KR101365816B1 - Sintered valve guide material and method for manufacturing the same - Google Patents

Abstract

In the sintered alloy for valve guides, the overall composition is, by mass ratio, C: 1.3 to 3%, Cu: 1 to 4%, and the balance is composed of Fe and unavoidable impurities, and has a base structure except pores and pores. The matrix structure is composed of a mixed structure of a pearlite phase, a ferrite phase, an iron carbide phase, and a copper phase, and represents a metal structure in which graphite is dispersed in a part of the pores, and when the cross-sectional metal structure is observed, By area ratio, an iron carbide phase is 3 to 25%, and the said copper phase shall be 0.5 to 3.5%.

Description

Sintered valve guide material and manufacturing method thereof {SINTERED VALVE GUIDE MATERIAL AND METHOD FOR MANUFACTURING THE SAME}

TECHNICAL FIELD The present invention relates to a sintered valve guide material used for an internal combustion engine and a method for manufacturing the same, and more particularly, to a technique for further improving wear resistance while suppressing manufacturing cost.

The valve guide used for the internal combustion engine is a circular pipe that supports, on its inner circumferential surface, a stem (column) of an intake valve for injecting fuel mixture gas into the combustion chamber of the internal combustion engine and an exhaust valve for exhausting combustion gas from the combustion chamber. It is necessary to maintain a smooth sliding state for a long time without wear of the valve stem with its wear resistance. As such a valve guide, cast iron has been used conventionally, but a sintered alloy can obtain an alloy of a special metal structure that cannot be obtained from a solvent material and can provide wear resistance. Products can be manufactured in large quantities and are suitable for mass production, can be molded into near net shapes, and the yield of materials due to machining is high. -34858, Japanese Patent No. 2680927, Japanese Patent No. 4323069, Japanese Patent No. 4323467, etc. have been used a lot.

The sintering valve guide material disclosed in Japanese Unexamined Patent Application Publication No. 55-34858 has a weight ratio of 1.5 to 4% of carbon (C), 1 to 5% of copper (Cu), 0.1 to 2% of tin (Sn), and phosphorus (P). It is a sintering valve guide material which consists of an iron type sintering alloy of less than 0.1 to 0.3% and remainder of iron (Fe). The metal structure photograph and the schematic diagram of this sintering valve guide material of Unexamined-Japanese-Patent No. 55-34858 are shown to FIG. 3A and 3B. As shown in Figs. 3A and 3B, in the sinter valve guide material disclosed in Japanese Unexamined Patent Application Publication No. 55-34858, an iron-phosphorus-carbon compound phase is precipitated in a pearlite matrix reinforced with copper and tin. In addition, as the iron-phosphorus-carbon compound absorbs C from the surrounding matrix and grows into a plate shape, the ferrite phase is dispersed in the portion in contact with the iron-phosphorus-carbon compound phase. Moreover, the copper alloy phase which melt | dissolved in the matrix at the time of the cooling of Cu which melt | dissolved once in the matrix beyond the solid solution limit at normal temperature under the high temperature at the time of sintering is disperse | distributed. In addition, in the metallographic photograph of FIG. 3A, the graphite phase cannot be dropped and observed when the sample is polished in order to observe the metallographic structure. However, as shown in the schematic diagram of FIG. 3B, graphite remains inside the large pores. Are dispersed as. Since the sintered valve guide material of JP 55-34858 A shows excellent wear resistance by the said iron-phosphorus-carbon compound phase, it is a standard material of the valve guide for internal combustion engines of automobiles, and is utilized by domestic and foreign automobile manufacturers. It's going on.

In addition, the sintering valve guide member disclosed in Japanese Patent No. 2680927 is a sintering valve disclosed in Japanese Patent Application Laid-Open No. 55-34858 in order to improve the machinability of the sintering valve guide member of JP 55-34858 A. In the metal matrix of the guide material, magnesium metasilicate mineral, orthosilicate silicate mineral, and the like are dispersed as intergranular inclusions, similar to the sintering valve guide material of Japanese Patent Application No. 55-34858. Commercialization is advancing in car makers.

The sintered valve guide member disclosed in Japanese Patent No. 4323069 and Japanese Patent No. 4323467 aims at further improving machinability, and by reducing the amount of phosphorus, the amount of dispersion of the hard iron-phosphorus-carbon compound phase is reduced. In order to maintain the wear resistance of the guide by reducing the amount necessary, the machinability is improved, and practical use has begun in domestic and overseas automobile manufacturers.

In recent years, the demand for low cost is increasing in various industrial machine parts, and the demand for low cost is also increasing for automobile parts. Among these, as a sintering valve guide material for internal combustion engines, the demand for cost reduction is increasing.

On the other hand, with the recent improvement in fuel efficiency and fuel efficiency of automotive internal combustion engines, the valve guides in which the internal combustion engines are operating are exposed to higher temperatures and higher surface pressures, and in recent years, the valves have become more environmentally aware. There exists a tendency for the supply amount of the lubricating oil supplied to the interface of a guide and a valve stem to fall, and it becomes a more severe sliding environment in a valve guide. From this background, wear resistance corresponding to the sintering valve guide material disclosed in Japanese Patent Application Laid-Open No. 55-34858 and Japanese Patent No. 2680927 is demanded.

Accordingly, the present invention provides a valve guide material capable of reducing manufacturing costs while having a wear resistance equivalent to that of a conventional sintered valve guide material, that is, Japanese Patent Application Laid-Open No. 55-34858, Japanese Patent No. 2680927, and the like. It is an object to provide a manufacturing method.

As for the 1st sintering valve guide material of this invention which achieves the said objective, the total composition is C: 1.3-3%, Cu: 1-4%, and remainder consists of Fe and an unavoidable impurity by mass ratio, pore and pore In addition to the base structure except for the above, the base structure is composed of a mixed structure of a pearlite phase, a ferrite phase, an iron carbide phase, and a copper phase, and represents a metal structure in which graphite is dispersed in a part of the pores. The iron carbide phase is 3 to 25%, and the copper phase is 0.5 to 3.5% as an area ratio with respect to the metal structure when it is observed.

Moreover, as for the 2nd sintering valve guide material of this invention which achieves the said objective, the whole composition is C: 1.3 to 3%, Cu: 1 to 4%, Sn: 0.05 to 0.5%, and remainder by Fe by mass ratio. It consists of unavoidable impurities and consists of matrix structures except pores and pores, and the matrix structures consist of a pearlite phase, a ferrite phase, an iron carbide phase, and a mixed structure of a copper and / or copper tin alloy phase. Particularly, a metal structure in which graphite is dispersed is represented, and the iron carbide phase is 3 to 25%, and the copper and / or copper tin alloy phase is 0.5 to the area ratio with respect to the metal structure when the cross-sectional metal structure is observed. It is characterized in that 3.5%.

In the above-mentioned first and second sintered valve guide materials of the present invention, the iron carbide phase can be identified as a plate-shaped iron carbide having an area ratio of 0.05% or more in the field of view of a cross-sectional structure of 200 times the magnification. . In this case, wear resistance can be improved as long as the total area of the plate-shaped iron carbide whose area ratio with respect to the said visual field is 0.15% or more is 3-50% of the total area of the said plate-shaped iron carbide.

Moreover, it is preferable that at least 1 sort (s) of a manganese sulfide particle, a magnesium silicate mineral particle, and a calcium fluoride particle disperse | distributes 2 mass% or less in the powder grain boundary of a known structure, and the said pore.

In the manufacturing method of the 1st sintering valve guide material of this invention which achieves the said objective, the whole composition of raw material powder is C: 1.3-3%, Cu: 1-4%, and remainder is Fe and an unavoidable impurity in mass ratio. The raw material powder preparation step of adding and mixing copper powder and graphite powder to iron powder, and filling and compressing the raw material powder in a cylindrical tubular cavity of a mold to pressurize the raw powder to form a cylindrical tube pressure. It is characterized by having the process of shape | molding with powder, and the said green compact in the non-oxidizing atmosphere, and the process of sintering at the heating temperature of 970-1070 degreeC.

Moreover, in the manufacturing method of the 2nd sintering valve guide material of this invention which achieves the said objective, the whole composition of raw material powder is C: 1.3-3%, Cu: 1-4%, Sn: 0.05-0.5% by mass ratio. The raw powder which adds and mixes graphite powder, copper powder, tin powder, copper tin alloy powder, and copper powder and copper tin alloy powder to iron powder so that remainder may consist of Fe and an unavoidable impurity. A preparation step, a step of filling and compressing the raw material powder into a cylindrical tubular cavity of a mold, and molding the raw material powder into a cylindrical green compact, and the green compact in a non-oxidizing atmosphere, heating temperature 950 It is characterized by having a process of sintering at -1050 degreeC.

In the manufacturing method of said 1st and 2nd sintering valve guide material of this invention, it is preferable that the holding time in heating temperature is 10 to 90 minutes. Moreover, in the cooling process from a heating temperature to room temperature, it is preferable that the cooling rate at the time of cooling from 850 degreeC to 600 degreeC is 5-20 degreeC / min. Moreover, in the cooling process from a heating temperature to room temperature, it is preferable to cool after hold | maintaining constant temperature for 10 to 90 minutes in the area | region between 850 degreeC and 600 degreeC. In addition, in the preparation step of the raw material powder, it is preferable to further add at least one powder selected from manganese sulfide powder, magnesium silicate mineral powder, and calcium fluoride powder to be 2% by mass or less of the raw material powder.

The sintering valve guide material of the present invention maintains abrasion resistance by dispersing the iron carbide phase in a form and amount equivalent to that of the conventional one while reducing phosphorus in the overall composition, and achieving both low cost and abrasion resistance. Moreover, the manufacturing method of the sintering valve guide material of this invention exhibits the effect that the said sintering valve guide material of this invention can be manufactured by the simple method equivalent to the conventional one.

Accordingly, the present invention provides a valve guide material capable of reducing manufacturing costs while having a wear resistance equivalent to that of a conventional sintered valve guide material, that is, Japanese Patent Application Laid-Open No. 55-34858, Japanese Patent No. 2680927, and the like. A manufacturing method can be provided.

1A and 1B are metal structure photographs and schematic diagrams when the sintering valve guide material of the present invention is etched with nital, FIG. 1A is a metal structure photograph, and FIG. 1B is a schematic diagram of the metal structure photograph of FIG. 1A.
2A and 2B are schematic diagrams showing the metallographic photograph and the image processing result when the sintering valve guide material of the present invention is etched with the Murakami reagent, and FIG. 2A is a metallographic photograph and FIG. 2B is a metallographic photograph of FIG. 2A. It is a schematic diagram which shows the result of image-processing and extracting an iron carbide phase.
3A and 3B are metal structure photographs and a schematic diagram thereof of a conventional sintered valve guide material, FIG. 3A is a metal structure photograph, and FIG. 3B is a schematic diagram of the metal structure photograph of FIG. 3A.

In general iron-copper-carbon sintered materials, iron carbide dispersed in a plate shape which improves abrasion resistance in a matrix has not been obtained. On the other hand, in the conventional sintering valve guide material containing P (Japanese Patent Application Laid-Open No. 55-34858), the iron-phosphorus-carbon compound is dispersed in the matrix, and C is released from the surrounding matrix. Absorbs and grows in plate shape. From this, P is considered to be essential for the production of the iron-phosphorus-carbon eutectic compound in order to obtain iron carbide dispersed in a plate shape. Under these circumstances, the present inventors first examined the cause of the plate-shaped iron carbide not being produced in the iron-copper-carbon sintered material.

Examples of the iron-copper-carbon sintered material obtained by molding and sintering raw material powders containing copper powder and graphite powder to iron powder include those used as general structural materials and those used as sliding materials such as bearings.

The iron-copper-carbon sintered material used as the structural material is generally sintered at a heating temperature (sintering temperature) of at least Cu melting point (1084.5 ° C). Under this temperature, the added copper powder melts to generate a liquid phase, and this liquid phase is filled in the gap of the raw material powder by capillary force, wet the iron powder to cover it, and from the liquid powder covering the iron powder into the iron powder. By the diffusion of Cu, Cu is uniformly diffused and dissolved in the iron base. C added in the form of graphite powder also begins to diffuse into the iron base from about 800 ° C. in the sintering process, and C diffuses completely into the iron base under the above heating temperature because the diffusion rate into the iron base is high. The graphite powder disappears. As described above, in the iron-copper-carbon sintered material, Cu and C are diffused relatively uniformly in the iron matrix.

By the way, Cu is an element which makes the critical cooling rate of steel small, and has the effect of improving the hardenability of steel. That is, it has the effect of moving the pearlite nose of a continuous cooling transformation degree to the slower time (right side). When Cu having such an effect is cooled from the heating temperature in the state of being uniformly diffused in the iron base, the pearlite nose shifts to a slower time, and as a result, iron carbide (Fe ₃ C) at a cooling rate in a normal sintering furnace. Since it is cooled without gaps to grow sufficiently, it is considered that it becomes difficult to obtain iron carbide which becomes a fine pearlite structure and disperses in plate shape.

In addition, the iron-copper-carbon sintered material (for example, Japanese Patent Application Laid-Open No. 2005-082867, Japanese Patent Application Laid-Open No. 2008-202123, etc.) to be used as a sliding material may leave graphite powder to function as a solid lubricant. Therefore, sintering is performed at the heating temperature of about 750-800 degreeC which graphite powder does not diffuse easily. In this case, since the diffusion amount of C to the iron base is suppressed and the pore is formed, the metal structure obtained after sintering becomes a mixed phase of pearlite and ferrite, and the iron carbide (Fe ₃ C) dispersed in a plate shape. ) Is not considered to be obtained.

From this, the present inventors thought that the plate-shaped iron carbide (Fe ₃ C) could be precipitated at the time of cooling after sintering by controlling the diffusion state of Cu, and examined and desired without containing P. It was found that a plate-shaped iron carbide (Fe ₃ C) was obtained. This invention is made | formed by this knowledge.

[First sintering valve guide material]

The 1st sintering valve guide material of this invention by the said knowledge suppresses the diffusion of Cu in an iron base, and sets it as the base whose Cu density | concentration which the part with high Cu concentration and the part with low Cu concentration is nonuniform is mixed. The plate-shaped iron carbide (Fe ₃ C) was precipitated and dispersed in the low concentration part.

1A and 1B show the metal structure when the cross-sectional structure of the sintered valve guide material of the present invention is mirror polished and etched with nital (1% by mass alcohol nitrate solution). FIG. 1A is a metal structure photograph, and FIG. 1B is a schematic diagram thereof. As shown to FIG. 1A and 1B, the metal structure of the sintering valve guide material of this invention consists of a base except a pore and a pore, and the pore is disperse | distributed in the base. These pores are formed by the gap between the raw material powders when the raw material powder is molded, and the iron powder portion of the raw material powder forms a matrix (iron base). The matrix consists of a mixed structure of a pearlite phase, a ferrite phase, an iron carbide phase, and a copper phase. In the metallographic photograph of FIG. 1A, the graphite phase cannot be dropped and observed when the sample is polished to observe the metallographic structure. However, as shown in the schematic diagram of FIG. 1B, graphite remains inside the large pores and black. It is dispersed as association.

The iron carbide (Fe ₃ C) phase is precipitated in a plate shape, and has a shape and an amount almost equivalent to those of the conventional sintering valve guide material shown in Figs. 3A and 3B. In addition, the copper phase shows that a part of copper powder remains in a matrix in a non-diffusion state, and Cu is not fully spread | diffused.

In addition, the metal structure of the sintered valve guide material of the present invention was analyzed with an EPMA (Electron Probe MicroAnalyser) apparatus, whereby the iron carbide (Fe ₃ C) phase precipitated in the above-described plate shape had a Cu concentration. It confirmed that it precipitated in the low part. From this, if the diffusion of Cu in the iron matrix is suppressed and the Cu concentration where the portion with the high Cu concentration and the portion with the low Cu concentration is mixed is a non-uniform matrix, even if P is not contained, the portion having a low Cu concentration is known. Plate-shaped iron carbide (Fe ₃ C) is obtained.

FIG. 2A is a photograph of metallographic structure when the same sintered valve guide material is etched with a Murakami reagent (10% by mass aqueous potassium hexacyanoate, potassium hydroxide solution), and FIG. 2B is a schematic diagram of the image analysis of FIG. 2A. 2A and 2B, the plate-shaped iron carbide (Fe ₃ C) is etched thickly (grey part), and the pearlite part is etched lightly (white part). In addition, the black portions in FIGS. 2A and 2B are pores. Therefore, the plate-shaped iron carbide (Fe ₃ C) phase can be distinguished from the iron carbide (Fe ₃ C) constituting pearlite as described above.

In the sintering valve guide material of the present invention, Cu is essential for the strength of the sintering valve guide material, and in order to form a copper phase and improve the compatibility with the counterpart material (valve stem), the amount of Cu is 1% by mass. If it does not fall short, since the said effect is lacking, it shall be 1 mass% or more. On the other hand, when the amount of Cu exceeds 4 mass%, the amount of Cu diffused in the iron matrix becomes excessive, and it becomes difficult to obtain a plate-shaped iron carbide in the cooling process after sintering. From this, the amount of Cu in a sintering valve guide material shall be 1-4 mass%.

In the sintering valve guide material of the present invention, C is essential for forming the iron carbide phase and forming the graphite phase as a solid lubricant. For this reason, C shall be 1.3% or more. On the other hand, although C is provided in the form of graphite powder, when the addition amount of the graphite powder in the raw material powder exceeds 3.0 mass%, the fluidity decrease, the decrease in packing property, and the compressibility decrease of the raw material powder become remarkable. Becomes difficult. From this, the amount of C in a sinter valve guide material is made 1.3 to 3.0 mass%.

Since the amount of plate-shaped iron carbide phases decreases abrasion resistance at a small amount, 3% or more is required as an area ratio with respect to the metal structure containing pores when the cross-sectional metal structure is observed. On the other hand, when the amount of plate-shaped iron carbide phase becomes excessive, the aggression to the counterpart member (valve stem) becomes high, causing wear of the counterpart member, deterioration of the strength of the valve guide, deterioration of machinability of the valve guide, and the like. Since a problem arises, the upper limit of the plate-shaped iron carbide phase is 25%. In addition, pearlite is a layered structure of fine iron carbide and ferrite, and the plate-shaped iron carbide phase of this invention does not contain the iron carbide of pearlite. In the plate-shaped iron carbide phase of the present invention, as shown in Fig. 2B, a dark colored portion, i.e., iron, is formed in the cross-sectional metal structure by image analysis software (e.g., WinROOF manufactured by Mitani Corporation). Area ratio can be calculated | required only by extracting a carbide phase and analyzing the area.

When the plate-shaped iron carbide is subjected to the above-described image analysis, all of the plate-shaped iron carbides are identified as 0.05% or more in the field of view of the cross-sectional structure having a magnification of 200 times. Therefore, even if it integrates the part whose area ratio is 0.05% or more in image analysis, it can obtain | require. In addition, in the plate-shaped iron carbide, the cross-sectional area ratio described above, and in the field of view of the cross-sectional structure of 200 times magnification, when the large plate-shaped iron carbide having an area ratio of 0.15% or more is 3 to 50% of the plate-shaped iron carbide, wear resistance Preferred from the standpoint of also described.

If the amount of the copper phase is small, the aggression to the counterpart (valve stem) becomes high, causing wear of the counterpart (valve stem) material. For this reason, the quantity of a copper phase shall be 0.5% or more in area ratio with respect to metal structure when the cross-sectional metal structure containing pores is observed. On the other hand, although the copper phase is formed from the copper powder added to the raw material powder, when the copper phase is excessive, that is, when the amount of the copper powder added in the raw material powder is excessive, the amount of diffusion of Cu to the iron base increases and plate-shaped iron is increased. It becomes difficult to obtain a carbide phase. For this reason, the quantity of a copper phase shall be 3.5% or less in area ratio with respect to metal structure when the cross-sectional metal structure containing pores is observed.

[Second sintering valve guide material]

It is the 2nd sintering valve guide material of this invention that Sn was contained in the said 1st sintering valve guide material, and the strength of the sintering valve guide material was improved. In order to improve this strength, the amount of Sn additionally added is 0.05% by mass or more. On the other hand, when the amount of Sn becomes excessive, as will be described later, the amount of generation of the Cu-Sn eutectic liquid phase becomes excessive, the diffusion of Cu into the iron matrix also increases, and it is difficult to obtain plate-shaped iron carbide in the cooling process after sintering. Lose. For this reason, the upper limit of Sn amount is made into 0.5 mass%.

In the second sintering valve guide material, Sn is dissolved in a part or all of the copper phase in the first sintering valve guide material according to the addition of Sn, and dispersed as a copper phase, a copper tin alloy phase, or a copper tin alloy phase. . In addition, these copper-based phases (copper phase and copper tin alloy phase or copper tin alloy phase) are 0.5% or more in area ratio with respect to the metal structure when the cross-sectional metal structure is observed from the point of compatibility with the counterpart. do. On the other hand, when the cross-sectional metal structure is observed when the area ratio to the metal structure exceeds 3.5%, the amount of diffusion of Cu to the iron base increases, making it difficult to obtain a plate-shaped iron carbide phase. For this reason, in the 2nd sintering valve guide material, the quantity of a copper system phase (copper phase, a copper tin alloy phase, or a copper tin alloy phase) is 0.5-3.5 in area ratio with respect to the metal structure when a cross-sectional metal structure is observed. %.

[Production Method of First Sintering Valve Guide Material]

The diffusion of Cu in the iron matrix is suppressed, and the Cu concentration in which the portion with high Cu concentration and the portion with low Cu concentration are mixed is non-uniform, and the plate-shaped iron carbide (Fe ₃₎ In obtaining the sintered valve guide material obtained by depositing and dispersing C), the method for producing the first sintered valve guide material according to the present invention uses a mixed powder obtained by mixing copper powder and graphite powder with iron powder as a raw material powder. The heating temperature (sintering temperature) at the time of sintering is less than Cu melting | fusing point (1085 degreeC), the generation | occurrence | production of Cu liquid phase is eliminated, and sintering is carried out only by the diffusion of Cu to iron base by solid phase diffusion.

At this time, if the graphite powder diffused at the above heating temperature is provided to the raw material powder in an amount of graphite or more, the portion of C added in the form of graphite powder is iron-based (austenite). In the state of uniform diffusion and melting, and the remaining portion remains as a graphite phase functioning as a solid lubricant.

When cooling from such a state, the effect of the iron-base hardenability improvement becomes small in the location where the Cu density | concentration of iron base is low, and the transition after the time of the pearlite nose of continuous cooling transformation degree becomes less, and the cooling after sintering The growth time of the iron carbide (Fe ₃ C) precipitated from the austenite in the process is secured and can be sufficiently grown to obtain a plate-shaped iron carbide (Fe ₃ C) of the desired shape without containing phosphorus (P) Can be.

Although sintering is performed in a non-oxidizing atmosphere as is conventionally performed, the upper limit of the heating temperature at the time of sintering should just be less than melting | fusing point of copper, but it sets it as 1070 degreeC from a viewpoint of suppressing diffusion of Cu. On the other hand, Cu is essential for improving the strength of the sintering valve guide material, and if the diffusion of Cu into the iron base is too short, the strength of the sintering valve guide material is insufficient. From this viewpoint, the lower limit of the heating temperature at the time of sintering shall be 970 degreeC.

In sintering at the heating temperature at the time of said sintering, the addition amount of copper powder shall be 1-4 mass%. If the addition amount of the copper powder is less than 1% by mass, the strength of the sintering valve guide material is insufficient. On the other hand, when the addition amount of copper powder exceeds 4 mass%, the amount of Cu diffused in an iron base becomes excessive, and it becomes difficult to obtain plate-shaped iron carbide in the cooling process after sintering. From this, the addition amount of the copper powder in raw material powder is made into 1-4 mass%.

In addition, in sintering at the heating temperature at the time of said sintering, the amount of graphite powder added, while the C diffused to the iron matrix in the said temperature range becomes a vacancy composition or a vacancy composition, It is necessary to make it into the quantity which a part remains as a solid lubricant. For this reason, the addition amount of the graphite powder in raw material powder needs to be 1.3 mass% or more. On the other hand, when the addition amount of the graphite powder in raw material powder exceeds 3.0 mass%, the fluidity | liquidity fall of a raw material powder, the fall of packing property, and the fall of compressibility become remarkable, and it becomes difficult to manufacture. From this, the addition amount of the graphite powder in raw material powder shall be 1.3-3.0 mass%.

Further, the diffusion of elements such as Cu and C has the greatest influence of the heating temperature and the influence of the heating time is relatively small. However, if the holding time during heating is too short, the diffusion of these elements may not be sufficiently performed. Therefore, it is preferable to make the holding time at the time of heating into 10 minutes or more. If the holding time at the time of heating is too long, the diffusion of Cu may proceed too much. Therefore, the holding time at the time of heating is preferably 90 minutes or less.

In the cooling process after sintering, when cooling from 850 degreeC to 600 degreeC in the cooling process from a heating temperature to room temperature, when the cooling rate in this temperature range shall be 20 degrees C / min or less, the precipitated iron carbide will plate | board. Since it becomes easy to grow in shape, it is preferable. On the other hand, if the cooling rate is too slow, the time required for cooling becomes long and the manufacturing cost increases. For this reason, it is preferable to limit the cooling rate in this temperature range to 5 degree-C / min or more.

Moreover, in the cooling process after sintering, when cooling from 850 degreeC to 600 degreeC in the cooling process from a heating temperature to room temperature, it is kept constant in this temperature range once, and the iron carbide which precipitates is grown in plate shape, You may cool. It is preferable to make constant temperature holding time at this time into 10 minutes or more. On the other hand, when the constant temperature holding time becomes excessive, the time required for cooling becomes long and the manufacturing cost increases. For this reason, it is preferable to limit the constant temperature holding time in this temperature range to 90 minutes or less.

 As mentioned above, in the manufacturing method of the 1st sintering valve guide material of this invention, the whole composition of raw material powder consists of C: 1.3-3%, Cu: 1-4% by weight ratio, and remainder consists of Fe and an unavoidable impurity. To the iron powder, copper powder and graphite powder are added, and a raw material powder preparation step of mixing is performed. Subsequently, the raw material powder obtained in the raw material powder preparation step is filled and pressurized into a cylindrical cylindrical cavity, and the raw material powder is molded into a cylindrical green compact. This molding process is conventionally performed as a manufacturing process of a sintering valve guide. The green compact obtained in the molding step is sintered at a heating temperature of 970 ° C to 1070 ° C in a non-oxidizing atmosphere.

[Production Method of Second Sintering Valve Guide Material]

In the manufacturing method of the said 1st sintering valve guide material, although copper powder is used and sintering is performed by solid-phase diffusion in order to control the diffusion amount of Cu, since the joining by diffusion of iron powders becomes only solid-state diffusion, The strength is lower than that of the iron-copper-carbon sintered material used as the structural material. Then, the manufacturing method of a 2nd sintering valve guide material is characterized by improving liquid phase sintering using Sn which has a low melting point like Japanese Unexamined-Japanese-Patent No. 55-34858, and improved the intensity | strength of a sintering valve guide material.

Sn has a melting point of 232 ° C., and the copper-tin alloy has a liquid phase generation temperature different depending on the Sn content. The higher the Sn content, the lower the liquid phase generation temperature, but the copper tin alloy having a Sn content of about 15% by mass. Even at 798 ℃ generates a liquid phase. Sn imparted in the form of tin powder and / or copper tin alloy powder generates a Sn liquid phase during a temperature rising process during sintering when tin powder is used. The Sn liquid phase is filled in the gap between the raw material powders by capillary force, covering the copper powder in part, and generating Cu-Sn process liquid phase on the surface of the copper powder. In addition, when copper tin alloy powder is used, Cu-Sn process liquid phase is generated according to temperature in the temperature rising process at the time of sintering. The Cu-Sn liquid phase is filled in the gap between the raw material powders by capillary force, wets and covers the iron powder, and promotes the diffusion bonding between the iron powders by promoting the growth of the necks of the iron powders.

In order to acquire the effect of the sintering acceleration by Sn mentioned above, Sn which is 0.05 mass% or more is required. However, when the amount of Sn becomes excessive, the amount of generation of the Cu-Sn eutectic liquid phase becomes excessive, the diffusion of Cu into the iron matrix also increases, and it becomes difficult to obtain plate-shaped iron carbide in the cooling process after sintering. For this reason, the upper limit of Sn amount is made into 0.5 mass%.

In the case of using Sn, the effect of promoting sintering by the Cu-Sn liquid phase is obtained, so that the lower limit of the heating temperature at the time of sintering is at a temperature of 950 ° C. lower than the manufacturing method of the above-mentioned first sintering valve guide material. You can get it. On the other hand, since the diffusion of Cu into the iron matrix also increases, it is necessary to set the upper limit of the heating temperature at the time of sintering to 1050 ° C in order to suppress the diffusion of Cu into the iron matrix.

In addition, when using a copper tin alloy powder, in order to generate | occur | produce a Cu-Sn eutectic liquid phase in the range of said heating temperature (950-1050 degreeC), the amount of Sn is 8 mass% or more as copper tin alloy powder (process liquid generation temperature) : 900 degreeC) may be used. Moreover, the preferable manufacturing conditions, such as the heating time at the time of sintering, the cooling rate at the time of cooling, and the constant temperature maintenance at the time of cooling, are the same as the case of said 1st sintering valve guide material.

 As mentioned above, in the manufacturing method of the 2nd sintering valve guide material of this invention, the whole composition of raw material powder is C: 1.3-3%, Cu: 1-4%, Sn: 0.05-0.5%, and a remainder by mass ratio. A raw material powder preparation step of adding and mixing graphite powder, copper powder and tin powder, copper tin alloy powder, and copper powder and copper tin alloy powder to iron powder so as to consist of additional Fe and unavoidable impurities. Do it. Subsequently, the raw material powder obtained in the raw material powder preparation step is filled and pressurized into a cylindrical cylindrical cavity, and the raw material powder is molded into a cylindrical green compact. This molding process is conventionally performed as a manufacturing process of a sintering valve guide. And the green compact obtained by the shaping | molding process is sintered by heating temperature 950-1050 degreeC in non-oxidizing atmosphere.

In said 1st sintered valve guide material and 2nd sintered valve guide material, machinability can be improved by the conventionally performed method, such as Unexamined-Japanese-Patent No. 2680927. That is, the sintering valve guide material obtained by adding, molding and sintering at least one powder selected from manganese sulfide powder, magnesium silicate mineral powder, and calcium fluoride powder to be 2 mass% or less of the raw material powder, is formed into the raw material powder. The machinability can be improved by dispersing at least one of manganese sulfide particles, magnesium silicate mineral particles, and calcium fluoride particles in the grain boundary of the structure and the pores by 2 mass% or less.

<Examples>

[First Example]

Iron powder, copper powder, and graphite powder are prepared, the copper powder of the ratio shown in Table 1, and 2 mass% graphite powder are added and mixed to iron powder, the raw material powder is prepared, the obtained raw powder is shape | molded Pressurized and compressed at a pressure of 650 MPa to form an outer diameter of 11 mm, an inner diameter of 6 mm, and a length of 40 mm, a cylindrical green compact (for abrasion test), and an outer diameter of 18 mm, inner diameter of 10 mm, and a length of 10 mm long cylindrical green compact (for rolling strength test). The obtained tubular green compact was sintered at a heating temperature of 1000 ° C. and a holding time of 30 minutes in an ammonia decomposition gas atmosphere, and then cooled to prepare a sintered compact sample of Samples 01 to 10. In addition, at the time of cooling from heating temperature to normal temperature, the cooling rate of the temperature range from 850 degreeC to 600 degreeC was 10 degreeC / min.

Moreover, as a conventional example, the alloy powder whose Sn content is 10 mass% and remainder is the copper tin alloy powder of Cu, and the iron content of 20 mass% P is prepared separately, and 5 mass% copper tin alloy powder is made to iron powder, 1.4 mass% iron phosphorus powder and 2 mass% graphite powder are added and mixed to prepare a raw powder. The raw powder is also molded into the above two kinds of shapes, and sintered under the above sintering conditions to prepare a sample. A sintered compact sample of No. 11 was produced. This conventional example is corresponded to the sintering valve guide material of Unexamined-Japanese-Patent No. 55-34858. The total composition of these samples is shown in Table 1 together.

The abrasion test was performed about the sintered compact sample obtained above, and the abrasion amount of the valve guide and the abrasion amount of the valve stem were measured, and a pressure test was performed and the crushing strength was measured. Moreover, the cross-sectional metal structure was observed and the area ratio of the iron carbide phase and the area ratio of the copper phase were measured.

The abrasion test is performed by a wear tester attached to the lower end of the piston for reciprocating the valve in a vertical direction while inserting the valve stem of the valve into the inner diameter of the fixed cylindrical sintered compact sample. While applying to the piston, the valve is reciprocated under a stroke speed of 3000 cycles / minute and a stroke length of 8 mm in an exhaust gas atmosphere at 500 ° C. After 30 hours of reciprocating movement, the amount of wear (μm) on the inner circumferential surface of the sintered body and the valve stem outer circumference The amount of wear (μm) was measured.

The pressure test is carried out in accordance with the method specified in JIS Z2507, pressurizing the cylindrical sintered sample of the outer diameter D (mm), wall thickness e (mm), length L (mm) in the radial direction to increase the pressure load, The maximum load F (N) when the sintered body sample was broken was measured, and the compressive strength K (N / mm ² ) was calculated by the following equation.

K = F × (De) / (L × e ² ). (One)

The measurement of the area ratio of the copper phase is performed by mirror polishing the cross section of the sample, corroding with nital, microscopic observation of the metal structure, image analysis by WinROOF manufactured by Mitani Corporation, and measuring the area to measure the area ratio. It was. The measurement of the area ratio of the iron carbide phase was performed in the same manner as the measurement of the area ratio of the copper phase, except that Murakami reagent (potassium hexacyano ferrate, potassium hydroxide 10% by mass aqueous solution) was used as the corrosion solution. In addition, the area ratio of the image identified by image analysis is 0.05% or more with respect to a visual field.

These results are combined with Table 1 and shown. In the table, "VG" is the wear amount of the valve guide, "VS" is the wear amount of the valve stem, and "total" is the total value of the wear amount of the valve guide and the wear amount of the valve stem. In the following examination, as a level which can be used as a valve guide, the target value of a pressurizing strength was made into about 500 MPa or more, and the target value of the amount of abrasion was evaluated as a total wear amount of 75 micrometers or less.

The samples of Table Nos. 01 to 10 in Table 1 show the influence of the amount of Cu in the overall composition of the sintered valve guide material and the effect of the amount of copper powder added in the raw material powder. In the samples of Sample Nos. 01 to 06 whose Cu amount (copper powder addition amount) was 2.5% by mass or less, the area ratio of the plate-shaped iron carbide phase in the cross section of the metal structure was almost constant, and the iron equivalent to the conventional example (Sample No. 11). The carbide phase is deposited and dispersed. However, when Cu amount (copper powder addition amount) exceeds 2.5 mass%, the area ratio of the plate-shaped iron carbide phase in a metal structure cross section shows the tendency to decrease, and in the sample (sample number 09) whose Cu amount is 4.0 mass%, The area ratio of the plate-shaped iron carbide phase is reduced to about 3%, and the area ratio of the iron carbide phase is lowered to 1% in the sample (Sample No. 10) in which the amount of Cu exceeds 4.0% by mass.

The copper phase showed a tendency to increase in proportion to the amount of copper (copper powder addition amount), and in the sample (sample number 03) in which the amount of copper (copper powder addition amount) was 1.0% by mass, the area ratio of the copper phase in the metal structure cross section was 0.5%. In the sample (sample number 09) whose Cu amount (copper powder addition amount) is 4.0 mass%, the area ratio of a copper phase increases to 3.5%, and the sample (sample number 10) whose Cu amount (copper powder addition amount) exceeds 4.0 mass% ), The area ratio of the copper phase is increased to about 4%.

Although the rolling strength does not contain Cu in the sample of the sample number 01 whose Cu amount (copper powder addition amount) is 0 mass%, it has a low known strength and shows a low rolling strength, but Cu amount (copper powder addition amount) As the) increases, the known reinforcing action by Cu increases, indicating a tendency for the rolling strength to increase in proportion to the amount of Cu (copper powder addition). Here, in the samples of Sample Nos. 01 and 02 whose Cu amount (copper powder addition amount) is less than 1.0 mass%, the sample has low pressure-reduction strength and cannot tolerate use as a valve guide, but the Cu (copper powder addition amount) amount is 1.0 mass% or more. In (Sample Nos. 03 to 10), the compressive strength is 500 MPa or more, and strength that can be sufficiently used as a valve guide is obtained.

The valve stem wear amount is slightly worn in the sample of Sample No. 01 in which the Cu amount (copper powder addition amount) is 0% by mass, so that there is no copper phase to improve the compatibility, but the Cu amount (copper powder addition amount) is 0.5. In the sample of the sample number 02 which is the mass%, by disperse | distributing a copper phase, affinity improves and abrasion amount decreases, and the sample of sample numbers 03-10 whose Cu amount (copper powder addition amount) is 1.0 mass% or more is sufficient By dispersing a positive copper phase, the valve stem wear amount is low and becomes a constant value.

In the sample of Sample No. 01 in which the Cu amount (copper powder addition amount) is 0% by mass, the valve guide wear amount has a low known strength because it does not contain Cu. Therefore, the wear amount is also a large value, and the total wear amount is also a large value. It is. On the other hand, in the sample of the sample No. 02 whose amount of copper (copper powder addition amount) is 0.5 mass%, the known strength is improved by the known strengthening effect of Cu, and the amount of valve guide wear is reduced, and the total amount of wear is also reduced. Moreover, in Sample No. 03-06 whose Cu amount (copper powder addition amount) is 1.0-2.5 mass%, since the matrix reinforcement effect | action by Cu is fully acquired and the amount of precipitation of plate-shaped iron carbides is large, the valve guide wear amount is It is equivalent to the conventional example (Sample No. 11), and has a substantially constant low value. As a result, the total wear amount is also the same as the conventional example (Sample No. 11) and has a substantially constant low value. However, in the sample of Sample No. 07-09 whose Cu amount (copper powder addition amount) is 3.0-4.0 mass%, the fall of abrasion resistance by reduction of plate-shaped iron carbide rather than the known strengthening effect by Cu increases, and valve guide wear amount It shows a tendency to increase slightly. And in the sample of the sample No. 10 whose Cu amount (copper powder addition amount) exceeds 4.0 mass%, the fall of abrasion resistance by the reduction of iron carbide becomes remarkable, the valve guide wear amount increases and the total wear amount tends to increase. It is shown.

 From the above result, Cu amount (copper powder addition amount) shows the wear resistance substantially equivalent to the sintering valve guide material of Unexamined-Japanese-Patent No. 55-34858 in the range which is 1.0-4.0 mass%, and as a valve guide in this range. It was confirmed that it was the strength which can be used. Moreover, it was confirmed that the area ratio of the copper phase in a metal structure cross section in the said range is 0.5 to 3.5%. Moreover, it was confirmed that about 3% or more of area ratio of the plate-shaped iron carbide phase in a metal structure cross section is needed.

[Second Embodiment]

Using the iron powder, the copper powder, and the graphite powder used in the first embodiment, 2 mass% copper powder and graphite powder in the ratios shown in Table 2 were added to and mixed with the iron powder to prepare a raw powder. The obtained raw powder was shape | molded and sintered on the conditions similar to Example 1, and the sample of Sample Nos. 12-17 was produced. The whole composition of these samples is combined with Table 2, and is shown. In addition, in the same manner as in the first example, the abrasion test and the compression test were conducted on these samples, and the area ratio of the iron carbide phase and the area ratio of the copper phase were measured. This result is combined with Table 2 and shown. In addition, Table 2 also showed the value of the sample of sample number 05 of a 1st Example as an example that the addition amount of graphite powder is 2 mass%.

The sample numbers 05 and 12 to 17 of Table 2 show the influence of the amount of C in the overall composition of the sintered valve guide material and the effect of the graphite powder addition amount in the raw material powder. In the sample of Sample No. 12 having an amount of C (graphite powder addition amount) of 1% by mass, C diffused to a known base was insufficient, and a plate-like iron carbide phase was not precipitated. On the other hand, in the sample of Sample No. 13 in which the amount of C (graphite powder addition amount) is 1.3% by mass, C diffused to a known level is sufficient, and the area ratio of the plate-shaped iron carbide phase in the cross section of the metal structure is about 3%. . And as the amount of C (graphite powder addition amount) increases, the area ratio of the plate-shaped iron carbide phase in the metal structure cross section shows a tendency to increase, and the amount of C (graphite powder addition amount) of Sample No. 16 is 3% by mass. In the sample, in the sample of the sample No. 17 in which the area ratio of the plate-shaped iron carbide phase exceeded about 25% and the amount of C (the graphite powder addition amount) exceeded 3% by mass, the area ratio of the plate-shaped iron carbide phase increased to about 28%. On the other hand, in the copper phase, the amount of Cu (copper powder addition) is constant and the sintering conditions are constant, so that the area ratio in the metal structure cross section is a constant value regardless of the amount of C (graphite powder addition).

The rolling strength tends to decrease as the sample of Sample No. 12 in which the plate-shaped iron carbide phase is not precipitated in the matrix is the highest, and the amount of C (graphite powder added) is increased and the amount of the iron carbide phase precipitated in the matrix increases. It is shown. However, the sample (sample number 16) whose C amount (graphite powder addition amount) is 3 mass% has a rolling strength of about 500 MPa, and if C amount (graphite powder addition amount) is up to 3 mass%, it can be used sufficiently as a valve guide. Intensity is obtained.

In the sample of Sample No. 12 in which the amount of C (graphite powder addition amount) was 1% by mass, the iron carbide phase contributing to the improvement of wear resistance was not precipitated in the matrix, and the valve guide wear amount was a large value. On the other hand, in the sample of the sample No. 13 whose C amount (graphite powder addition amount) is 1.3 mass%, the plate-shaped iron carbide phase precipitates in a matrix, and the valve guide wear amount is reduced, and C amount (graphite powder addition amount) increases, The amount of plate-shaped iron carbide phases precipitated therein increases, and the wear amount of the valve guide is reduced due to the effect of improving the wear resistance caused by the plate-shaped iron carbide phases. This tendency is recognized even by the sample of sample number 15 whose C amount (graphite powder addition amount) is 2.5 mass%. However, in the sample of the sample No. 16 whose C amount (graphite powder addition amount) is 3 mass%, since the intensity | strength of a sintered compact sample falls because the plate-shaped iron carbide phase increases, the valve guide wear amount increases slightly and C amount (graphite powder) In the sample of the sample No. 17 whose addition amount) exceeds 3 mass%, the valve guide wear amount is increasing. The valve stem wear amount shows a tendency to increase as the amount of C (graphite powder added) increases because the amount of hard plate-shaped iron carbide phase precipitated in the matrix increases as the amount of C (graphite powder added) increases. From these abrasion conditions, it was confirmed that the total amount of abrasion is reduced in a range where the amount of C (graphite powder addition amount) is 1.3 to 3% by mass.

 From the above result, while the amount of C (graphite powder addition amount) is 1.3-3 mass%, it shows the wear resistance substantially equivalent to the sintering valve guide material of Unexamined-Japanese-Patent No. 55-34858, and as a valve guide in this range It was confirmed that it was the strength which can be used. Moreover, it was confirmed that the area ratio of the iron carbide phase in the metal structure cross section is 3 to 25% in the above range.

[Third Embodiment]

2 mass% copper powder and 2 mass% graphite powder are added and mixed to iron powder using the iron powder, copper powder, and graphite powder used in the 1st Example, the raw material powder is prepared, and is obtained. The raw material powder was molded under the same conditions as in the first example, and the samples of Sample Nos. 18 to 24 were sintered under the same conditions as in the first example except that the heating temperature at the time of sintering was changed to the temperature shown in Table 3. Produced. These samples were subjected to the abrasion test and the compression test in the same manner as in the first example, and the area ratio of the iron carbide phase and the area ratio of the copper phase were measured. This result is combined with Table 3 and shown. In addition, Table 3 also showed the value of the sample of sample number 05 of a 1st Example as an example of heating temperature of 1000 degreeC.

The influence of the heating temperature at the time of sintering is understood by the sample of 05, 18-24 of sample number of Table 3. The area ratio of the copper phase in the cross section of the metal structure shows a tendency to decrease and decrease the amount remaining as the copper phase because the amount of diffusion of Cu into the matrix increases as the heating temperature at the time of sintering increases. In the sample (Sample No. 24) whose heating temperature over 1 degreeC is 1100 degreeC, all the Cu added as copper powder diffuses into a matrix, and the copper phase is almost lost.

In a sample having a heating temperature of 900 ° C. (sample number 18) and a sample having a heating temperature of 950 ° C. (sample number 19), the heating temperature at the time of sintering is low, the diffusion of C is insufficient, and the plate-shaped iron carbide phase hardly precipitates. . On the other hand, in the sample (Sample No. 20, 05, 21) whose heating temperature is 970-1020 degreeC, sufficient C diffusion is acquired and the area ratio of the plate-shaped iron carbide phase in a metal structure cross section is a conventional example (Sample No. 11). Almost equal to However, as the heating temperature increases, the amount of Cu diffused to the matrix increases, making it difficult to form a plate-shaped iron carbide phase. Therefore, the precipitation amount of the plate-shaped iron carbide phase decreases and the area ratio of the plate-shaped iron carbide phase in the cross section of the metal structure decreases. . And in the sample (Sample No. 24) whose heating temperature exceeding melting | fusing point (1085 degreeC) of Cu is 1100 degreeC, as a result of spreading Cu uniformly in a matrix, it is not precipitated as a large plate-shaped iron carbide phase, and most are pearlite It is precipitated in shape and the area ratio of the plate-shaped iron carbide phase in the cross section of the metal structure is extremely small.

The crush strength shows a tendency to increase as the amount of Cu which contributes to the strengthening of the base increases as the heating temperature at the time of sintering increases. However, in the sample (Sample No. 19) whose heating temperature is 950 degreeC, since diffusion of Cu is inadequate, the compressive strength is less than 500 Mpa, and the strength required as a valve guide is not obtained. On the other hand, in the sample (Sample No. 20, 05, 21-24) whose heating temperature is 970 degreeC or more, as a result of the increase in the amount of diffusion of Cu to a base, the compressive strength of 500 Mpa or more is obtained, and sufficient strength is obtained as a valve guide. .

In a sample (Sample No. 18) having a heating temperature of 900 ° C., the diffusion of C is insufficient and the plate-shaped iron carbide phase contributing to wear resistance does not precipitate, so the valve guide wear amount is large. Moreover, also in the sample (Sample No. 19) whose heating temperature is 950 degreeC, C diffusion is still inadequate and some plate-shaped iron carbide phase precipitation occurs, but since the quantity is still inadequate, the amount of valve guide abrasion is still It is a large value. On the other hand, in the sample (sample number 20) whose heating temperature is 970 degreeC, C spread | diffusion is fully performed, and the precipitation amount of plate-shaped iron carbide phase becomes substantially the same as the conventional example (sample number 11), and valve guide wear amount is We reduce. Moreover, in the sample (sample numbers 05 and 21) whose heating temperature is 1000-1020 degreeC, the valve guide wear amount shows a lower value by said action. However, as the heating temperature increases, the amount of diffusion of Cu to the matrix also increases, and thus, in samples (Sample Nos. 22 and 23) having a heating temperature of 1050 to 1070 ° C, the plate-shaped iron precipitated as the heating temperature increases. The amount of carbide phase tends to decrease, and the amount of valve guide wear tends to increase slightly. For samples with a heating temperature exceeding 1070 ° C. (Sample No. 24), the amount of precipitated plate-shaped iron carbide phase decreases markedly and wear resistance is increased. It decreases and the valve guide wear amount is increasing. The valve stem wear amount is substantially constant regardless of the heating temperature. For this reason, the total amount of abrasion is reduced in the range of the heating temperature of 970-1070 degreeC.

 From the above results, when the sintered valve guide material is composed of an iron-copper-carbon sintered alloy, the heating temperature at the time of sintering shows good wear resistance in the range of 970 to 1070 ° C and can be used as the valve guide in this range. It was confirmed that it was strength.

[Fourth Embodiment]

Iron powder, copper powder, graphite powder, copper tin alloy powder (Sn content is 10 mass% and the balance remainder is Cu) used for the sample preparation of the prior art example (Sample No. 11), and tin used in Example 1, Powder was prepared, 3 mass% copper powder, 2 mass% graphite powder, and tin powder of the ratio shown in Table 4 were added and mixed with iron powder, the raw material powder was prepared, the obtained raw powder was prepared, Molded and sintered under the same conditions as in Example 1, samples of Sample Nos. 25 to 34 were prepared. The total composition of these samples is shown in Table 4 together. In addition, the abrasion test and the compression test were carried out on these samples in the same manner as in the first example, and the area ratio of the iron carbide phase and the area ratio of the copper alloy phase were measured. This result is combined with Table 4 and shown. In addition, in Table 4, the value of the sample of sample No. 07 of a 1st Example was shown together as an example of addition of tin powder.

The sample numbers 07 and 25 to 33 in Table 4 show the influence of the Sn content in the case of containing Sn. Moreover, the sample by the sample number 30 and the sample number 34 can be compared with the addition form of Sn.

By containing Sn in the sintering valve guide material, the area ratio of the plate-shaped iron carbide phase and the copper alloy phase in the metal structure cross section decreases, and as the amount of Sn increases, the degree of reduction of the area ratio of the iron carbide phase and the area ratio of the copper alloy phase Is growing. This is thought to be due to the increase in the amount of Cu—Sn liquid phase generated during sintering as the amount of Sn increases, and hence the amount of diffusion of Cu into the matrix. And in the sample (sample number 32) whose Sn amount is 0.5 mass%, the area ratio of the plate-shaped iron carbide phase in a metal structure cross section has about 5%, and the area ratio of copper alloy phase has about 0.5%, but Sn amount is 0.5 In the sample exceeding the mass% (Sample No. 33), the area ratio of the plate-shaped iron carbide phase in the metal structure cross section is reduced to less than 5% and the area ratio of the copper alloy phase to less than 0.5%.

The sample containing Sn (Samples Nos. 25 to 33) has a higher compressive strength as compared with the sample containing no Sn (Sample No. 07), and it can be seen that the compressive strength increases as the amount of Sn increases. . This is because the amount of Cu-Sn liquid generated at the time of sintering increases as the amount of Sn increases, thereby increasing the amount of diffusion of Cu into the matrix, and by covering the surface of the iron powder with wet Cu-Sn liquid. It is thought to be due to promoting the growth of the neck of iron powders. However, in the sample (Sample No. 25) which Sn amount is less than 0.05 mass%, the effect of the improvement of a rolling strength is small, and in the sample (Sample No. 26-33) whose Sn amount is 0.05% or more, The effect is remarkable.

The amount of valve guide wear is about the same as that of the sample (Sample Nos. 25 to 28) containing 0.01 to 0.2 mass% of Sn, and the amount of Sn is 0.3 to 0.5 mass%. (Sample Nos. 29-32) As described above, the amount of Sn increases and the plate-shaped iron carbide phase decreases as described above, whereas the amount of wear of the valve guide is considered to be insignificant, which is considered to be an effect of strength improvement due to the growth of the necks of the iron powders. However, in the sample (Sample No. 33) in which Sn amount exceeded 0.5 mass%, the fall of abrasion resistance by the reduction of a plate-shaped iron carbide phase became remarkable, and the valve guide wear amount is increasing rapidly. The valve stem wear amount is almost constant regardless of the Sn amount. For this reason, the total amount of abrasion is small in the range of 0.5 mass% or less, and shows favorable wear resistance.

 From the above, the strength of the sintering valve guide material can be improved by containing Sn in the sintering valve guide material by 0.05% by mass or more. However, when the amount of Sn exceeds 0.5% by mass, the wear resistance decreases. It was confirmed that it was necessary to be 0.05-0.5 mass%.

In addition, the sample (Sample No. 30) given in the form of tin powder as the provision form of Sn, and the sample (Sample No. 34) given in the form of copper tin alloy powder are the area ratio of the plate-shaped iron carbide phase in a metal structure cross section, The area ratio of the copper alloy phase is equal, and the compressive strength and the amount of wear are also equal. Therefore, it was confirmed that the form to which Sn is given does not have any problem in the form of tin powder and copper tin alloy powder. In addition, the copper tin alloy powder in sample number 34 contains 3.0 mass% of Cu and 0.33 mass% of Sn with respect to the whole composition.

[Fifth Embodiment]

2 mass% copper tin alloy powder and 2 mass% graphite powder are added to the iron powder using the iron powder and the graphite powder used in the first embodiment, and the copper tin alloy powder used in the fourth embodiment, The raw material powder was prepared by mixing, and the obtained raw powder was molded under the same conditions as in the first embodiment, and the sintered under the same conditions as in the first embodiment except that the heating temperature at the time of sintering was changed to the temperature shown in Table 5. The samples of Sample Nos. 35 to 42 were prepared in which the total composition was Cu: 1.8%, Sn: 0.2%, C: 2.0% by mass, and the balance consisting of Fe and unavoidable impurities. These samples were subjected to the abrasion test and the compression test in the same manner as in the first example, and the area ratio of the plate-shaped iron carbide phase and the area of the copper alloy phase were measured. This result is combined with Table 5 and shown.

The influence of the heating temperature at the time of sintering can be understood by the sample of the sample numbers 35-42 of Table 5. The area ratio of the copper phase in the cross section of the metal structure shows a tendency for the amount of Cu to diffuse into the matrix to decrease and decrease as the heating temperature during sintering increases.

In the sample (Sample No. 35) whose heating temperature is 900 degreeC, the heating temperature at the time of sintering is low, C diffusion is inadequate and an iron carbide phase hardly precipitates. On the other hand, in the sample (Sample No. 36) whose heating temperature is 950 degreeC, sufficient C diffusion is obtained, and the area ratio of the plate-shaped iron carbide phase in the metal structure cross section is increasing, and the sample whose heating temperature is 970-1050 degreeC ( In the sample numbers 37-40, the area ratio of the plate-shaped iron carbide phase in a metal structure cross section is substantially equivalent to the conventional example (sample number 11). However, in samples (Sample Nos. 41 and 42) having a heating temperature exceeding 1050 ° C, the amount of Cu diffused to the matrix increases, making it difficult to form a plate-shaped iron carbide phase. The area ratio of the plate-shaped iron carbide phase is decreasing.

The crush strength shows a tendency to increase as the amount of Cu which contributes to the strengthening of the base increases as the heating temperature at the time of sintering increases. However, in the sample (sample number 35) whose heating temperature is 900 degreeC, since diffusion of Cu is inadequate, the pressure reduction strength is less than 500 Mpa, and the strength required as a valve guide is not acquired. On the other hand, in the sample (Sample No. 36-42) whose heating temperature is 950 degreeC or more, as a result of the increase in the diffusion amount of Cu to a matrix, the compressive strength of 500 Mpa or more is obtained, and sufficient strength is obtained as a valve guide.

In a sample (Sample No. 35) having a heating temperature of 900 ° C., the diffusion of C is insufficient and the iron carbide phase contributing to wear resistance is not precipitated, so the valve guide wear amount is large. On the other hand, in the sample (sample number 36) whose heating temperature is 950 degreeC, C spread | diffusion is fully performed, the area ratio of the plate-shaped iron carbide phase increases to 11%, and the valve guide wear amount is reduced. Moreover, in the sample (Sample No. 37-39) whose heating temperature is 970-1020 degreeC, when the area ratio of the plate-shaped iron carbide phase increased to the grade equivalent to the conventional example (Sample No. 11), the valve guide wear amount was lowered. Indicates. However, as the heating temperature increases, the amount of diffusion of Cu to the matrix also increases, so that in the sample having a heating temperature of 1050 ° C. (Sample No. 40), the area ratio of the plate-shaped iron carbide phase that precipitates decreases to about 11%, so that the valve The amount of guide wear tends to increase slightly, and in samples (Sample Nos. 41 and 42) with a heating temperature exceeding 1050 ° C, the amount of precipitated iron carbide phase is significantly reduced, which lowers the wear resistance and the amount of valve guide wear increases. Doing. The valve stem wear amount is substantially constant regardless of the heating temperature. For this reason, the total amount of abrasion is reduced in the range of the heating temperature of 950-1050 degreeC.

 From the above result, when Sn was used, it was confirmed that the heating temperature at the time of sintering is the intensity | strength which can be used as a valve guide in this range while showing the favorable wear resistance in the range of 950-1050 degreeC.

[Sixth Embodiment]

2 mass% copper powder and 2 mass% graphite powder are added and mixed to iron powder using the iron powder, copper powder, and graphite powder used in the 1st Example, the raw material powder is prepared, and is obtained. When the raw material powder is molded and sintered under the same conditions as in the first embodiment, and cooled from the heating temperature to the normal temperature, the cooling rate in the temperature range is shown in Table 6 when cooling from 850 ° C to 600 ° C. The sample of Sample No. 43-47 was produced by changing into. These samples were subjected to the abrasion test and the compression test in the same manner as in the first example, and the area ratio of the plate-shaped iron carbide phase and the area of the copper phase were measured. This result is combined with Table 6 and shown. In addition, Table 6 also showed the value of the sample of the sample No. 05 of a 1st Example as an example that the cooling rate in the said temperature range is 10 degreeC / min.

The slower the cooling rate in the temperature range when cooling from 850 ° C to 600 ° C, the larger the area ratio of iron carbide in the cross section of the metal structure, and the faster the cooling rate, the smaller the area ratio of iron carbide. . That is, the supersaturation of C at room temperature, in the heating temperature region during sintering, but get dissolved in the austenite, and is precipitated as a supersaturated C is iron carbide (Fe ₃ C) in this temperature range. Slowly passing through this temperature range causes the precipitated iron carbide to grow, increasing the amount of iron carbide phase, and passing quickly through this temperature range has no time for the precipitated iron carbide to grow, resulting in a proportion of the pearlite structure in which fine iron carbides are dispersed. The amount of iron carbide phase decreases. Here, when the cooling rate in the temperature range at the time of cooling from 850 degreeC to 600 degreeC accelerates to 25 degree-C / min, the area ratio of the iron carbide phase in a metal structure cross section will be about 5%, and it is faster than that. The area ratio of ground iron carbides is less than 5%.

On the other hand, in the copper phase, supersaturated Cu is not precipitated and dispersed, but unspread copper powder remains as the copper phase, so that the area ratio of the copper phase in the metal structure cross section becomes a constant value regardless of the cooling rate.

The compressive strength shows a tendency to increase as the fine iron carbide increases and the amount of the plate-shaped iron carbide phase decreases as the cooling rate in the temperature range when cooling from 850 ° C to 600 ° C is faster. In addition, the valve guide wear amount shows a tendency to decrease as the amount of iron carbide phase contributing to wear resistance decreases as the cooling rate in the temperature range when cooling from 850 ° C to 600 ° C is faster. When the cooling rate in the temperature range at the time of cooling to more than 25 ° C is faster than 25 ° C / minute, the area ratio of the iron carbide phase is less than 5%, and the amount of valve guide wear is rapidly increasing.

 From the above result, the quantity of plate-shaped iron carbide phase can be adjusted by controlling the cooling rate in the temperature range when cooling from 850 degreeC to 600 degreeC, and the temperature range when cooling from 850 degreeC to 600 degreeC By making the cooling rate in 25 degrees C / min or less, it was confirmed that the area ratio of the plate-shaped iron carbide phase in a metal structure cross section can be 5% or more, and wear resistance can be made favorable. Moreover, if the cooling rate in the temperature range at the time of cooling from 850 degreeC to 600 degreeC is too slow, since the cooling time from heating temperature to room temperature will lengthen and manufacturing cost will increase by that much, it will be from 850 degreeC to 600 degreeC. It is preferable to make the cooling rate in the temperature range at the time of cooling into 5 degreeC / min or more.

[Seventh Embodiment]

2 mass% copper powder and 2 mass% graphite powder are added and mixed to iron powder using the iron powder, copper powder, and graphite powder used in the 1st Example, the raw material powder is prepared, and is obtained. When the raw material powder is molded and sintered under the same conditions as in the first example, and cooled from the heating temperature to the normal temperature, the cooling rate in the temperature range from 850 ° C to 780 ° C is set to 30 ° C / min. The temperature shown in 7 was kept constant once, and it cooled after making the cooling rate from 780 degreeC to 600 degreeC into 30 degreeC / min, and produced the sample of the sample numbers 48-51. These samples were subjected to the abrasion test and the compression test in the same manner as in the first example, and the area ratio of the plate-shaped iron carbide phase and the area of the copper phase were measured. This result is combined with Table 7 and shown. In addition, in Table 7, the cooling rate of this temperature range is 30 degreeC / min, and also showed the value of the sample of the sample number 47 of 6th Example as an example which does not hold constant temperature.

When cooling from heating temperature to normal temperature, in the sample (Sample No. 48-51) hold | maintained at constant temperature in the temperature range of 850 degreeC to 600 degreeC, in the 6th Example, plate-shaped iron carbide form in the metal structure cross section It can be seen that even when the area ratio is less than 5%, the area ratio of the plate-shaped iron carbide phase can be increased to 5% or more. Moreover, it turns out that the area ratio of plate-shaped iron carbides increases as a constant temperature holding time becomes long. That is, by maintaining constant temperature in the temperature range where C dissolved due to supersaturation in austenite is precipitated as iron carbide, the area ratio of the plate-shaped iron carbide phase can be increased by giving time for the precipitated iron carbide to grow. If the constant temperature holding time at the station becomes long, the area ratio of the plate-shaped iron carbide can be increased by that amount. Therefore, in the case of constant temperature holding at this temperature range, the plate-shaped iron carbide phase grows during constant temperature holding, so even if the cooling rate before and after the constant temperature holding temperature is not a problem.

On the other hand, since the supersaturated Cu does not precipitate and disperse | distribute, but the copper phase remains as a copper phase, the area ratio of the copper phase in a metal structure cross section becomes a fixed value irrespective of constant temperature holding time.

The shorter the constant temperature holding time in the temperature range of 850 ° C to 600 ° C, the less time the plate-shaped iron carbide grows, so that the area ratio of the plate-shaped iron carbide phase decreases, and the longer the constant temperature holding time, the longer the iron carbide grows. Since the area ratio of the plate-shaped iron carbide phase increases, the compressive strength shows a tendency to decrease as the constant temperature holding time becomes longer. Moreover, the valve guide wear amount tends to decrease with constant temperature holding time as the amount of plate-shaped iron carbide phase which contributes to abrasion resistance increases as the constant temperature holding time in the temperature range of 850 degreeC to 600 degreeC increases.

From the above results, the amount of the plate-shaped iron carbide phase can be adjusted by constant temperature holding at a temperature range of 850 ° C to 600 ° C. In the case of constant temperature holding, the holding time is set to 10 minutes or more, thereby the plate shape in the cross section of the metal structure. It was confirmed that the area ratio of the iron carbide phase of the phase was 5% or more, and the wear resistance could be made good. If the constant temperature holding time is too long, the cooling time from the heating temperature to the room temperature becomes long, and the manufacturing cost increases by that amount. Therefore, the constant temperature holding time is preferably 90 minutes or less.

Claims (15)

The total composition is, by mass ratio, C: 1.3 to 3%, Cu: 1 to 4%, and the balance consists of Fe and inevitable impurities,
In addition to the pores and the base structure except the pores, the base structure is composed of a mixed structure of a pearlite phase, a ferrite phase, an iron carbide phase, and a copper-based phase, and represents a metal structure in which graphite is dispersed in a part of the pores. ,
Area ratio to the metal structure when the cross-sectional metal structure is observed, wherein the iron carbide phase is 3 to 25%, the copper-based phase is the copper phase, and the area ratio to the metal structure when the cross-sectional metal structure is observed, 0.5 Sintering valve guide material, characterized in that ~ ~ 3.5%. The method according to claim 1,
Sn: 0.05-0.5 mass% is further contained in the whole composition, and the said copper system phase is a copper and / or copper tin alloy phase, The sintering valve guide material characterized by the above-mentioned. The method according to claim 1,
The said iron carbide phase is plate-shaped iron carbide whose area ratio with respect to this field | view is 0.05% or more in the visual field of the cross-sectional structure of 200 times the magnification, and the total area of the plate-shaped iron carbide whose area ratio with respect to the said field | field is 0.15% or more is said Sintering valve guide material, characterized in that 3 to 50% of the total area of the plate-shaped iron carbide. The method according to claim 1,
At least one of the manganese sulfide particles, the magnesium silicate mineral particles, and the calcium fluoride particles is dispersed by 2 mass% or less in the powder grain boundary and the pores of the matrix structure. Copper for forming graphite powder and copper-based phase in iron powder so that the total composition of raw material powder may be C: 1.3-3%, Cu: 1-4%, and remainder consists of Fe and an unavoidable impurity by mass ratio. Raw material powder preparation process to add and mix powder,
A step of filling and pressurizing and compressing the raw material powder into a mold-shaped cylindrical tube cavity, and molding the raw material powder into a cylindrical green compact;
And a step of sintering the green compact at a heating temperature of 970 ° C to 1070 ° C in a non-oxidizing atmosphere. The method according to claim 5,
Sn: 0.05 to 0.5% is added to the total composition of the raw material powder, and the powder for forming the copper-based phase is any one of copper powder and tin powder, copper tin alloy powder, and copper powder and copper tin alloy powder, The said heating temperature is 950-1050 degreeC, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method according to claim 5,
The holding time in the said heating temperature is 10 to 90 minutes, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method according to claim 5,
In the cooling process from the said heating temperature to room temperature, the cooling rate in the said temperature range at the time of cooling from 850 degreeC to 600 degreeC is 5-20 degreeC / min, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method according to claim 5,
The cooling method from said heating temperature to room temperature WHEREIN: The manufacturing method of the sintering valve guide material characterized by cooling after hold | maintaining constant temperature for 10 to 90 minutes in the area | region between 850 degreeC and 600 degreeC. The method according to claim 5,
In the raw material powder preparation step,
At least one powder selected from manganese sulfide powder, magnesium silicate mineral powder, and calcium fluoride powder is further added so that it may become 2 mass% or less of the said raw material powder, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method according to claim 2,
At least one of the manganese sulfide particles, the calcium fluoride particles, and the magnesium silicate-based mineral particles is dispersed at 2% by mass or less in the powder grain boundary and the pores of the matrix structure. The method of claim 6,
In the cooling process from the said heating temperature to room temperature, the cooling rate in the said temperature range at the time of cooling from 850 degreeC to 600 degreeC is 5-20 degreeC / min, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method of claim 6,
The cooling method from said heating temperature to room temperature WHEREIN: The manufacturing method of the sintering valve guide material characterized by cooling after hold | maintaining constant temperature for 10 to 90 minutes in the area | region between 850 degreeC and 600 degreeC. The method of claim 6,
In the raw material powder preparation step,
At least one powder selected from manganese sulfide powder, magnesium silicate mineral powder, and calcium fluoride powder is further added so that it may become 2 mass% or less of the said raw material powder, The manufacturing method of the sintering valve guide material characterized by the above-mentioned. The method according to claim 2,
The said iron carbide phase is plate-shaped iron carbide whose area ratio with respect to this field | view is 0.05% or more in the visual field of the cross-sectional structure of 200 times the magnification, and the total area of the plate-shaped iron carbide whose area ratio with respect to the said field | field is 0.15% or more is said Sintering valve guide material, characterized in that 3 to 50% of the total area of the plate-shaped iron carbide.

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