WO2015099148A1 - Élément résistant à l'usure et dispositif support d'enroulement doté de celui-ci, et dispositif d'étanchéification d'arbre - Google Patents

Élément résistant à l'usure et dispositif support d'enroulement doté de celui-ci, et dispositif d'étanchéification d'arbre Download PDF

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WO2015099148A1
WO2015099148A1 PCT/JP2014/084604 JP2014084604W WO2015099148A1 WO 2015099148 A1 WO2015099148 A1 WO 2015099148A1 JP 2014084604 W JP2014084604 W JP 2014084604W WO 2015099148 A1 WO2015099148 A1 WO 2015099148A1
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Prior art keywords
wear
less
resistant member
silicon nitride
columnar crystals
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PCT/JP2014/084604
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English (en)
Japanese (ja)
Inventor
和洋 石川
健司 小松原
諭史 清田
織田　武廣
裕也 中尾
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京セラ株式会社
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Priority to JP2015555057A priority Critical patent/JP6075811B2/ja
Publication of WO2015099148A1 publication Critical patent/WO2015099148A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
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    • F16C33/32—Balls
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    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Definitions

  • the present invention relates to a wear-resistant member, a rolling support device including the same, and a shaft seal device.
  • a wear-resistant member made of a ceramic sintered body is used for the required portion.
  • Such a ceramic sintered body is usually manufactured by molding and firing ceramic powder, and then densifying using a hot isostatic pressing method (HIP method), and is a wear-resistant member.
  • HIP method hot isostatic pressing method
  • Various silicon nitride sintered bodies have been studied as ceramic sintered bodies.
  • Patent Document 1 contains silicon nitride particles and a sintering aid component containing a rare earth element in the range of 1 to 6% by mass and Al in the range of 0.5 to 6% by mass, Further, at least one metal element selected from Ti, Zr, Hf, W, Mo, Ta, Nb and Cr is contained in a range of 0.01% by mass to 5% by mass as a single metal element or a compound of the metal element.
  • the needle-like crystal particles having a major axis L of 10 ⁇ m or less and a ratio of the major axis L to the minor axis S (L / S) of 5 or more are sintered with silicon nitride.
  • the area ratio is in the range of 50% to 80%, the maximum diameter of voids present in the silicon nitride sintered body is 2 ⁇ m or less, and the number of voids is 30 ⁇ 30 ⁇ m
  • a silicon nitride sintered body having 5 or less in the range has been proposed. .
  • a lubricant is used in order to suppress direct contact, but the silicon nitride-based sintering proposed in Patent Document 1 is used.
  • the maximum diameter of pores is as small as 2 ⁇ m or less, such as the body, or when the number is small, the amount of lubricant that can be retained during sliding is small, wear-resistant members or wear-resistant The durability is lowered by the direct contact between the sex member and the member holding the sex member, or by adhesion.
  • the present invention has been devised to satisfy the above-described requirements, and provides a wear-resistant member having a high durability for a lubricant and having a high durability, a rolling support device including the same, and a shaft seal device.
  • the purpose is to do.
  • the wear-resistant member of the present invention is made of a silicon nitride ceramic having a columnar crystal of silicon nitride, the first columnar crystal and pores made of silicon nitride are present on the surface, and the first column is formed inside the pores.
  • the second columnar crystals made of silicon nitride having a diameter larger than that of the columnar crystals are interlaced with each other, and the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface is 5 or more. The number is 28 or less.
  • the rolling support device of the present invention includes a first member and a second member each having a raceway surface, and a plurality of rolling elements, and the first member and the second member are arranged to face each other,
  • the rolling element is disposed between the raceway surfaces so as to be freely rotatable, and the rolling element is composed of the wear-resistant member having the above-described configuration.
  • the shaft seal device of the present invention includes a mechanical seal ring composed of a fixed member and a movable member, and at least one of the fixed member and the movable member is composed of an abrasion-resistant member having the above-described configuration. To do.
  • the lubricant can be appropriately retained and has high durability, so that it can be used for a long period of time.
  • the rolling support device and the shaft seal device of the present invention since it can be used for a long period of time, it has high reliability.
  • the rolling bearing which is an example of embodiment of the rolling support apparatus of this invention is shown, (a) is sectional drawing, (b) is a perspective view which shows the holder
  • the wear-resistant member of this embodiment is made of silicon nitride ceramics having a silicon nitride columnar crystal, and sometimes has a first columnar crystal (hereinafter simply referred to as a first columnar crystal) made of silicon nitride on the surface. ) And pores, and inside the pores, second columnar crystals made of silicon nitride having a diameter larger than that of the first columnar crystals (hereinafter sometimes simply referred to as second columnar crystals) are interlaced with each other.
  • the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface is 5 or more and 28 or less.
  • the silicon nitride ceramic is a material containing 78% by mass or more of silicon nitride among all components constituting the ceramic, and the content is, for example, nitrogen (N) or silicon obtained by quantitative analysis. from the value of (Si), it may be obtained in terms of silicon nitride (Si 3 N 4).
  • the surface on which the first columnar crystals and pores exist is a polished surface and a sliding surface. Note that the sliding surface is a sliding surface including not only the initial state but also a surface that newly appears after wearing after sliding.
  • the wear-resistant member of the present embodiment has the second columnar crystal because the second columnar crystal having a diameter larger than that of the first columnar crystal is present inside the pores so as to cross each other. Since the surface area inside the pores is larger than when the second columnar crystals are not interlaced, the amount of lubricant retained in the pores is increased. In addition, since the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface is 5 or more and 28 or less, an appropriate amount of lubricant is maintained without substantially impairing wear resistance. can do.
  • the sliding surface which is the surface, has 5 to 28 pores with a maximum diameter of 3 ⁇ m to 9 ⁇ m per 1.2 mm 2 area, and the inside of the pores is thicker than the first columnar crystal. Since the second columnar crystals are interlaced with each other, the lubricant can be gradually supplied to the sliding surface without causing the lubricant to flow out instantaneously.
  • the wear-resistant member of the present embodiment has a high durability because it becomes difficult for a shortage of lubricant to occur on the sliding surface and the sliding characteristics can be maintained over a long period of time.
  • the state in which the diameter of the second columnar crystal is larger than that of the first columnar crystal can be confirmed by the following method.
  • 5 to 10 columnar crystals existing on the surface and pores are selected in an image with a magnification of 4000 to 10000 times taken using a scanning electron microscope (SEM), and the first existing on the surface.
  • the width (W1) in the vertical direction (minor axis direction) at the midpoint in the longitudinal direction of one columnar crystal is measured.
  • the width (W2) at the midpoint in the longitudinal direction of the second columnar crystal existing in the pores is measured.
  • a state where the average value of W2 is larger than the average value of W1 is that the diameter of the second columnar crystal is larger than that of the first columnar crystal.
  • the average value of W2 is preferably 1.5 times or more of the average value of W1.
  • the effect of suppressing grain growth in the second columnar crystal existing inside the pores is adjusted by adjusting the nitrogen partial pressure during firing.
  • a large amount of the metal element oxide may be volatilized to grow the second columnar crystal.
  • the columnar crystals protruding on the surface of the silicon nitride ceramics are also grown, but the columnar crystals protruding on the surface of the siliconized ceramic are removed by polishing. There is no protrusion on the surface of the wear resistant member of this embodiment.
  • the first columnar crystal existing on the polished surface is constrained by the adjacent crystal, and the volatilization of the oxide of the metal element in the first columnar crystal is small, and the grains of the first columnar crystal Since the growth is suppressed, the mechanical strength of the wear resistant member is maintained.
  • the state in which the second columnar crystals are interlaced is an SEM image taken at a magnification of 4000 to 10,000 times, where the second columnar crystals are in contact with each other and their axes are at an arbitrary angle.
  • the second columnar crystals need only be crossed on the image. Actually, the second columnar crystals may be close to each other even if they are not in contact with each other.
  • the pores on the surface of the wear-resistant member of the present embodiment have a function of holding the lubricant.
  • the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area is less than 5, the pores are retained.
  • the amount of lubricant that can be produced is not sufficient and the sliding properties cannot be maintained over a long period of time.
  • the number of pores with a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area exceeds 28, the mechanical properties are low, and there are problems such as chipping around the pores when sliding, resulting in durability. Lower.
  • the sliding resistance at the start of sliding between the wear-resistant members or between the wear-resistant members and the members holding them may increase rapidly.
  • the wear resistant member of this embodiment has a variation coefficient represented by ⁇ V / X of 0.05 or more, where ⁇ V is the standard deviation of the maximum pore diameter and X is the average value of the maximum pore diameter. It is preferable that it is 0.6 or less.
  • the coefficient of variation represented by ⁇ V / X is 0.05 or more and 0.6 or less, foreign substances contained in the lubricant, wear-resistant material generated during sliding, and the like can be accommodated in the pores. Since the lubricant can be retained, the sliding characteristics can be maintained over a long period of time. In addition, since abnormally large pores are less likely to be present on the surface, the occurrence of problems due to lack of pore outline portions is reduced, and high durability is achieved.
  • the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface, the average value (X) of the maximum diameter of the pores, and the standard deviation ( ⁇ V) of the maximum diameter of the pores are optically measured.
  • a microscope set the magnification to 100 times, select the area where the pore size and distribution are observed on average, and the area is 1.2 mm 2 (for example, the horizontal length is 1.2 mm and the vertical length is A method called particle analysis of image analysis software “A image-kun” (registered trademark, manufactured by Asahi Kasei Engineering Co., Ltd., hereinafter simply referred to as image analysis software) is applied to an image in a range of 1.0 mm).
  • image analysis software A image-kun” (registered trademark, manufactured by Asahi Kasei Engineering Co., Ltd., hereinafter simply referred to as image analysis software) is applied to an image in a range of 1.0 mm).
  • the setting conditions of this method are the brightness of the particles, the method of binarization, and the small figure removal area are dark, manual, and 0 ⁇ m, respectively, and a threshold value that is an index indicating the brightness of the image is set to each point ( Each pixel) is measured by setting it to 0.88 times the peak value of the histogram indicating the brightness of each pixel.
  • pores having a maximum diameter of less than 3 ⁇ m are not included in the measurement because they do not contribute to retention of the lubricant and it is difficult to determine whether the pores are pores.
  • “averagely observed” means that a region where crystals or pores having an abnormally large diameter exist only in one place is intentionally selected in a region observed at a magnification of 100 times. It's just an exclusion.
  • the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface, the average value (X) and standard deviation of the maximum diameter of the pores ( ⁇ V) can be obtained.
  • the coefficient of variation ( ⁇ V / X) can be obtained by dividing the standard deviation ( ⁇ V) by the average value (X) of the maximum diameter of the pores.
  • the maximum pore diameter on the surface is the maximum length of a certain pore obtained using the image analysis software.
  • the first columnar crystal on the surface has an average aspect ratio of 1.2 or more and 3.5 or less.
  • the average value of the aspect ratio of the first columnar crystals is 1.2 or more and 3.5 or less, the first columnar crystals are interlaced to increase fracture toughness and to form a dense structure with high hardness. Therefore, the durability of the wear resistant member is improved.
  • the average aspect ratio is more preferably 1.8 or more and 3.5 or less.
  • the average value of the aspect ratio of the first columnar crystal on the surface may be obtained in accordance with JIS R 1670-2006. Specifically, using an image with a magnification of 2000 times taken with an SEM, an area in which the size and distribution of columnar crystals are observed on the surface on average (the area is 2730.5 ⁇ m 2 (the lateral length is 63.5 ⁇ m The vertical length is 43 ⁇ m)), and at least 100 of the first columnar crystals are measured. Then, the major axis and minor axis of the target first columnar crystal are measured, the aspect ratio (major axis / minor axis) is obtained, and the average value may be calculated.
  • the total area of the first columnar crystals whose major axis is less than 3 ⁇ m is 50% or more, and the major axis is 5 ⁇ m or more.
  • the total area of the first columnar crystals is preferably 10% or more.
  • the remaining area corresponds to the first columnar crystal, grain boundary phase, and pores having a major axis of 3 ⁇ m or more and less than 5 ⁇ m.
  • the length of the cracks generated at the initial stage during sliding depends on the crystal grain size, but the total area of the first columnar crystals whose major axis is less than 3 ⁇ m 50% or more, the resulting cracks tend to be fine cracks, and even if these cracks progress, the growth of cracks stops due to the presence of large columnar crystals with a major axis of 5 ⁇ m or more.
  • the wear resistant member has excellent durability.
  • the percentage of the total area of the first columnar crystals whose major axis is less than 3 ⁇ m and the percentage of the total area of the first columnar crystals whose major axis is 5 ⁇ m or more out of 100% of the area of the surface observation area is SEM. 4 areas where the distribution of crystals is observed on average from the area of 24574.5 ⁇ m 2 (the length in the horizontal direction is 190.5 ⁇ m and the length in the vertical direction is 129 ⁇ m) Select.
  • the area per range is set to be, for example, 2730.5 ⁇ m 2 (63.5 ⁇ m in the horizontal direction and 43 ⁇ m in the vertical direction).
  • the major axis and minor axis of the first columnar crystal in each range are measured, the area is calculated assuming that both crystals are elliptical, and the major area is less than 3 ⁇ m with the total area (4 ⁇ 2730.5 ⁇ m 2 ) as the denominator.
  • the total area of the first columnar crystals and the total area of the first columnar crystals whose major axis is 5 ⁇ m or more may be expressed as a percentage.
  • the wear-resistant member of the present embodiment has a silicide formed of at least one of iron and tungsten (hereinafter sometimes simply referred to as silicide) on the surface, and an equivalent circle diameter of 0.05 ⁇ m or more.
  • the number of silicides having a size of 5 ⁇ m or less is preferably 2.0 ⁇ 10 4 pieces / mm 2 or more and 2.0 ⁇ 10 5 pieces / mm 2 or less.
  • the first columnar crystal is exposed to a high temperature. Even if a microcrack occurs in the inside, the presence of the silicide in the above-described range can suppress or deflect the microcrack, and thus has high fracture toughness at high temperatures. Further, in the sintering process, the presence of the silicide in the above-mentioned range is unlikely to hinder the growth of the first columnar crystals in the sintering process, and the first columnar crystals exist in an interlaced manner. Therefore, it has excellent mechanical properties.
  • the presence of silicide consisting of iron and tungsten on the surface may be measured and identified using an X-ray diffractometer (XRD). It can also be confirmed by detecting iron and silicon or tungsten and silicon in a measurement using an energy dispersive X-ray analyzer (Energy Dispersive X-ray Spectroscopy: EDS). Further, the dispersal can be confirmed by SEM observation because these silicides are different in color tone from the crystal of silicon nitride, but in mapping using an electron beam microanalyzer (EPMA) This can also be confirmed by the fact that the location of silicon and the location of silicon overlap, or the location of tungsten and the location of silicon overlap.
  • XRD X-ray diffractometer
  • the number of silicides having an equivalent circle diameter of 0.05 ⁇ m or more and 5 ⁇ m or less can utilize a color tone difference from a silicon nitride crystal.
  • a portion where the presence of silicide is observed on the surface on average is selected using a SEM at a magnification of 2000 times, and an image in a range where the area becomes 2730.5 ⁇ m 2 may be analyzed by image analysis software.
  • the measurement conditions are as follows: the brightness of the particles is bright, the binarization method is manual, the small figure removal area is 0 ⁇ m, and the threshold value, which is an index indicating the brightness of the image, is set to 200 Good.
  • the average value of the circularity in the above-described silicide is 0.6 or more and 0.9 or less.
  • the average circularity of the silicide is 0.6 or more and 0.9 or less, even if it is exposed to high temperature and thermal stress is generated in the silicide, the residual stress is easy to disperse.
  • microcracks originating from the periphery of the silicide are less likely to occur, so that excellent mechanical properties can be maintained even at high temperatures.
  • the average value of the circularity of the silicide may be obtained by analyzing with image analysis software in the same manner as when measuring the number of silicides.
  • the silicon nitride ceramic constituting the wear resistant member of the present embodiment may contain a metal element oxide.
  • the metal element oxide is at least one of aluminum oxide, calcium oxide, magnesium oxide, and rare earth element (RE) oxide.
  • the metal element oxide is contained in the grain boundary phase and the columnar crystal. Will exist.
  • the sintering of the silicon nitride ceramics that become the wear resistant member is promoted, so that the mechanical characteristics can be enhanced.
  • an oxide of a rare earth element is included, and the rare earth element is at least one of erbium (Er), ytterbium (Yb), and lutetium (Lu). Is preferred.
  • the rare earth element oxide has a small volume expansion due to temperature change (small thermal expansion coefficient)
  • the inclusion of the rare earth element oxide can improve the thermal shock resistance of the wear resistant member made of silicon nitride ceramics. .
  • silicon nitride ceramics having columnar crystals of silicon nitride contain a metal element oxide.
  • the silicon nitride content is 78% by mass or more, and among the total 100% by mass of calcium oxide, aluminum oxide and rare earth element oxide, the content of calcium oxide is 0.3% by mass or more and 1.5% by mass or less.
  • the content is 14.2% by mass or more and 48.8% by mass or less, and the balance is a rare earth element oxide.
  • the bulk density of the silicon nitride ceramic is increased and the wear resistance is high. It can be a sex member.
  • each content in the total of 100 mass% of the oxide of aluminum oxide, calcium oxide, and rare earth elements can be calculated
  • the contents of Al, Ca, and RE are determined using an X-ray fluorescence analyzer (XRF) or an inductively coupled plasma (ICP) emission spectrometer (ICP), and aluminum oxide (Al 2 O 3 ) and oxidation are respectively obtained.
  • the values converted into oxides may be summed, the summed value may be used as the denominator, and the numerator may be expressed in percentage as the value converted into each oxide.
  • the value converted into an oxide is the content of 100% by mass of all components constituting the silicon nitride ceramic.
  • the content of silicon nitride (Si 3 N 4) is or obtained by conversion from the Si content obtained by XRF or ICP on Si 3 N 4, Si 3 from the N content was determined by nitrogen analysis apparatus it may be obtained in terms of N 4. Further, the content of components other than Si and N contained in the silicon nitride ceramics is obtained by XRF or ICP, and the values converted into oxides are totaled, and the value obtained by subtracting the total value from 100% by mass is nitrided. It is good also as content of silicon.
  • silicon nitride ceramics contains silicon oxide formed by oxidation of part of silicon nitride, all oxygen contained in the silicon nitride ceramics using an oxygen analyzer (LE-CO, model TC-136) Measure the amount, determine the content of components other than Si and N determined by XRF or ICP, subtract the total amount of oxygen required for conversion of oxides of these components from the total amount of oxygen, The content of silicon oxide may be obtained by converting the content of O) to silicon oxide (SiO 2 ).
  • the content of silicon nitride (Si 3 N 4 ) is determined from the content of Si (total silicon amount) obtained by XRF or ICP. What is necessary is just to convert using the value which deducted content of the silicon required for conversion.
  • FIG. 1 shows a rolling bearing which is an example of an embodiment of a rolling support device of the present embodiment, (a) is a sectional view, and (b) is a perspective view showing a cage of the rolling bearing shown in (a).
  • FIG. 1 shows a rolling bearing which is an example of an embodiment of a rolling support device of the present embodiment, (a) is a sectional view, and (b) is a perspective view showing a cage of the rolling bearing shown in (a).
  • the rolling bearing 10 in the example shown in FIG. 1A includes a first member (outer ring) 11 and a second member (inner ring) 12 having raceway surfaces 11a and 12a arranged to face each other, And a plurality of rolling elements 13 which are arranged between the raceway surfaces 11a and 12a so as to be freely rollable.
  • the size of the rolling element 13 is, for example, a sphere having a diameter of 40 mm or more and 60 mm or less.
  • a counter bore 12b is formed on one side of the rolling element 13 on the raceway surface of the second member (inner ring) 12 so as to be inclined from the raceway surface 12a of the second member (inner ring) 12.
  • the counter bore 12b is for facilitating the attachment of the rolling element 13 between the first member (outer ring) 11 and the second member (inner ring) 12.
  • the cage 14 shown in FIG. 1 (b) has an annular shape and holds the rolling elements 13 by pockets 14a arranged at equal intervals in the circumferential direction.
  • the rolling element 13 is made of the wear resistant member of the embodiment.
  • the rolling elements 13 constituting the rolling support device 10 of the present embodiment are made of the wear-resistant member of the present embodiment, so that good sliding characteristics can be maintained even if used for a long time. Can be used continuously for a long time. Moreover, since the replacement frequency of the members is small, the operation efficiency can be improved.
  • the first member (outer ring) 11 and the second member (inner ring) 12 are preferably made of the wear-resistant member of this embodiment.
  • FIG. 2 is a cross-sectional view showing an example of a shaft seal device including a mechanical seal ring made of an abrasion-resistant member according to this embodiment.
  • the shaft seal device 20 includes a mechanical seal ring 21 including a fixed member 21a that is an annular body and a movable member 21b that is an annular body having a convex portion, and at least one of the fixed member 21a and the movable member 21b is a main member. It consists of the abrasion-resistant member of embodiment.
  • the mechanical seal ring 21 is attached between a rotating shaft 22 that transmits a driving force by a driving mechanism (not shown) and a casing 23 that rotatably supports the rotating shaft 22, and is movable with the fixed member 21a.
  • Sliding surfaces 21 as and 21 bs with the member 21 b are installed so as to form a vertical surface with respect to the rotation shaft 22.
  • the fixing member 21a is supported by a buffer rubber 27 attached to the inside of the casing 23 that is an outer frame of the shaft seal device 20.
  • a collar 26 fixed by a set screw 28, a coil spring 25, and a packing 24 are installed on the rotary shaft 22 in this order toward the mechanical seal ring 21, and the movable member 21b is supported by the packing 24 in a buffered manner. ing.
  • the fluid 30 is moved outside the shaft seal device 20 by the sealing action by the O-ring 29 provided between the packing 24 and the rotary shaft 22 and the sealing action of the sliding surfaces 21as and 21bs of the mechanical seal ring 21. Prevents leakage. A part of the fluid 30 enters between the sliding surfaces 21as and 21bs of the mechanical seal ring 21 and acts as a lubricating liquid.
  • the shaft seal device 20 of the present embodiment when the movable member 21b starts to slide, dynamic pressure is generated between the sliding surfaces 21as and 21bs, and the generated hydraulic pressure causes the lubricating liquid to flow into the sliding surface. It tends to flow out of 1as and 21bs, but at least one of the sliding surfaces 21as and 21bs as the surface has 5 to 28 pores with a maximum diameter of 3 to 9 ⁇ m per 1.2 mm 2 area. Since the second columnar crystals having a diameter larger than that of the first columnar crystals are mixed with each other in the pores, the lubricating liquid does not instantaneously flow out by the dynamic pressure, and the sliding surfaces 21as and 21bs Can be gradually supplied.
  • the shaft seal device 20 of the present embodiment includes the mechanical seal ring 21 made of the wear-resistant member of the present embodiment, it maintains good sliding characteristics even if it is used for a long period of time. Can be used continuously for a long time. Moreover, since the replacement frequency of the members is small, the operation efficiency can be improved.
  • silicon nitride powder and powders of calcium oxide, aluminum oxide and rare earth element oxide as a sintering aid are wet mixed using a barrel mill, rotary mill, vibration mill, bead mill or attritor, etc. Grind into a slurry.
  • each sintering aid includes, for example, a calcium oxide content of 0.3% by mass or more and 1.5% by mass or less, out of a total of 100% by mass of calcium oxide, aluminum oxide and rare earth element oxide, and aluminum oxide.
  • the content of is 14.2 mass% or more and 48.8 mass% or less, and the balance is oxides of rare earth elements.
  • the silicon nitride powder used has a particle size (D 90 ) of 3 ⁇ m or less with a cumulative volume of 90% when the sum of the cumulative volume of the particle size distribution curve is 100%, or in the pulverization described above. It is preferable to grind to 3 ⁇ m or less from the viewpoint of improving the sinterability and making the crystal structure columnar.
  • organic binders such as paraffin wax, polyvinyl alcohol (PVA), and polyethylene glycol (PEG), are mixed with a slurry at 1 mass% or more and 10 mass% or less with respect to the total 100 mass% of the added powder. Is preferred for formability.
  • the slurry is passed through a sieve having a particle size number of 200 described in ASTM E 11-61 or a finer mesh than this mesh, and then granules are obtained by using a spray dryer.
  • the maximum diameter of the pores existing on the surface of the wear-resistant member can be controlled by the average particle diameter of the granules.
  • the average particle diameter of the granules May be 30 ⁇ m or more and 80 ⁇ m or less.
  • the average particle diameter of a granule by adjusting the rotational speed of the rotary atomizer (atomizer) with which the spray dryer was equipped.
  • the obtained granule is filled in a mold and molded by a uniaxial pressing method, and then a predetermined shape having a relative density of 45% or more and 60% or less by a cold isostatic pressing (CIP) method, for example, A spherical, flat or annular shaped body is used.
  • the molding pressure in the uniaxial pressing method is preferably 10 to 30 MPa
  • the molding pressure in the CIP method is preferably 50 to 100 MPa.
  • the obtained molded body is degreased in a nitrogen atmosphere or a vacuum atmosphere.
  • the degreasing temperature varies depending on the kind of the added organic binder, but it is preferably 900 ° C. or lower, and particularly preferably 500 ° C. or higher and 800 ° C. or lower.
  • the shaped body is placed in a firing furnace in which a graphite resistance heating element used for firing a general silicon nitride shaped body is placed and fired.
  • the temperature is raised from room temperature to 300 to 1000 ° C. in a vacuum atmosphere, and then nitrogen gas is introduced to maintain the nitrogen partial pressure at 10 to 100 kPa.
  • the open porosity of the compact is about 40 to 55%, the compact is sufficiently filled with nitrogen gas.
  • the temperature is continuously increased and the temperature is maintained at 1750 ° C. for 1 to 2 hours in order to obtain a fine crystal structure.
  • the temperature is further raised, and the firing temperature is set to 1800 ° C. or higher and 1860 ° C. or lower, and the holding time is 3 to 5 hours.
  • the baking may be performed at a baking temperature of 1730 ° C. or higher and 1750 ° C. or lower and a holding time of 12 to 16 hours.
  • the firing temperature is set to 1800 ° C. or higher and 1860 ° C. or lower and the holding time is set to 3 to 5 hours
  • the oxide of the metal element in the second columnar crystal which has the effect of suppressing grain growth, is volatilized.
  • the second columnar crystal which is less constrained from the adjacent crystal than the first columnar crystal, grows more grains, and the second columnar crystals having a diameter larger than the first columnar crystal cross each other inside the pores. There will be more than one.
  • the same result as described above can be obtained even when the firing temperature is set to 1730 ° C. or higher and 1750 ° C. or lower and the holding time is set to 12 to 16 hours.
  • the nitrogen pressure when held at the firing temperature may be controlled to 100 kPa or more and 100 kPa or less.
  • a pressure of 150 MPa or more and 250 MPa or less by a hot isostatic pressing method (HIP method) after firing Should be added.
  • HIP method hot isostatic pressing method
  • the firing temperature may be 1810 ° C. or more and 1850 ° C. or less.
  • the total area of the first columnar crystals whose major axis is less than 3 ⁇ m is 50% or more, and the total area of the first columnar crystals whose major axis is 5 ⁇ m or more is
  • a silicon nitride powder having a particle size (D 50 ) with a cumulative volume of 50% of 1 ⁇ m or more and 2 ⁇ m or less is wet-mixed for 5 to 10 hours using a bead mill
  • particle size (D 50) is, for example, may be a slurry ground to be 0.5 ⁇ m or more 2 ⁇ m or less.
  • a silicide composed of at least one of iron and tungsten exists on the surface, and the number of silicides having an equivalent circle diameter of 0.05 ⁇ m or more and 5 ⁇ m or less is 2.0 ⁇ 10 4 pieces / mm 2 or more and 2.0 ⁇ 10 5 pieces.
  • at least one of ferric oxide powder and tungsten carbide powder is added to the silicon nitride powder and the sintering aid powder in the following amounts. That's fine.
  • ferric oxide powder having a specific surface area of 0.5 m 2 / g or more and 50 m 2 / g or less per 100 parts by mass of the silicon nitride powder and the sintering aid powder.
  • the powder of tungsten carbide having a specific surface area of 0.5 m 2 / g or more and 50 m 2 / g or less may be added in an amount of 0.6 parts by mass or more and 0.9 parts by mass or less.
  • both iron silicide and tungsten silicide are interspersed, and the number of silicides having an equivalent circle diameter of 0.05 ⁇ m or more and 5 ⁇ m or less is 2.0 ⁇ 10 4 pieces / mm 2 or more and 2.0 ⁇ 10 5 pieces / mm.
  • 0.5 m 2 / g to 50 m 2 / g of ferric oxide and tungsten carbide powders of 0.5 to 1 part by mass and 0.25 parts by mass, respectively. What is necessary is just to add more than 0.6 parts by mass.
  • ferric oxide powder added in this way reacts with silicon nitride in the firing step to release oxygen and produce iron silicide.
  • tungsten carbide powder reacts with silicon nitride in the firing step to desorb carbon and produce tungsten silicide.
  • the specific surface area of the ferric oxide powder and tungsten carbide powder to be added is 0.52 m 2 / g or more. It may be 0.65 m 2 / g or less.
  • the above-described manufacturing method can provide a highly durable wear-resistant member having an appropriate lubricant holding performance, and can be suitably used for a rolling support device, a shaft seal device, and the like.
  • a silicon nitride powder having an average particle size of 2.6 ⁇ m and calcium oxide, aluminum oxide, and yttrium oxide powders were mixed to obtain a mixed powder. Then, this mixed powder was put into a vibration mill together with water as a solvent, and pulverized and mixed for 72 hours to prepare a slurry.
  • Example Nos. 1 to 9 After degreasing in a nitrogen atmosphere at 600 ° C., it is placed in a firing furnace in which a graphite resistance heating element is installed, and fired at the nitrogen partial pressure, firing temperature and holding time shown in Table 1, A ligature was obtained. Then, the obtained sintered body was polished to obtain rolling elements (sample Nos. 1 to 9) having a diameter of 47.63 mm.
  • the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less on the surface is determined by an image with a magnification of 100 using an optical microscope (area 1.2 mm 2 (horizontal length 1.2 mm, vertical length 1.0 mm). )) was obtained by applying a technique called particle analysis of image analysis software.
  • the setting conditions in the particle analysis are as follows: the brightness of the particle is dark, the binarization method is manual, the small figure removal area is 0 ⁇ m, and the threshold value, which is an index indicating the brightness of the image, is set for each point in the image. It was measured by setting it to 0.88 times the peak value of the histogram indicating brightness.
  • the width at the midpoint in the longitudinal direction of the first columnar crystal existing on the surface is W1
  • the longitudinal direction of the second columnar crystal existing inside the pores The width at the midpoint was W2, and the number of samples was five.
  • the average value of the widths W1 of the first columnar crystals each having five samples was M (W1)
  • the average value of the widths W2 of the second columnar crystals was M (W2).
  • Sample No. Samples Nos. 4 to 8 are sample Nos.
  • the life is longer than 1 to 3, 9 and is made of a silicon nitride ceramic having a silicon nitride columnar crystal, the first columnar crystal and pores exist on the surface, and the first columnar shape is inside the pores.
  • Second columnar crystals having a diameter larger than that of the crystals are interlaced with each other, and the number of pores having a maximum diameter of 3 ⁇ m or more and 9 ⁇ m or less per 1.2 mm 2 area of the surface is 5 or more and 28 or less. It was found that the wear resistance was excellent.
  • Example No. shown in Example 1 No. 6 is fired by the same method as above, and then the temperature is 1580 ° C., the time is 1 hour, and the HIP treatment is performed at the pressure shown in Table 2, and the obtained sintered body is polished, whereby the diameter is 47.63 mm. Rolling elements (Sample Nos. 10 to 16) were obtained.
  • the coefficient of variation represented by ⁇ V / X was determined by calculating the average value and standard deviation of the maximum pore diameter by the same method as the method for calculating the number of pores described in Example 1. Calculated from the deviation.
  • sample no. Samples 11 to 15 are sample Nos. It has been found that when the lifetime is longer than 10 and 16, and the coefficient of variation represented by ⁇ V / X is 0.05 or more and 0.6 or less, the wear resistance is further improved.
  • Example 1 Degreasing is carried out by the same method as in No. 6, and then calcined at the calcining temperature shown in Table 3, and the obtained sintered body is polished to obtain a rolling element having a diameter of 47.63 mm (sample Nos. 17 to 23). Obtained.
  • the average value of the aspect ratio of the first columnar crystal on the surface was determined according to JIS R1670-2006 using an image with a magnification of 2000 times taken with an SEM.
  • sample No. Samples 18 to 22 are sample Nos. Fracture toughness higher than 17
  • the hardness is higher than 23, and the average value of the aspect ratio of the first columnar crystal on the surface is 1.2 or more and 3.5 or less, and it turns out to be a wear-resistant member with excellent fracture toughness and hardness. It was.
  • Sample No. shown in Example 1 A mixed powder similar to that of No. 6 was prepared, put into a bead mill with water as a solvent, and pulverized and mixed for the time shown in Table 4 to prepare a slurry. Then, except that it was a molded body from which a spherical body having a diameter of 10 mm was obtained after polishing, degreasing was performed in the same manner as shown in Example 1, nitrogen partial pressure was 600 kPa, firing temperature was 1740 ° C., holding time Was fired for 14 hours, and the obtained sintered body was polished to obtain rolling elements (sample Nos. 24-27) having a diameter of 10 mm.
  • the major axis and minor axis of the first columnar crystal in each range are measured, the area is calculated assuming that both crystals are elliptical, and the major area is less than 3 ⁇ m with the total area (4 ⁇ 2730.5 ⁇ m 2 ) as the denominator.
  • the total area of the first columnar crystals and the total area of the first columnar crystals whose major axis is 5 ⁇ m or more are expressed as percentages as molecules.
  • a wear test was performed using sample Nos. 24-27.
  • the disc-shaped test piece that is in sliding contact with the sample is made of SUJ2
  • the applied load is 10 N
  • the sliding speed of the disc-shaped test piece is 0.37 m / s
  • the sliding circle diameter is 14 mm
  • the sliding distance was 2000 m
  • ion-exchanged water was used as the lubricating fluid.
  • sample no. 24 to 26 are sample Nos.
  • the total area of the first columnar crystals whose major axis is less than 3 ⁇ m is 50% or more, and the major axis is 5 ⁇ m or more. It was found that the wear resistance is improved when the total area of a certain first columnar crystal is 10% or more.
  • Example 1 6 Sample No. shown in Example 1 6 and a ferric oxide powder and a tungsten carbide powder having a specific surface area shown in Table 5 were prepared, and the ferric oxide powder and the tungsten carbide powder with respect to 100 parts by mass of the mixed powder were prepared.
  • the addition amount was the addition amount shown in Table 5.
  • the sample No. 1 of Example 1 was prepared from the slurry preparation step except that a molded body having a size capable of forming a test piece for measuring fracture toughness and mechanical strength was obtained. 6 was prepared by the same method as in Sample No. 6. 28-42 were obtained.
  • silicide names measured and identified by XRD are shown in Table 5.
  • the number of silicides having an equivalent circle diameter of 0.05 ⁇ m or more and 5 ⁇ m or less is obtained by analyzing the SEM image at a magnification of 2000 times using image analysis software by utilizing the color difference with the crystal of silicon nitride. Asked.
  • the setting conditions were measured by setting the brightness of the particles to light, the binarization method to be manual, the small figure removal area to 0 ⁇ m, and the threshold value, which is an index indicating the brightness of the image, to 200.
  • test pieces for measuring the fracture toughness value and mechanical strength were cut out from each sample, and the fracture toughness value at 500 ° C. was measured according to JIS R 1617-2010. Also, JIS In accordance with R 1601-2008 (ISO 14704-2000 (MOD)), the four-point bending strength F 0 at room temperature was measured. The results are shown in Table 5.
  • sample no. Samples Nos. 29-31, 34-36 and 39-41 are sample Nos.
  • the fracture toughness value at a higher temperature is higher than that of Samples Nos. 28, 33 and 38.
  • Number of silicides whose four-point bending strength is higher than 32, 37 and 42, and there are silicides of at least one of iron and tungsten on the surface, and the equivalent circle diameter is 0.05 ⁇ m or more and 5 ⁇ m or less Is 2.0 ⁇ 10 4 pieces / mm 2 or more and 2.0 ⁇ 10 5 pieces / mm 2 or less, it was found that excellent mechanical properties are obtained.
  • Sample No. shown in Example 1 6 and a ferric oxide powder and a tungsten carbide powder having a specific surface area shown in Table 6 were prepared, and the ferric oxide powder and the tungsten carbide powder with respect to 100 parts by mass of the mixed powder were prepared.
  • the addition amount was the addition amount shown in Table 6.
  • sample No. 1 in Example 1 was obtained except that a molded body having a size capable of forming a test piece for measuring mechanical strength was used. 6 was prepared by the same method as in Sample No. 6. 43-60 were obtained.

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Abstract

　L'invention vise à procurer un élément résistant à l'usure très durable présentant une aptitude appropriée à retenir un lubrifiant, un dispositif support d'enroulement doté de l'élément résistant à l'usure, et un dispositif d'étanchéification d'arbre. L'invention concerne un élément résistant à l'usure comprenant une céramique au nitrure de silicium ayant des cristaux colonnaires de nitrure de silicium, des trous et des premiers cristaux colonnaires comprenant du nitrure de silicium présent sur la surface de la céramique au nitrure de silicium, des deuxièmes cristaux colonnaires comprenant du nitrure de silicium présentant un diamètre plus grand que les premiers cristaux colonnaires entremêlés au sein des trous, le nombre de trous ayant un diamètre maximum de 3 µm à 9 µm pour 1,2 mm2 d'aire dans la surface étant de 5 à 28. L'invention concerne un dispositif support d'enroulement doté de l'élément résistant à l'usure, et un dispositif d'étanchéification d'arbre.
PCT/JP2014/084604 2013-12-26 2014-12-26 Élément résistant à l'usure et dispositif support d'enroulement doté de celui-ci, et dispositif d'étanchéification d'arbre WO2015099148A1 (fr)

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JP2020117419A (ja) * 2019-01-24 2020-08-06 Ntn株式会社 セラミックス体及び転動体
WO2022050290A1 (fr) 2020-09-03 2022-03-10 Ntn株式会社 Corps fritté de nitrure de silicium, corps roulant l'utilisant, et palier

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JPWO2021225158A1 (fr) 2020-05-07 2021-11-11

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Publication number Priority date Publication date Assignee Title
JP2011016716A (ja) * 2010-07-14 2011-01-27 Toshiba Corp 窒化けい素焼結体
JP2011208676A (ja) * 2010-03-29 2011-10-20 Kyocera Corp 耐磨耗性部材およびこれを用いた転がり支持装置
JP2012106920A (ja) * 2010-10-27 2012-06-07 Kyocera Corp 溶湯金属用部材およびヒーターチューブ
JP2013234120A (ja) * 2007-03-15 2013-11-21 Toshiba Corp 窒化珪素焼結体とそれを用いた摺動部材

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JP2013234120A (ja) * 2007-03-15 2013-11-21 Toshiba Corp 窒化珪素焼結体とそれを用いた摺動部材
JP2011208676A (ja) * 2010-03-29 2011-10-20 Kyocera Corp 耐磨耗性部材およびこれを用いた転がり支持装置
JP2011016716A (ja) * 2010-07-14 2011-01-27 Toshiba Corp 窒化けい素焼結体
JP2012106920A (ja) * 2010-10-27 2012-06-07 Kyocera Corp 溶湯金属用部材およびヒーターチューブ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020117419A (ja) * 2019-01-24 2020-08-06 Ntn株式会社 セラミックス体及び転動体
JP7177711B2 (ja) 2019-01-24 2022-11-24 Ntn株式会社 セラミックス体及び転動体
WO2022050290A1 (fr) 2020-09-03 2022-03-10 Ntn株式会社 Corps fritté de nitrure de silicium, corps roulant l'utilisant, et palier

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