JP3427078B2 - Manufacturing method of ceramic-based composite spray material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a ceramics composition in which a main component is ceramics, a subcomponent is a metal (a metal or a metal compound or a mixture thereof), and the main component ceramics is coated with a subcomponent metal. about manufacturing <br/> granulation method based composite thermal spray material.

[0002]

2. Description of the Related Art There is a high-speed air current impact method as a technique for modifying the surface of powder by coating the surface of the powder with another material. This method is a method in which powder of the main component is coated with a subcomponent by a dry mechanical treatment to form a composite, and as shown in FIG. 9, ceramics 2 is used as the main component, and this is used as a metal of the subcomponent. A ceramics-based composite thermal spray material 1 is coated with a class 3. As shown in FIG. 10, the ceramic-based composite thermal spray material 1 is prepared by mixing the metals 2a with the ceramics 2a in advance to form the metal 3 on the surface of the ceramics 2a.
Make ordered mixture powder 1a with a attached,
This prepared by treatment with apparatus as shown in FIGS. 11 and 12. In the figure, 5 is a rotor rotating at high speed, 6 is a plurality of blades for striking around the outer periphery of the rotor 5 at intervals, 7 is a case body surrounding the rotor 5, 8 is the rotor 5 and the case body 7 A processing chamber provided in a space between the and, a circulation circuit 9 that opens in a part of the processing chamber 8 and opens in the vicinity of the center of the rotor 5, 10 is an inlet for powder of material, and 11 is an inlet. An inlet passage connecting 10 to the vicinity of the end of the circulation circuit 9 and an outlet 12 for the treated powder. The ordered mixture powder 1a is charged from the charging port 10 of this device, and the blade 6 of the rotor 5 rotating at high speed
Add mechanical shock by. The circulation circuit 9 circulates the powder, and the impact is repeatedly applied. As a result, the metal 3a is driven into the surface of the ceramics 2a, and both are slightly deformed to obtain the ceramic-based composite thermal spray material 1 as shown in FIG.

[0003]

The ceramic-based composite thermal spray material thus produced contains ceramics, which, unlike resins and metals, have little plastic deformation unlike the resin and metal, and therefore the impact force of the rotor of the apparatus is insufficient. Then, metal 3
There is a problem that the holding of the metal 3a by the ceramics 2a after the implantation of a is incomplete, the composite rate is lowered , and the processing time is long. On the other hand, if the impact force of the rotor is excessive, the ceramics 2a will be completely held by the metal 3a, but the ceramics 2a
It induces the crushing of the, and causes the reduction of the composite rate. When the compounding ratio of the subcomponent metal 3a to the main component ceramics becomes low, there is a problem in that the degree of compounding varies. The present invention has been made in view of the above circumstances,
And to provide a method of manufacturing a ceramic-based composite thermal spraying material which solves the above problems.

[0004]

According to the present invention, in the case of producing a ceramic-based composite thermal spray material by subjecting ceramic particles and metals to impact, the present invention provides impact.
During the obtaining step, by treating while applying heat by pairs by pressurized heat sink to be treated powders were solved the problems.

[0005] by <br/> production method of engaging Rousset La mix based composite thermal spray material in the present invention, the ceramics and metals to obtain a composite thermal spray material tightly bound by the binding layer by mechanical binding and chemistry be able to.

[0006]

DETAILED DESCRIPTION FIG. 1 shows the apparatus used in the production of the present invention conceptually, the Chi also the same structure and function and the apparatus described in the prior art, rotary rotor 25, blades 26,
It is provided with a case body 27, a processing chamber 28, a circulation circuit 29, a material input port 30, a feed path 31, and a discharge port 32. 35
Is a heater provided in the circulation circuit 29, and the powder passing through the circulation circuit 29 is heated by the heater 35. 36 is a water cooling jacket provided on the case body 27 for cooling;
Is an on-off valve that opens and closes the discharge port 32. Using this device, the dry powder mixture comprising a ceramic 2a and metals 3a, the inlet 30 is supplied to the device. This mixed powder is used for the blade 26 of the rotor 25 that rotates at high speed.
As shown by the arrow,
It passes through the circulation circuit 29 and is heated by the heater 35 when passing. In this way, the impact and heating are repeated on the mixed powder. The inside of the processing chamber 28 is kept at a constant temperature by the water cooling jacket 36. After processing for a certain period of time, the open / close valve 37 may be moved to the position shown by the broken line to open the discharge port 32 and take out the processed ceramic-based composite thermal spray material.

The powder thus treated gives a ceramic-based composite thermal spray material 41 consisting of ceramics 42 and metals 43 covering the same as shown in FIG. As shown in FIG. 3, in the enlarged cross section of the E portion, fine uneven portions 44 are formed in the vicinity of the interface where the ceramics 42 and the metals 43 contact each other. This is ceramics 4
Micro cracks or open pores formed on the surface of the ceramic during the manufacturing process of No. 2, and the ductile metals 43 enter into the uneven portion 44 by mixing and collision, and at the same time, the ceramic 42 is slightly deformed by the impact. repeating, metals 43 having entered the concave-convex portion 44 by Re their is a state of the ceramic 42 and metals 43 plays the role of the anchor is attached. And of the circulation process
In the meantime, for example, by heating by the heater 35 in the circulation circuit 29, a chemical bonding layer of ceramics and metals is formed on a part of the uneven portion 44. This chemical bond, with metals 43 ceramics 42 after it has been implanted coercive <br/> and lifting, preventing both separation other than collision surface at the time of collision, ceramics 4 by a relatively small impact force
It is possible to enhance the binding force between the metal 2 and the metal 43.

FIG. 4 shows typical ceramics (Si
C, Si ₃ N ₄ , Al ₂ O ₃ ) show reflection characteristics in the far infrared region, and these have special absorption characteristics at wavelengths exceeding 10 μm. Therefore, if a far-infrared radiation type heater is used as the heater 35, the ceramics 42 will be more effective than the mixed powder metal 43 and the circulation circuit 29 near the heater.
It itself can be selectively heated, and because it is heated by irradiation, the surface of the ceramic 42 is mainly heated to promote a chemical reaction. Therefore, it is preferable to use a far infrared radiation type heater.

[0009]

[Specific Example] Ceramics were mixed with 100 parts by weight of commercially available α-Al ₂ O ₃ (average particle size 30 μm), and metals were mixed with 10 parts by weight of commercially available Ni (average particle size 0.2 μ).
g in the apparatus shown in FIG. 1, the rotor is rotated at a peripheral speed of 80 m /
It was rotated for 5 seconds and the heater was activated to process for 5 minutes. In addition,
As Comparative Example 1, the same amount of mixed powder was treated under the same conditions without heating. Further, the peripheral speed of the rotor was set to 100 m / s, and the other conditions were the same as those of the comparative example 1, and the comparative example 2 was obtained.

The results are shown in Table 1. This table shows that among the thermal spray materials obtained by the above treatment , Ni that has fallen out without becoming a composite thermal spray material and α-Al ₂ O ₃ that has been crushed to classify α-Al ₂ O ₃ 20μ which is the minimum particle size
It is a comparison of the weight of the thermal spray material remaining on the sieve when passing through a sieve with an opening of m (# 635) for each sample. From this, it was confirmed that the yield was high in the order of the present invention, Comparative Example 1 and Comparative Example 2.

[0011]

[Table 1]

Table 2 shows the volume ratio and the weight ratio of Ni content in the thermal spray material on the sieve calculated from the true specific gravity of the thermal spray material on the sieve shown in Table 1. From this table, it can be seen that the ratio of Ni content increases in the order of the present invention, Comparative Example 2, and Comparative Example 1.

[0013]

[Table 2]

Table 3 shows the yield of Table 1 and the weight ratio of Table 2,
The weight of Ni content in the sieve is calculated, and the ratio with the input amount is shown as a composite rate.

[0015]

[Table 3]

Rotor peripheral speed is from 80 m / s to 100 m
In Comparative Example 2 in which the ratio was increased to / s to achieve high compositeness, the α-Al ₂ O ₃ of the ceramics was crushed and the yield was reduced, and as a result, the composite rate could not be improved. On the other hand, in the case of the present invention, both the yield and the composite rate were significantly improved as compared with those in Comparative Example 1.

FIG. 5 shows the present invention, FIG. 6 shows the comparative example 1, FIG.
Are X-ray diffraction patterns of α-Al ₂ O ₃ which is the main component. In each figure, A is the main diffraction peak of α-Al ₂ O ₃ , B is the main diffraction peak of Ni, and C is The main diffraction peak of NiAl ₂ O ₄ is shown. In FIG. 5 , Al ₂ O is generated by heating.
In part of the interface ₃ and _{Ni, 2Ni + O 2 → 2NiO} NiO + Al 2 O 3 → chemical reaction NiAl ₂ O ₄ happened, since the formation of the chemical bond layer of NiAl ₂ O _4, Ru Tei appear main diffraction peak of C . The formation of this chemical bond layer completes the retention of Ni by Al ₂ O ₃ , and the impact force can be applied without causing the separation of the two, so that the composite ratios shown in Tables 1 to 3 above are obtained. Can be improved.

Next, using these composite thermal spray materials, SUS
FIG. 8 shows the result of comparing the adhesion strength of a thermal spray coating formed on a system substrate by a plasma jet of an argon arc. For reference, the case of α-Al ₂ O ₃ alone is also shown. According to FIG. 8, similar to the result of Table 3,
In the case of Comparative Example 2, the adhesion strength is higher than that of α-Al ₂ O ₃ alone, but the adhesion strength of Comparative Example 1 cannot be exceeded. On the other hand, the adhesion strength of the film according to the present invention depends on the NiAl ₂
The chemical bond layer of O ₄ improves the bonding force between Al ₂ O ₃ and Ni, so that it is higher than any of them, indicating that the complexing by coating is sufficiently completed. As described above, in the examples, the case where α-Al ₂ O ₃ is used as the ceramics and Ni is used as the metals is explained. However, other ceramics and metals, which are mechanically coupled to each other by heating, and their contact It suffices that a chemical bond layer can be formed on the portion, and the present invention is not limited to the above-mentioned embodiment.

[0019]

According to the method of the present invention , ceramics and
In addition to mechanical connection with metals, at the contact part of both
Adhesion strength of coating layer, where bonding layer is formed by chemical reaction
With high ceramic-based composite thermal spray material ,
Since it is possible to form a composite with low impact force, the main component ceramic is less crushed, and the secondary component metals are less likely to drop from the ceramic due to the impact, so that the yield is increased. Furthermore, even if the compounding ratio of the metal that is the accessory component is low, a thermally sprayed material uniformly compounded can be obtained.

[Brief description of drawings]

FIG. 1 is a conceptual explanatory diagram of an apparatus used in the present invention.

FIG. 2 Enlargement of ceramic-based composite thermal spray material according to the present invention
It is a figure and it is explanatory drawing shown in the cross section which expanded half of the particle.

FIG. 3 is an explanatory view showing a further enlarged portion E of the ceramic-based composite thermal spray material in FIG.

FIG. 4 is a diagram showing reflection characteristics of ceramics in a far infrared region.

FIG. 5 is a main component of α-Al ₂ O _{3 according} to the present invention,
The X-ray diffraction pattern of the ceramics-based composite thermal spray material containing Ni as an accessory component is shown.

FIG. 6 shows an X-ray diffraction pattern of a ceramic-based composite thermal spray material of Comparative Example 1.

FIG. 7 shows an X-ray diffraction pattern of only α-Al ₂ O ₃ which is a main component of ceramics.

FIG. 8 is a diagram comparing and comparing the adhesion strength of a thermal spray coating by plasma jet.

FIG. 9 is an explanatory view showing the enlarged particles of a conventional ceramic-based composite thermal spray material, and showing a half of the particles in cross section.

FIG. 10 is an explanatory view showing an enlarged state of particles before treatment, in which metals are adhered to ceramics in order to produce a ceramic-based composite thermal spray material, and a half thereof is shown in cross section.

FIG. 11 is a conceptual explanatory diagram of an apparatus corresponding to FIG. 1 used in a conventional method.

FIG. 12 is a side view of the device shown in FIG.

[Explanation of symbols]

25 rotating rotor 29 Circulation circuit 35 heater 42 Ceramics 43 Metals 44 uneven part

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C04B 41/87 C04B 41/87 W (72) Inventor Kenji Miyai 300, Takatsuka-cho, Hamamatsu-shi, Shizuoka Suzuki Co., Ltd. (56) References JP-A-1-287263 (JP, A) JP-A-59-64766 (JP, A) JP-A-55-41948 (JP, A) JP-A-3-277763 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) C23C 4/00-4/18 B01J 2 / 00,2 / 10 B22F 1 / 00,9 / 02-9/04 C04B 35 / 66,41 / 87-41 / 88

Claims (2)

(57) [Claims] 1. A hitting blade provided in a case body is rotated.
The mixed powder containing ceramic particles and metals is impacted by moving the mixed powder , and the mixed powder is ejected from the case body to form a case.
A method of manufacturing a ceramic-based composite thermal spraying material is circulated through the circulation circuit back to the body, be located outside the case body
Place a heater in the circulation circuit to heat the mixed powder to be treated.
Then, the mixed powder is treated by repeating impact and heating to form a mechanically coupled structure and a chemical reaction layer, which are intertwined with each other at the contact portion between the ceramic and the metal, and the ceramic-based composite thermal spraying. Method of manufacturing wood. 2. A striking blade provided in the case body is rotated.
The mixed powder containing ceramic particles and metals is impacted by moving the mixed powder , and the mixed powder is ejected from the case body to form a case.
A method of manufacturing a ceramic-based composite thermal spraying material is circulated through the circulation circuit back to the body, be located outside the case body
A far-infrared radiation type heater is placed in the circulation circuit to
Heat the mixed powder and subject the mixed powder to shock and heating.
A process for producing a ceramic-based composite thermal spray material, characterized in that a mechanically bonded structure and a chemical reaction layer, which are intertwined with each other, are formed in a contact portion between ceramics and metals by treating them while returning them.