, the maximum extrusion load of the apparatus, and the like. If extrusion at 500 ° C. is possible, the temperature is an appropriate condition, but in practice, it seems that 550 ° C. or more is required to carry out the extrusion process.
  • the present inventors have found that a material of higher strength can be obtained by controlling the extrusion rate at the time of extruding a chromium-containing brass alloy powder aggregate.
  • extrusion conditions for obtaining a material of higher strength extrusion at low temperature is effective, and further improvement in strength can be expected by reducing the extrusion speed. This point will be described later based on the experimental results.
  • graphite particles may be added to and mixed with the chromium-containing brass alloy powder, and this mixed powder aggregate may be extruded. In order to exhibit the effect of improving the machinability, it is necessary to add 0.2 to 2.0% by weight of graphite particles to the chromium-containing brass alloy powder.
  • the particle size of the additive graphite particles is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the addition amount of chromium is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
  • the upper limit value of the chromium content is 5.0% by mass. Due to limitations at the powder production stage, the upper limit of the chromium concentration in the copper-chromium liquid phase state is 4%. When zinc is added here, the chromium content is 2.4% by mass. It is possible to increase the chromium content by raising the melting temperature of copper-chromium. For example, when the dissolution temperature is raised to 1300 ° C., chromium can be dissolved to a concentration of 8%, and the chromium content when zinc is added is 5.0 mass%. However, at this temperature, the vapor pressure of zinc becomes too high, making composition control difficult. Therefore, the upper limit value of the more preferable chromium content is 2.4 mass%.
  • vanadium should be added to the vicinity of the upper limit in order to make the most of the effect of vanadium.
  • the concentration of vanadium is 0.3% by mass by the addition of zinc.
  • it is necessary to raise the melting temperature.
  • the vapor pressure of zinc becomes too high, making it difficult to make a powder with an optimal composition. Therefore, the effect of the addition of vanadium can not but be limited, and strengthening in combination with other elements is required.
  • the brass alloy can be further strengthened by supplementarily adding manganese in combination with the above chromium addition or chromium and vanadium addition.
  • the addition amount of manganese it was confirmed that a sufficient effect can be obtained at 0.5% by mass.
  • the more preferable addition amount of manganese is 1 to 3% by mass, and when the amount is exceeded, the elongation may be reduced, which may result in the deterioration of the processability of brass.
  • nickel Since nickel is completely dissolved in copper, it can be alloyed by adding an arbitrary amount in the Cu—Zn—Ni system. Therefore, in the present invention, there is no upper limit in particular about the addition amount of nickel.
  • the addition of nickel has a special effect of increasing only the proof stress value, and a proof stress value exceeding 300 MPa can be realized with an addition amount of 1% by mass.
  • the proof stress is more important than the tensile strength.
  • the greatest effect of the present invention is the inclusion of a predetermined amount of chromium in 6/4 brass, but the addition of more nickel provides more advantages. Since chromium has a high melting point, it is not easy to add even trace amounts. The use of thermal equilibrium in metallurgy has already been described as a means of overcoming this. Naturally, both elements should be added to simultaneously exhibit the effects of chromium and nickel. There is an easier method as an addition method in this case. That is, in order to add only chromium, the process described above is to be taken, but in order to add also nickel at the same time, it is preferable that the mother alloy initially contains chromium and nickel.
  • Nickel-chromium alloys are commercially available and their melting point is lowered to 1345 ° C. by alloying. It is possible to melt this alloy and copper using a high frequency furnace. Although the mixing ratio of nickel to chromium is 1: 1, the melt can be made much easier than manufacturing using a copper-chromium master alloy. If it is carried out to add nickel using this method, the preferable upper limit of the amount of added nickel is 2.4% by mass like chromium.
  • the upper limit of the amount of addition of nickel is not particularly limited, but it is desirable to keep the addition of 5% by mass or less as a range that does not impair the characteristics as brass. If the content of nickel is in this range, it is possible to make an alloy having desired mechanical properties, and it becomes applicable to a wide range of application.
  • the additive effect is exhibited at about several percent, at least 0.1% or more.
  • the appropriate amounts and combinations of various elements differ depending on the mechanical properties to be obtained. From the viewpoint of improving the strength, zirconium exhibits a grain refining effect, so even if it is added at 0.1%, its effect is sufficiently recognized, and it can be said from the hole-pitch's rule of thumb that it is a clear strengthening element.
  • Titanium, aluminum and the like increase the strength of the matrix by solid solution strengthening, and therefore the addition of a small amount of 1% or less exerts the effect.
  • Silicon is usually an element used for dispersion strengthening, and addition of about 3% is an appropriate amount. However, due to the balance with other elements, addition may not always lead to strengthening. In particular, in the alloy system of the present invention, if the chromium precipitation site and the silicon dispersion site are at the same location, the strengthening effect can not be obtained. Therefore, the addition amount of silicon is in a relation of being limited by the addition amount of chromium, and it can be said that the total amount of chromium and silicon is 3% or less.
  • Tin forms a solid solution at about 0.3% to exhibit the effect as a strengthening element, but when the addition amount is increased, a ⁇ phase appears, which causes embrittlement, and a large amount addition is not preferable, 0.1 It can be said that the range of% to 0.5% is preferable.
  • the X-ray-diffraction result of the produced powder is shown in FIG. Only the ⁇ phase was detected in the Cr-free brass alloy powder and the brass alloy powder to which 0.5% by mass of Cr was added. In the brass alloy powder to which 1.0 mass% of Cr was added, two phases of ⁇ phase and ⁇ phase were detected. In the case of the 6/4 brass composition, when the liquid phase is crossed the solid-liquid line, it becomes a ⁇ phase, and the rapidly solidified powder is generally cooled without ⁇ transformation. As a result of investigating in detail the brass alloy powder of 1.0 mass% Cr addition, it was a mixed state of alpha phase powder and beta phase powder.
  • Extrusion of 1.0 mass% Cr-added brass alloy powder A powder of composition 59% Cu-40% Zn-1% Cr prepared by a water atomizing method was pressed at 600 MPa to make a billet for extrusion.
  • the billet was heated in an electric furnace and extruded.
  • the temperature conditions of the electric furnace for heating were set to four types of 650 ° C., 700 ° C., 750 ° C. and 780 ° C.
  • the billet was processed by an extruder at an extrusion speed of 3 mm / s and an extrusion ratio of 37 to obtain a bar.
  • a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm was cut out of the bar and subjected to a tensile test to measure a 0.2% proof stress value and a maximum tensile strength. The results are shown in Table 2.
  • the billet was heated to a temperature of 650 ° C. and extruded showed high values in maximum tensile strength and 0.2% proof stress value. These mechanical strengths tended to decrease as the heating temperature was raised. Therefore, as for the heating temperature of the billet before extrusion, 650 degrees C or less is desirable.
  • a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm was cut out of the bar and subjected to a tensile test to measure a 0.2% proof stress value and a maximum tensile strength. The results are shown in Table 3.
  • the billet heated at a temperature of 650 ° C. and extruded showed high values in maximum tensile strength and 0.2% proof stress value. These mechanical strengths tended to decrease as the heating temperature was raised. Therefore, as for the heating temperature of the billet before extrusion, 650 degrees C or less is desirable.
  • the values of 0.5% Cr addition and 1.0% Cr addition showed substantially the same value. Therefore, it was found that the proof stress is maintained even if the amount of chromium added is small. However, the maximum tensile strength decreases as the amount of chromium decreases. While this shows that the proof stress value is determined by the amount of chromium which is forced to form a solid solution, the maximum tensile stress supports the increase of the degree of work hardening due to the precipitation of excess chromium at grain boundaries.
  • a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm was cut out of the bar and subjected to a tensile test to measure a 0.2% proof stress value and a maximum tensile strength.
  • the one obtained by heating and extruding the billet at 650 ° C. had a 0.2% proof stress value of 311 MPa and a maximum tensile strength of 479 MPa.
  • These mechanical strengths tended to decrease as the heating temperature was raised. Therefore, as for the heating temperature of the billet before extrusion, 650 degrees C or less is desirable.
  • Extrusion of 0.7 mass% Mn-added brass alloy powder A powder of composition 59% Cu-40% Zn-0.7 %% Mn prepared by a water atomizing method was pressed at 600 MPa to make a billet for extrusion.
  • the billet was heated in an electric furnace and extruded.
  • the temperature conditions of the electric furnace for heating were set to four types of 650 ° C., 700 ° C., 750 ° C. and 780 ° C.
  • the billet was processed by an extruder at an extrusion speed of 3 mm / s and an extrusion ratio of 37 to obtain a bar.
  • a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm was cut out of the bar and subjected to a tensile test to measure a 0.2% proof stress value and a maximum tensile strength.
  • the one obtained by heating and extruding the billet at 650 ° C. had a 0.2% proof stress value of 291 MPa and a maximum tensile strength of 503 MPa.
  • These mechanical strengths tended to decrease as the heating temperature was raised. Therefore, as for the heating temperature of the billet before extrusion, 650 degrees C or less is desirable.
  • Extrusion of Cr-free brass alloy powder A powder of composition 60% Cu-40% Zn prepared by a water atomizing method was compressed at 600 MPa to be a billet for extrusion. The billet was heated in an electric furnace and extruded. The temperature conditions of the electric furnace for heating were set to four types of 650 ° C., 700 ° C., 750 ° C. and 780 ° C. The billet was processed by an extruder at an extrusion speed of 3 mm / s and an extrusion ratio of 37 to obtain a bar.
  • a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm was cut out of the bar and subjected to a tensile test to measure a 0.2% proof stress value and a maximum tensile strength. The results are shown in Table 4.
  • the billet heated at a temperature of 650 ° C. and extruded showed high values in maximum tensile strength and 0.2% proof stress. These mechanical strengths tended to decrease as the heating temperature was raised. Therefore, as for the heating temperature of the billet before extrusion, 650 degrees C or less is desirable.
  • a tensile test was carried out by cutting a tensile test specimen having a distance between scores of 10 mm and a waist circumference of 3 mm from the bar.
  • the one obtained by heating and extruding the billet at 650 ° C. had a 0.2% proof stress value of 226 MPa and a maximum tensile strength of 442 MPa.
  • the powder billet exhibits higher numerical values in both of the maximum tensile strength and the 0.2% proof stress value than the molten billet. Specifically, by using a green compact billet, the maximum tensile strength is improved by 5.4%, and the 0.2% proof stress value is improved by 20.7%. From this point of view alone, the superiority of powder metallurgy is clear.
  • the extruded material of the green compact billet to which 1.0 mass% of Cr is added has the maximum tension
  • the strength is improved by 27.8%
  • the 0.2% proof stress value is improved by 40.2%. It is considered that the fact that the 0.2% proof stress value is greatly improved is the solid solution strengthening by the forced-solid solution chromium.
  • the maximum tensile strength of the powder billet added with Cr is greatly improved as compared to the powder billet with no addition of Cr. This is because, during the solidification process of the powder production process, chromium which did not form a solid solution is concentrated at grain boundaries to cause segregation of chromium at grain boundaries, resulting in spherical precipitates having a diameter of about 100 nm to 500 nm. It is considered that the cause is mainly existing at grain boundary triple points and grain boundaries. Such fine precipitates act as a large resistance to grain boundary sliding during plastic deformation, and as a result, exhibit a high degree of work hardening.
  • FIG. (A) of FIG. 4 is an extruded material of a brass alloy green compact billet added with 1 mass% Cr
  • (b) is an extruded material of a brass alloy green compact billet added with 0.5 mass% Cr
  • (c) is Cr.
  • (d) shows an extruded material of the additive-free billet brass alloy infused with Cr.
  • the powder billet extruded material has finer crystal grains as compared with the molten billet extruded material.
  • the grain size is 3 to 10 ⁇ m
  • the grain size of a brass alloy compacted billet extruded material with no Cr added is as fine as 1 to 6 ⁇ m.
  • the grain size is progressing to further submicron to 5 ⁇ m.
  • FIG. 5 shows an SEM image of an extruded material of a 1% by mass Cr-added brass alloy green compact billet.
  • the brass alloy powder or brass alloy powder extruded material is mainly described, but the present invention is also applicable to a brass alloy member. That is, the brass alloy member has a brass composition composed of a mixed phase of ⁇ phase and ⁇ phase, contains 0.5 to 5.0% by mass of chromium, and further, nickel, manganese, zirconium, vanadium, titanium, silicon, It contains at least one element selected from the group consisting of aluminum and tin.
  • the difference between the yield stress of the chromium-free brass alloy member and the yield stress of the chromium-added brass alloy member is represented on the vertical axis, and the concentration (%) of the chromium component in solid solution in the matrix is represented on the horizontal axis.
  • the increase in yield stress was 34 MPa when the solid solution amount of chromium was 0.22%, and the increase amount of yield stress was 54 MPa when the solid solution amount of chromium was 0.35%.
  • the yield stress increased in proportion to the concentration of chromium in solid solution in the matrix of brass.
  • the average particle size of the graphite particles used was 5 ⁇ m.
  • the chromium-containing brass powder produced by the water atomizing method and the graphite particles were mixed by a mechanical stirring method. This mixed powder was made into a powder compact billet in the same manner as the above-mentioned method, and subjected to hot extrusion processing to obtain a bar.
  • the amount of graphite particles to be added was three types of 0.5 wt%, 0.75 wt% and 1.0 wt% with respect to the chromium-containing brass alloy powder.
  • FIG. 7 is a graph showing the relationship between the amount of graphite particles added and the machinability. It was found that when the graphite particles were added to the chromium-containing brass alloy powder and extrusion processing was performed, the machinability was dramatically improved. Evaluation of machinability was performed by measuring the test time of the penetration test by a drill. The test piece was a round bar cut to a length of 5 cm, which was subjected to a penetration test with a drill diameter of 4.5 mm. A load of 1.3 kgf was applied to the drill, and the spindle rotational speed was 900 rpm. Ten tests were conducted, and the time required for penetration was averaged and displayed in the graph of FIG.
  • the relationship between the amount of graphite added and the time required for drill penetration was investigated.
  • the drill penetrated in a time of an average of 28 seconds at a graphite addition amount of 0.5%, though it was 180 seconds or more when no graphite was added.
  • the amount of graphite added was 0.75% or more, the penetration time was 20 seconds or less, and a drastic improvement in the machinability was observed. Therefore, in the case of a 0.5% chromium-containing brass alloy, it can be said that the addition of 0.75% or more of graphite is a condition suitable for greatly improving the machinability.
  • the penetration time was 180 seconds or more even when 0.5% of graphite was added.
  • the drill penetration occurred in an average of 38 seconds as the graphite loading was increased to 0.75%.
  • the penetration time was 20 seconds or less. Therefore, in the case of a 1.0% chromium-containing brass alloy, it can be said that the addition of 1.0% or more of graphite is a suitable condition for greatly improving the machinability.
  • the present invention can be advantageously utilized in the manufacture of 6/4 brass alloy members having excellent mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
PCT/JP2009/058142 2008-05-07 2009-04-24 黄銅合金粉末、黄銅合金押出材およびその製造方法 WO2009136552A1 (ja)

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EP09742676.1A EP2275582A4 (en) 2008-05-07 2009-04-24 MEASURING ALLOY POWDER, EXTRUDED MEASUREMENT ALLOY MATERIAL, AND METHOD FOR PRODUCING THE EXTRUDED MEASUREMENT ALLOY MATERIAL
US12/991,259 US20110056591A1 (en) 2008-05-07 2009-04-24 Brass alloy powder, brass alloy extruded material, and method for producing the brass alloy extruded material
CN200980116310.7A CN102016089B (zh) 2008-05-07 2009-04-24 黄铜合金粉末、黄铜合金挤出材料及其制造方法
JP2010511043A JP5376604B2 (ja) 2008-05-07 2009-04-24 鉛フリー黄銅合金粉末、鉛フリー黄銅合金押出材およびその製造方法

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US11459639B2 (en) 2018-03-13 2022-10-04 Mueller Industries, Inc. Powder metallurgy process for making lead free brass alloys
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CN111621667A (zh) * 2020-06-30 2020-09-04 兰州理工大学 一种铜钛合金及其制备方法
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KR20210137589A (ko) * 2016-05-18 2021-11-17 알마그 에스.피.에이. 납-없는 또는 낮은 납 함량의 황동 빌렛을 제조하는 방법 및 이에 따라 수득된 빌렛
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