JP2979838B2 - Guide member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a guide member which can be preferably used for guiding a yarn or a film in a fiber manufacturing process or a synthetic resin film manufacturing process.

[0002]

2. Description of the Related Art Many guide members are used for stably running a yarn or a film or changing a running direction in a fiber manufacturing process or a synthetic resin film manufacturing process.

[0003] As such a guide member, a member made of carbon steel plated with hard chromium and a member made of carbon steel having an alumina sprayed film formed on the surface thereof are known. Further, ceramics such as alumina ceramics and silicon carbide ceramics are known.

[0004] However, in the former, the metal generally has low wear resistance, so that the surface wears quickly and the friction coefficient changes due to the plating or the sprayed film being peeled off. There is a problem that it is easy to cause cutting or to generate streaks on the surface.

[0005] Further, although the latter made of ceramics is excellent in abrasion resistance, ceramics are generally low in mechanical strength, so that the ceramics may be damaged by a slight impact at the time of mounting on a device or the like, or may be damaged during operation. There is a problem that it is easily damaged by vibration. In addition, alumina ceramics and silicon carbide ceramics have a low strength at the crystal grain boundaries, and when the yarn or film comes in contact at high speed, the crystal grains easily fall off.In that case, the coefficient of friction also changes, resulting in fluffing, yarn breakage, There is also a problem that streaks and the like are generated.

On the other hand, Japanese Patent Application Laid-Open No. Sho 59-138571 describes a guide member made of a ceramic mainly composed of zirconia having a fine crystal grain size. This guide member has excellent mechanical strength because it contains zirconia as a main component, but because of its fine crystal grain size, the contact area with the yarn or film is large, the frictional force becomes large, and fluffing or yarn breakage occurs. In addition, there is a problem that line scars and the like are easily generated.
In addition, in synthetic fibers and films, ceramic particles such as titania are often compounded. In this case, zirconia having a lower hardness than alumina or the like is worn in a relatively short period of time.

[0007] As attempts to solve such problems, JP-A 2-229758 Patent invention, the guide member comprising a composite ceramic of A1 ₂ O ₃ and ZrO _2, A1
_It has been proposed that crystal grains are coarsened by further containing ₂ TiO ₅ to improve frictional properties and to increase strength by ZrO ₂ . According to this, the friction characteristic is improved with increasing grain size, while, ZrO ₂ grains is taken into the abnormal grain growth was A1 ₂ O ₃ crystal grains, and the ZrO ₂ grains protruding There is a problem that yarn breakage, fluffing, streaks, and the like are easily caused.

As described above, it is difficult to say that all of the conventional guide members have well-balanced properties required for the guide member, such as abrasion resistance, mechanical strength, and friction characteristics with a yarn or a film. .

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional guide member, and to improve the abrasion resistance,
An object of the present invention is to provide a guide member having a good balance in mechanical strength and friction properties with a yarn or a film.

[0010]

In order to achieve the above-mentioned object, the present invention provides a Zr which contains A1 ₂ O ₃ as a main component and has at least 50% by volume of tetragonal crystal structure.
O ₂ and comprises in the range of 15 to 40 wt%, 1 to TiO ₂
5% by weight, MgO in a range of 0.1 to 1% by weight, average grain size in a range of 2 to 20 μm,
In addition, Z existing in the crystal grains of A1 ₂ O _{3 on} the surface
Provided is a guide member made of ceramics in which rO ₂ crystal grains are 2% or less of the whole ZrO ₂ . The average crystal grain size of ZrO ₂ is preferably in the range of 1.5 to 5 μm. Preferably, the center line average roughness of the surface is 0.2 to 3 μm.
m.

Although the wear mechanism of the guide member is not always clear, ceramics such as A1 ₂ O _{3 having} high hardness but low grain boundary strength preferentially suffer from particle detachment wear due to grain boundary destruction. Happen, and ZrO
It is presumed that those made of ceramics having high strength but low hardness, such as ₂ , have abrasion due to friction occurring preferentially. From this estimation, the present invention, the ZrO ₂ was dispersed in grain boundaries hardly A1 ₂ O ₃ is worn wear hardly occurs particles leaving wear of A1 ₂ O ₃ and, improves the abrasion resistance It is to improve the strength.

The ceramics constituting the guide member of the present invention contains A1 ₂ O ₃ as a main component and contains ZrO 2.
₂ in the range of 15 to 40% by weight. This ZrO
₂ is such that at least 50% by volume of the crystal structure is tetragonal and the balance is cubic and / or monoclinic. In ZrO ₂ is less than 15 wt%, the ZrO ₂ is less than 50% by volume with a tetragonal crystal structure,
No improvement in strength due to stress-induced transformation from tetragonal to monoclinic can be expected. On the other hand, when ZrO ₂ exceeds 40% by weight, the crystal grains of ZrO ₂ are aggregated to lower the strength, and the wear resistance and the friction characteristics are also reduced. Where Z
rO ₂ contains about 1.5 to 5.0 mol% of a stabilizer such as Y ₂ O ₃ or CeO _{2 in} order to obtain a tetragonal crystal of at least 50% by volume in the crystal structure. The tetragon is in a metastable state.

The ceramic used in the present invention has an average grain size of the entire crystal grains constituting the ceramic of 2 to 20 μm.
m. If the average crystal grain size is less than 2 μm, appropriate surface roughness cannot be obtained even by surface treatment as described below, the contact area with the yarn or film increases, the frictional resistance increases, and yarn breakage and fuzzing occur. Streaks and the like are generated. On the other hand, if it exceeds 20 μm, the area of the grain boundary in one crystal grain becomes large, so that the grain boundary detachment wear is apt to occur and the frictional resistance is increased, and the thread breakage, fuzzing, streaks and the like are liable to occur. A more preferable range of the average crystal grain size is 2 to 10 μm.

Further, the ZrO ₂ crystal grains existing in the crystal grains of A1 ₂ O _{3 on} the surface are 2% or less of the whole ZrO ₂ . If it exceeds 2%, the ZrO ₂ crystal grains are formed in a protruding shape on the surface, so that the frictional resistance is increased and yarn breakage, fluffing, streaks and the like are generated. More preferably, it is 1% or less.

Further, the average crystal grain size of ZrO ₂ is 1.
It is preferably in the range of 5-5 μm. When the average crystal grain size is less than 1.5 μm, the amount taken into the A1 ₂ O ₃ crystal grains increases, and for the same reason as described above, the tendency for yarn breakage, fluffing, stripe marks, and the like to increase. Also, 5
If it exceeds μm, the amount of ZrO ₂ having a tetragonal crystal structure decreases, and the strength tends to decrease.

The ceramic constituting the guide member of the present invention contains TiO ₂ in a range of 1 to 5% by weight. TiO ₂ is mainly A1 ₂ O in the sintering process
₃ of promoting grain growth, is necessary in order to obtain a ceramic having a predetermined grain size at a relatively low sintering temperature. When the amount of TiO ₂ is less than 1% by weight, the effect of promoting the crystal grain growth is small, and it is difficult to obtain a desired crystal grain size. However, if it exceeds 5% by weight, the crystal grain size becomes too large.

[0017] MgO is part of A1 ₂ O generated during sintering.
₃ of abnormal grain growth is suppressed, and a uniform grain size of A1 ₂ O _3, improves the abrasion resistance and strength, ZrO
₂ has a function of suppressing from being taken into the crystal grains of A1 ₂ O _3. When only TiO ₂ is contained,
During sintering, ZrO ₂ and TiO ₂ react to form ZrTiO ₄ , which grows abnormal grains to form needle-like crystals, or A1 ₂ O ₃ grows abnormal grains, causing ZrO ₂ to become intragranular. And a protruding ZrO ₂ crystal is formed on the surface. However, coexistence of MgO can suppress such a phenomenon. In order to expect such an effect, MgO must be at least 0.1% by weight. On the other hand, if it exceeds 1% by weight, the effect of suppressing the growth of the crystal grains of A1 ₂ O ₃ becomes too strong, and the average crystal grain size cannot be in the above-mentioned range.

Further, the guide member of the present invention preferably has a center line average roughness of the surface in the range of 0.2 to 3 μm. This roughness can be easily obtained by buffing a ceramic having an average crystal grain size in the range of 2 to 20 μm with diamond polishing abrasive grains of 0.5 to 2 μm. The surface shape of the crystal grains of the ceramic surface-treated in this way is composed of a smooth curved surface without corners, the contact area with the yarn or film is reduced, and the frictional resistance is reduced. Streaks are less likely to occur.

The guide member of the present invention can be manufactured, for example, by the following method.

That is, first, the main component A1 ₂ O ₃
A predetermined amount of a ZrO ₂ powder, a TiO ₂ powder and a MgO powder are added to the powder and mixed well to obtain a mixed powder.
The mixing operation may be a wet type or a dry type. The mixed powder is dried, if necessary, then coarsely pulverized, sieved, or granulated. The powder of A1 ₂ O ₃ preferably has an average particle size in the range of 0.3 to 2 μm because dense sintering can be performed. In addition, TiO ₂ , MgO, ZrO ₂
The powder having an average particle size of 1 μm or less is preferable in consideration of uniform dispersion in A1 ₂ O ₃ . Further, the purity of each of the above-mentioned powders is preferably 99% or more in order to prevent abnormal growth of crystal grains due to impurities and further improve mechanical properties such as abrasion resistance and strength.

Next, the above mixed powder is mixed with a well-known molding method,
For example, it is molded into a desired shape by using a mold molding method, a rubber press molding method, a casting molding method, and an injection molding method, and then sintered. The atmosphere during the sintering is an oxidizing atmosphere such as the air. The sintering temperature and time are set so that the average crystal grain size of the obtained ceramic is in the range of 2 to 20 μm.
Careful control is performed so that the average crystal grain size of O ₂ is in the range of 1.5 to 5 μm. Further, as ZrO ₂ crystal grains existing in A1 of ₂ O ₃ crystal grains of the surface does not exceed 2% of the total ZrO _2, in the vicinity sintering temperature was at a slow speed of 0.5 ° C. / min or less Warm up. On the other hand, after sintering, if the cooling rate is too slow, a large amount of monoclinic ZrO ₂ precipitates and it becomes impossible to reduce the tetragonal ZrO ₂ to at least 50% by volume. Cooling.

The sintering may be performed by a general sintering method such as normal pressure sintering. However, in order to further improve strength and wear resistance, the obtained ceramic is subjected to hot isostatic pressing. (HIP processing) is also preferred.

Next, the surface of the obtained ceramic is buffed or barrel-polished using abrasive grains such as diamond to obtain a desired guide member. At this time, the grain size and polishing time of the abrasive grains were such that the center line average roughness of the surface was 0.1 mm.
Careful selection is made to be 2-3 μm.

[0024]

【Example】

The average particle diameter in Example 1 is 99.8% purity with 0.5 [mu] m A1 ₂
O ₃ powder, 1% by weight, TiO ₂ powder having an average particle size of 0.7 μm and a purity of 99.9%, and 0.1% by weight,
Mg having an average particle size of 0.3 μm and a purity of 99.99%
O powder and 15% by weight, 1.5 mol% as stabilizer
ZrO ₂ powder having an average particle size of 0.7 μm containing Y ₂ O ₃ was wet-mixed in pure water for 24 hours using a ball mill, and then polyvinyl alcohol was added thereto, followed by spraying, granulation drying, and A mixed powder was obtained. The ZrO ₂ powder is made of ZrO ₂
C1 ₂ · 8H ₂ was added O aqueous solution of YCl ₃ in mixed, which was added aqueous ammonia to coprecipitate the hydroxide, washed with water coprecipitate was dried at 60 at 1000 ° C.
Prepared by calcining for minutes.

Next, the above mixed powder is filled in a mold,
A pressure of 00 kgf / cm ² was applied to obtain a molded body for a strength test having a length of 40 mm, a width of 5 mm, and a thickness of 4 mm. Similarly, a cylindrical molded body having a diameter of 10 mm and a length of 50 mm was obtained for measuring the friction coefficient.

Next, the above-mentioned two types of compacts were placed in the atmosphere for 1 hour.
Sintering was performed at 550 ° C. for 2 hours to obtain two types of test pieces for strength test and friction coefficient measurement. The heating rate was 1000 ° C.
Up to 2 ° C./min, above 0.5 ° C./min, and the cooling rate was 5 ° C./min.

[0027] Thus using the obtained strength test specimen was determined mean and crystal grain size, the average crystal grain size of the ZrO _2, and the amount of tetragonal ZrO _2, and a flexural strength. Further, the test piece for measuring the coefficient of friction was subjected to buff polishing using diamond polishing abrasive grains of 0.5 μm, and then the amount of ZrO ₂ crystal grains present in the Al ₂ O ₃ crystal grains on the surface and the center of the surface were measured. The linear average roughness, the initial coefficient of friction with the yarn, and the rate of change of the coefficient of friction with time were determined. The test results are shown below.

The average crystal grain size was determined by subjecting a test piece to surface grinding with a diamond grindstone, polishing the ground surface to a mirror surface using diamond abrasive grains, and then etching. The maximum length of the crystal grain in the direction was determined and a simple average was determined.

Further, the amount of tetragonal ZrO ₂ was determined by carefully mirror-polishing a test piece for strength test and analyzing it by X-ray diffraction method to determine the amount of tetragonal (111) plane appearing around 2θ = 30.2 °. Integrated intensity T (111) of the diffraction peak;
The integral intensity M (111) of the diffraction peak of the (111) plane of the monoclinic crystal which appears around 2θ = 28.2 °, and 2θ = 31.
From the integrated intensity M (111 ⁻ ) of the diffraction peak of the (111 ⁻ ) plane of the monoclinic crystal appearing at about 5 °, ΔT (111) / [T (111) + M (111) + M
(111 ⁻ )]｝ × 100. Incidentally, 1 ^- represents -1.

Further, the bending strength was determined by processing ten test pieces for strength test, the length of which was 36 mm in length, 4 mm in width, and 3 in thickness.
A three-point bending test was performed on a test piece of mm in accordance with JIS R1601, and a simple average was obtained. The span length was 30 mm and the crosshead speed was 0.5 mm / min.

Further, the amount of ZrO ₂ crystal grains present in the A1 ₂ O ₃ crystal grains on the surface can be determined from the microscopic photograph of the surface of the test piece for measuring the coefficient of friction, as follows: The number Nz of ZrO ₂ crystal grains existing in the crystal grains of ₂ O ₃ was read, and the number was determined by (Nz / N) × 100.

The center line average roughness of the surface is determined according to JIS.
It was measured using a stylus type surface roughness meter according to B0601.

For the friction characteristics, the initial friction coefficient and the rate of change of the friction coefficient with time were determined for the yarn. The initial coefficient of friction was determined from the following equation by running a 200-denier polyester drawn yarn around the test piece for measuring the coefficient of friction at a speed of 400 m / min. μ ₀ = (1 / θ) ln (T ₁ / T ₂ ) where μ ₀ : initial friction coefficient θ: thread contact angle (360 °) T ₁ : yarn tension before entering the test piece T ₂ : test The rate of change of the friction coefficient over time of the tension of the yarn coming out of the piece is calculated from the friction coefficient μ after a 100-hour yarn running test and the initial friction coefficient μ _{0 in} exactly the same way as the measurement of the initial friction coefficient. Δ = [(μ−μ ₀ ) / μ ₀ ] × 100 where δ is determined by the rate of change of friction coefficient with time.

The average particle size: 2.5 [mu] m ZrO ₂ Average particle diameter: 1.5 [mu] m tetragonal ZrO ₂ amounts: 93 vol% Flexural _{^{strength: 63.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.2% Surface center line average roughness: 0.30 μm Initial friction coefficient: 0.35 Change rate of friction coefficient with time: 7.8% Example 2: The amount of TiO ₂ powder was 3% by weight. , And a test piece was prepared in the same manner as in Example 1 except that the amount of the MgO powder was 0.5% by weight, and that the powder of ZrO ₂ contained 2.5 mol% of Y ₂ O ₃ . Tested. The test results are shown below.

The average particle size: 3.2 .mu.m ZrO ₂ Average particle diameter: 1.7 [mu] m tetragonal ZrO ₂ amounts: 92 vol% Flexural _{^{strength: 67.2kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.1% Surface center line average roughness: 0.32 μm Initial friction coefficient: 0.33 Change rate of friction coefficient with time: 5.6% Example 3: The amount of TiO ₂ powder was 5% by weight. , The amount of MgO powder is 1% by weight, and the amount of ZrO ₂ powder is 5%.
Example 1 except that the one containing mol% of Y ₂ O ₃ was used.
A test piece was prepared and tested in the same manner as described above. The test results are shown below.

Average particle size: 3.9 μm ZrO ₂ Average particle size: 2.3 μm Amount of tetragonal ZrO ₂ : 82% by volume Flexural strength: 65.0 kgf / mm ² A1 ₂ O ₃ ZrO ₂ present in crystal grains Amount: 1.2% Surface center line average roughness: 0.38 μm Initial friction coefficient: 0.32 Change with time of friction coefficient: 4.8% Example 4: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 20% by weight. The test results are shown below.

The average particle size: 3.0 [mu] m ZrO ₂ Average particle diameter: 1.7 [mu] m tetragonal ZrO ₂ amounts: 92 vol% Flexural _{^{strength: 81.2kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.0% Center line average roughness of surface: 0.30 μm Initial friction coefficient: 0.33 Temporal change rate of friction coefficient: 5.3% Example 5: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 30% by weight. The test results are shown below.

The average particle size: 2.9 .mu.m ZrO ₂ Average particle size: 2.1 .mu.m tetragonal ZrO ₂ amounts: 80 vol% Flexural _{^{strength: 85.7kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.7% Center line average roughness of surface: 0.30 μm Initial friction coefficient: 0.34 Temporal change rate of friction coefficient: 4.6% Example 6: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 40% by weight. The test results are shown below.

Average particle size: 2.7 μm ZrO ₂ Average particle size: 2.2 μm Amount of tetragonal ZrO ₂ : 75% by volume Flexural strength: 72.2 kgf / mm ² A1 ₂ O ₃ ZrO ₂ present in crystal grains Amount: 0.2% Surface centerline average roughness: 0.27 μm Initial friction coefficient: 0.35 Change rate of friction coefficient with time: 5.0% Example 7: The amount of TiO ₂ powder was 5% by weight. , The amount of MgO powder is 1% by weight, and the amount of ZrO ₂ powder is 5%.
A test piece was prepared and tested in the same manner as in Example 1 except that a material containing mol% of Y ₂ O ₃ was used and the amount was 40% by weight. The test results are shown below.

The average particle size: 3.5 [mu] m ZrO ₂ Average particle diameter: 2.4 [mu] m tetragonal ZrO ₂ amounts: 71 vol% Flexural _{^{strength: 71.0kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.8% Surface center line average roughness: 0.36 μm Initial friction coefficient: 0.32 Temporal change rate of friction coefficient: 4.7% Example 8: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 15% by weight and sintering was performed at 1650 ° C. The test results are shown below.

The average particle size: 6.3 [mu] m ZrO ₂ Average particle size: 2.8 .mu.m tetragonal ZrO ₂ amounts: 73 vol% Flexural _{^{strength: 59.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.3% Surface center line average roughness: 0.73 μm Initial friction coefficient: 0.30 Change rate of friction coefficient with time: 4.0% Example 9: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 20% by weight and sintering was performed at 1650 ° C. The test results are shown below.

Average particle size: 5.8 μm ZrO ₂ Average particle size: 2.7 μm Amount of tetragonal ZrO ₂ : 75% by volume Flexural strength: 65.3 kgf / mm ² Al ₂ O ₃ ZrO ₂ present in crystal grains Amount: 0.8% Surface center line average roughness: 0.58 μm Initial friction coefficient: 0.31 Temporal change rate of friction coefficient: 4.3% Example 10: The amount of TiO ₂ powder was 3% by weight. , MgO
The amount of the powder was 0.5% by weight, and a ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was 30% by weight. Other than that, a test piece was prepared and tested in the same manner as in Example 1. The test results are shown below.

The average particle size: 5.4 [mu] m ZrO ₂ Average particle size: 2.8 .mu.m tetragonal ZrO ₂ amounts: 70 volume% Flexural _{^{strength: 63.8kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.5% Surface center line average roughness: 0.52 μm Initial friction coefficient: 0.32 Change rate of friction coefficient with time: 4.5% Example 11: The amount of TiO ₂ powder was 3% by weight. , MgO
The amount of the powder was 0.5% by weight, and the powder of ZrO ₂ containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was 40% by weight. Other than that, a test piece was prepared and tested in the same manner as in Example 1. The test results are shown below.

The average particle size: 5.1 .mu.m ZrO ₂ Average particle size: 2.9 .mu.m tetragonal ZrO ₂ amounts: 68 vol% Flexural _{^{strength: 58.3kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.3% Surface center line average roughness: 0.52 μm Initial friction coefficient: 0.32 Change rate of friction coefficient with time: 4.3% Example 12: The amount of TiO ₂ powder was 3% by weight. , MgO
The amount of powder was 0.5% by weight, and a ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was 20% by weight. Other than that, a test piece was prepared and tested in the same manner as in Example 1. The test results are shown below.

The average particle size: 13.5 .mu.m ZrO ₂ Average particle diameter: 3.6 [mu] m tetragonal ZrO ₂ amounts: 57 vol% Flexural _{^{strength: 50.1kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.1% Center line average roughness of the surface: 1.35 μm Initial friction coefficient: 0.29 Change rate of friction coefficient with time: 2.4% Example 13: The amount of TiO ₂ powder was 5% by weight. , MgO
Except that the amount of the powder was 1% by weight, the ZrO ₂ powder containing 5 mol% of Y ₂ O ₃ was used, the amount was 40% by weight, and the powder was sintered at 1750 ° C. Test pieces were prepared and tested in the same manner as in Example 1. The test results are shown below.

The average particle diameter: 17.3Myuemu ZrO ₂ Average particle size: 3.8 .mu.m tetragonal ZrO ₂ amounts: 53 vol% Flexural _{^{strength: 49.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.7% Surface center line average roughness: 2.23 μm Initial friction coefficient: 0.27 Temporal change rate of friction coefficient: 1.8% Example 14: The amount of TiO ₂ powder was 3% by weight. , MgO
The amount of the powder was 0.5% by weight, and a ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, the amount was 20% by weight, and the powder was sintered at 1550 ° C. After that, in an argon atmosphere at 1350 ° C. and 2000 kgf / cm
^A test piece was prepared and tested in the same manner as in Example 1 except that hot isostatic pressing was performed in ² . The test results are shown below.

The average particle size: 3.0 [mu] m ZrO ₂ Average particle diameter: 1.7 [mu] m tetragonal ZrO ₂ amounts: 95 vol% Flexural _{^{strength: 101.8kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.0% Surface center line average roughness: 0.30 μm Initial friction coefficient: 0.33 Change rate of friction coefficient with time: 5.3% Example 15: The amount of TiO ₂ powder was 3% by weight. , MgO
The amount of the powder was 0.5% by weight, and a ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, the amount was 20% by weight, and the powder was sintered at 1750 ° C. After that, in an argon atmosphere at 1350 ° C. and 2000 kgf / cm
^A test piece was prepared and tested in the same manner as in Example 1 except that hot isostatic pressing was performed in ² . The test results are shown below.

Average particle size: 13.6 μm ZrO ₂ Average particle size: 3.7 μm Amount of tetragonal ZrO ₂ : 59% by volume Flexural strength: 59.3 kgf / mm ² A1 ₂ O ₃ ZrO ₂ present in crystal grains Amount: 1.0% Center line average roughness of the surface: 1.38 μm Initial friction coefficient: 0.29 Rate of change of friction coefficient with time: 2.3%

[0049]

[Comparative example]

Comparative Example 1: The amount of TiO ₂ powder was 5% by weight, the amount of MgO powder was 1% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and A test piece was prepared and tested in the same manner as in Example 1 except that the amount was changed to 10% by weight. The test results are shown below.

The average particle size: 4.3 [mu] m ZrO ₂ Average particle size: The amount of 1.6μm tetragonal ZrO _2: 91 vol% Flexural _{^{strength: 38.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.8% Surface center line average roughness: 0.35 μm Initial friction coefficient: 0.38 Temporal change rate of friction coefficient: 11.4% Comparative example 2: The amount of TiO ₂ powder was 5% by weight. , MgO powder was set to 1% by weight, ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was set to 50% by weight. A test piece was prepared and tested in the same manner as described above. The test results are shown below.

The average particle size: 3.2 .mu.m ZrO ₂ Average particle size: 2.8 .mu.m tetragonal ZrO ₂ amounts: 68 vol% Flexural _{^{strength: 42.0kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.4% Surface center line average roughness: 0.31 μm Initial friction coefficient: 0.39 Change rate of friction coefficient with time: 13.1% Comparative Example 3: 0.5 weight of TiO ₂ powder % And Mg
The amount of O powder was set to 0.1% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was set to 20% by weight. A test piece was prepared and tested in the same manner as in Example 1 except for tying. The test results are shown below.

[0052] Mean particle diameter: 4.9 [mu] m ZrO ₂ Average particle size: 2.2 .mu.m tetragonal ZrO ₂ amounts: 53 vol% Flexural _{^{strength: 39.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.5% Center line average roughness of the surface: 0.36 μm Initial friction coefficient: 0.38 Change rate of friction coefficient with time: 9.0% Comparative Example 4: 5.5 weight of TiO ₂ powder % And Mg
The amount of the O powder was set to 0.1% by weight, and the ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used, and the amount was set to 20% by weight. A test piece was prepared and tested in the same manner as in Example 1 except for tying. The test results are shown below.

[0053] Mean particle diameter: 18.5 ZrO ₂ Average particle size: 3.9 .mu.m tetragonal ZrO ₂ amounts: 51 vol% Flexural _{^{strength: 38.9kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 1.8% Surface center line average roughness: 2.7 μm Initial friction coefficient: 0.45 Change with time in friction coefficient: 15.5% Comparative Example 5: The amount of TiO ₂ powder was 3% by weight. , MgO powder was used in an amount of 0.05% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used. Tested. The test results are shown below.

[0054] Mean particle size: 3.4 .mu.m ZrO ₂ Average particle diameter: 1.5 [mu] m tetragonal ZrO ₂ amounts: 92 vol% Flexural _{^{strength: 59.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 2.2% Surface center line average roughness: 0.32 μm Initial friction coefficient: 0.42 Change rate of friction coefficient with time: 13.0% Comparative Example 6: The amount of TiO ₂ powder was 1% by weight. , MgO powder was used in an amount of 1.2% by weight, and a test piece was prepared in the same manner as in Example 1 except that ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ was used. Tested. The test results are shown below.

[0055] Mean particle size: 1.8 .mu.m ZrO ₂ Average particle size: The amount of 1.5μm tetragonal ZrO _2: 91 vol% Flexural _{^{strength: 61.3kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.3% Surface center line average roughness: 0.18 μm Initial friction coefficient: 0.45 Change with time of friction coefficient: 17.4% Comparative Example 7: The amount of TiO ₂ powder was 1% by weight. , The amount of MgO powder is 0.1% by weight, and ZrO ₂ powder containing 2.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 40% by weight and sintering was performed at 1450 ° C. The test results are shown below.

[0056] Mean particle diameter: 1.2 [mu] m ZrO ₂ Average particle size: The amount of 1.0μm tetragonal ZrO _2: 63 vol% Flexural _{^{strength: 58.7kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.2% Surface center line average roughness: 0.12 μm Initial friction coefficient: 0.46 Temporal change rate of friction coefficient: 18.1% Comparative Example 8: Assume that the amount of TiO ₂ powder is 5% by weight , MgO powder at 0.5% by weight, and ZrO ₂ powder containing 5 mol% of Y ₂ O ₃ at 40% by weight and sintering at 1750 ° C. Other than that, a test piece was prepared and tested in the same manner as in Example 1. The test results are shown below.

Average particle size: 21.8 μm ZrO ₂ Average particle size: 4.1 μm Amount of tetragonal ZrO ₂ : 51% by volume Flexural strength: 32.7 kgf / mm ² A1 ₂ O ₃ ZrO ₂ present in crystal grains Amount: 1.8% Surface center line average roughness: 2.73 μm Initial friction coefficient: 0.28 Change rate of friction coefficient with time: 15.9% Comparative Example 9: The amount of TiO ₂ powder was 3% by weight. , The amount of MgO powder is 0.5% by weight, and ZrO ₂ powder containing 0.5 mol% of Y ₂ O ₃ is used, and
A test piece was prepared and tested in the same manner as in Example 1 except that the amount was 20% by weight. The test results are shown below.

[0058] Mean particle size: 2.9 .mu.m ZrO ₂ Average particle diameter: 1.6 [mu] m tetragonal ZrO ₂ amounts: 45 vol% Flexural _{^{strength: 31.5kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 0.9% Center line average roughness of surface: 0.30 μm Initial friction coefficient: 0.38 Change rate of friction coefficient with time: 13.0% Comparative Example 10: Assume that the amount of TiO ₂ powder is 5% by weight. , MgO
The amount of the powder is 0.1% by weight, and a ZrO ₂ powder containing 5 mol% of Y ₂ O ₃ is used.
A test piece was prepared and tested in the same manner as in Example 1 except that the test piece was sintered at 750 ° C. The test results are shown below.

[0059] Mean particle diameter: 19.2 ZrO ₂ Average particle size: 2.9 .mu.m tetragonal ZrO ₂ amounts: 60 vol% Flexural _{^{strength: 42.1kgf / mm 2 A1 2 O}} 3 ZrO 2 present in crystal grains Amount: 2.2% Surface center line average roughness: 2.43 μm Initial friction coefficient: 0.31 Change with time in friction coefficient: 11.9% Comparative example 11: 2.5 mol% of Y ₂ O ₃ A test piece was prepared and tested in the same manner as in Example 1 except that only a ZrO ₂ powder having an average particle size of 0.7 μm and a sintering temperature of 1450 ° C. were used. The test results are shown below.

Average particle size: 0.4 μm Amount of tetragonal ZrO ₂ : 93% by volume Flexural strength: 124.0 kgf / mm ² Center line average roughness of surface: 0.21 μm Initial friction coefficient: 0.50 Change over time: 25.4% Comparative Example 12: Average particle size is 0.5 μm and purity is 99.9%
To A1 ₂ O ₃ powder is, the TiO ₂ powder with an average particle size of 99.9% purity in 0.7 [mu] m, TiO ₂ is A1 ₂
TiO ₅ was added so as to be 2.2% by weight, wet-mixed in pure water for 24 hours using a ball mill, dried, and coarsely pulverized to obtain a mixed powder.

Next, this mixed powder was calcined at 1300 ° C. for 2 hours, and the calcined powder was mixed with 2.5 mol% as a stabilizer.
Including the Y ₂ O _3, and a mean particle size ZrO ₂ powder 10 weight% of 0.7 [mu] m, using a ball mill for 24 hours, wet-mixed in pure water, spray further added polyvinyl alcohol, granulated The granules were dried to obtain a composite powder.

A test piece was prepared and tested in the same manner as in Example 1 except that the sintering temperature was changed to 1600 ° C. The test results are shown below.

[0063] Mean particle diameter: 6.5 [mu] m ZrO ₂ having an average particle size: 1.8 .mu.m tetragonal ZrO ₂ amounts: 82 vol% Flexural strength: ZrO present in 50.6kgf / mm _² A1 ² O ₃ crystal grains Amount of ₂ : 2.4% Surface center line average roughness: 0.75 μm Initial friction coefficient: 0.30 Change in friction coefficient with time: 8.9%

[0064]

Effect of the Invention guide member of the present invention includes an A1 ₂ O ₃ as a main component, comprises at least 50% by volume of ZrO ₂ in tetragonal in the range of 15 to 40 wt% in the crystal structure, the TiO ₂ MgO in the range of 1-5% by weight
Is contained in the range of 0.1 to 1% by weight, and the average crystal grain size is 2 to 2.
In the range of 20 μm, and A1 ₂ O ₃
Since the ZrO ₂ crystal grains existing in the crystal grains of the above are composed of ceramics that are 2% or less of the entire ZrO _2, as is clear from the comparison between the example and the comparative example, the wear resistance,
These are provided in a well-balanced manner in terms of mechanical strength and friction characteristics with yarn and film.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B65H 57/24

Claims (3)

(57) [Claims] 1. ZrO ₂ containing Al ₂ O ₃ as a main component and having at least 50% by volume of a tetragonal crystal structure.
Hints in the range of 15 to 40 wt%, the TiO ₂ comprises in the range of 1 to 5% by weight, comprises MgO in a range of 0.1 to 1 wt%, the average crystal grain size is in the range of 2~20μm And Zr present in the crystal grains of A1 ₂ O _{3 on} the surface
A guide member made of ceramics in which O ₂ crystal grains are 2% or less of the whole ZrO ₂ . _2. An average crystal grain size of ZrO ₂ is 1.5 to 5 μm.
The guide member according to claim 1, wherein the guide member is in a range of m. 3. The guide member according to claim 1, wherein the center line average roughness of the surface is in the range of 0.2 to 3 μm.