JP2739093B2 - Thermal spray material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal spray material for forming a thermal spray coating having a pink color tone.

[0002]

2. Description of the Related Art Conventionally, methods for coloring and coating a substrate surface include an enamel method, a plating method, an alumite treatment method, and a method of applying an organic paint. Of these, the enamel method,
In the plating method and the alumite processing method, the color tone can be easily controlled, and the colored coating layer is relatively strong, but the enamel method requires heating the base material. There is a drawback that you can not. The colored coating layer formed by the plating method or the alumite processing method has a drawback that the use environment is particularly severe, and when used for a long time, it is damaged or peels off.

[0003] In particular, the method of applying an organic paint has a vivid color and has a large number of colors, so that the base material can be colored in a vivid color. It does not have sufficient durability for long-term outdoor use such as buildings,
Discoloration and discoloration are remarkable. In addition, because of poor wear resistance,
For example, when applied to a manhole iron cover, not only does the applied surface peel off due to walking or traffic of a vehicle, but also under hot summer weather, the manhole iron cover reaches a temperature of 90 ° C. or higher, so that it fades or discolors in a short period of time. Furthermore, the application surface is slippery during rainfall, which is dangerous for walking and traffic of vehicles.

[0004] As a technique for improving the above-mentioned drawbacks, application of ceramic thermal spraying can be considered. That is, a ceramic sprayed material is sprayed on various base materials to form a sprayed film, and heat resistance, corrosion resistance, abrasion resistance, and friction can be imparted. However, most of the currently used thermal spray materials focus on the above-mentioned performances, and at present, little consideration is given to the color tone of the thermal spray coating. For example, white alumina exhibiting a white tone, alumina-titania exhibiting a black tone,
There are only an alumina-cobalt type exhibiting a blue color tone and a calcium silicate-chromia type exhibiting a green color tone.

[0005] Recently, as a thermal spray material for forming a pink thermal spray coating, an alumina-manganese dioxide thermal spray material has been proposed, and a thermal spray coating on a base material such as metal or concrete forms a coating exhibiting a pink color tone. it can. However, this is a very pale pink color, that is, a system color name
Is within the range of colors represented by pink,
Colors in areas that are fairly high and low in saturation,
Since only pale pink was obtained and the abrasion resistance of the film was inferior, there was a demand for deeper color and improved abrasion resistance.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a Munsell table.
In the color system, the hue is nRP or nR, provided that 0 <n ≦ 10
And the lightness is approximately 6 or more and the saturation is approximately 1 to 10.
Among the pink colors represented in the area, conventional sprayed materials
The pale pink color obtained in the above, that is,
Colors with a degree of 4 or less and a lightness of 8 or more,
Colors with high saturation and lightness equal to or less than the range,
Saturation of 6 or more and lightness of 8 in the pink color region
A deep pink color represented by the following range and relatively high
An object of the present invention is to provide a thermal spray material which forms a thermal spray coating having excellent wear resistance .

[0007]

As a result of various studies, the present inventors have found that (1) erbium oxide and alumina have silica,
At least one of a manganese compound and phosphorus pentoxide
When spraying the combined thermal spray material on the substrate, it has high wear resistance,
Hue was previously obtained in the beautiful and Munsell color system
It is similar or relatively similar to pale pink,
A sprayed coating with a relatively dark pink color with lightness equal to or less than that of the product and high saturation is obtained. (2) When the sprayed material obtained by firing the above composition is sprayed on a base material, a beautiful and excellent hue having excellent wear resistance is known as a conventional sprayed material.
It is similar or relatively similar to the pink color that was
The inventors have found that a thermal sprayed coating exhibiting a dark pink color having a lightness equal to or less than that and having a higher saturation can be obtained, and the present invention has been completed.

That is, the first invention is an erbium oxide
10 to 30% by weight of alumina, 60 to 80% by weight of alumina,
At least one of mosquito, manganese compound and phosphorus pentoxide
It is a thermal spraying material that is blended from 10 to 10% by weight.
The invention is based on 10 to 30% by weight of erbium oxide and 60 of alumina.
~ 80% by weight of silica, manganese dioxide, phosphorus pentoxide
140 to 1 to 10% by weight of at least one compound
Thermal sprayed material fired at 0 ° C or higher.

Hereinafter, the present invention will be described in more detail. It is preferable to use all the raw materials of erbium oxide, alumina, silica, manganese dioxide and phosphorus pentoxide having a purity of 90% or more in order to enhance the controllability of the color tone of the sprayed coating and the vividness of the color tone. In addition, since there are various production methods for alumina, coarse alumina, fine alumina, fused alumina, activated alumina, low soda alumina, ultrafine alumina, and the like can be used.

[0010] Erbium oxide, alumina, manganese dioxide
Down is a component for controlling the thermal spray coating to the color of pink, silica is a component of improving the wear resistance of the thermal spray coating, phosphorus pentoxide is a component to control the pink darkening.

The mixing ratio of the thermal spray material of the first invention is as follows:
Erbium oxide: 10 to 30% by weight, alumina: 60 to
80% by weight, silica, manganese dioxide or phosphorus pentoxide:
1 to 10% by weight. The compounding ratio of the thermal spray material of the second invention is the same as that of the first invention, and is obtained by firing.

The thermal spray material of the first invention has an average particle diameter of 5 from the flowability of the thermal spray material at the time of film formation and the meltability of the material.
１００100 μm, preferably 20-40 μm. Further, when using a spray dryer or the like to obtain a granular product, the primary particle size of each raw material is 0.05 to 100 μm, preferably 0.1 to
30 μm, methyl cellulose, polyvinyl alcohol, etc. are added in an amount of 0.5 to 5% by weight to obtain a granule diameter of 5 μm.
It is good to adjust it to ５００500 μm, preferably 10-100 μm.

The thermal spray material of the second invention can be obtained by firing in a known firing furnace such as an electric furnace or a rotary kiln. If the firing temperature is lower than 1000 ° C., sintering hardly proceeds, which is not preferable. Firing temperature proceeds and sintering at 1400 ° C. or higher, darkening of the film by at spraying, i.e.,
A highly saturated film color is exhibited in the pink color tone.
Other made easier, since the improvement of the wear resistance can be attained 1400 ° C.
It is preferable to bake as described above. After the fired product obtained at the above firing temperature is pulverized by a pulverizer such as a ball mill, the first
The sprayed material according to the second aspect of the present invention has a grain size or a granular shape so as to have the same particle size as that of the sprayed material, and is adjusted as a sprayed material.

The sprayed material of the first invention and the second
What is appropriately mixed with the thermal spray material of the present invention can also be used as the thermal spray material. The coating obtained by spraying them has an intermediate color between light and dark in the pink color tone.
It exhibits a color tone and exhibits relatively excellent wear resistance.

In applying the thermal spray material of the present invention, a plasma thermal spraying method, an explosive thermal spraying method, a high-speed gas thermal spraying method, a low-speed gas thermal spraying method, or the like can be used. In such a thermal spraying method, a film can be formed by explosive spraying or gas spraying, but in the case of ceramics having a high melting point, it is difficult to form a sufficiently melted good film. Therefore, in general, a plasma spraying method that can form a good film even on ceramics having a high flame temperature and a high melting point is preferable.

[0016]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. As raw materials, 99.9% pure erbium oxide (Er ₂ O ₃ ), 98% pure alumina (Al)
₂ O ₃ ), 98% pure silica (SiO ₂ ), 91% pure
Of manganese dioxide (MnO ₂ ) and phosphorus pentoxide (P ₂ O ₅ ) with a purity of 94% were used. These were sufficiently mixed by a ball mill according to the composition shown in Table 1 and adjusted to have an average particle size of 30 μm to obtain a sprayed material. Further, a mixture obtained by sufficiently mixing the respective raw materials according to the composition was fired at the temperature shown in Table 1, and then crushed and grain-adjusted to adjust the average particle size to 30 μm to obtain a sprayed material. Further, the mixture or the fired product was further pulverized into fine particles, spray granulated with a spray drier, and adjusted to granules having an average particle size of 30 μm to obtain a sprayed material. These sprayed materials are used as undercoat materials in advance.
Plasma coating was performed under the following conditions on a SUS base material subjected to plasma spraying of an i-Al system to form a coating.

Plasma gas: N ₂ / H ₂ gas pressure: 50 p. s. i. / 50p. s. i. Gas flow rate: 75 l / min / 10 l / min Current: 500 A Voltage: 70 V

The color tone of the formed thermal spray coating was examined using a Munsell color chart. In addition, JIS H
Based on the reciprocating motion abrasion test method of 8503, the number of reciprocations (DS / mg) of the abraded paper required to reduce the abrasion loss of 1 mg of the film was measured, and the value was taken as the abrasion resistance. Table 1 shows the results.

[0019]

[Table 1]

As can be seen from Table 1, the thermal spray material composed of 70% by weight of Al ₂ O _{3 and} 30% by weight of MnO ₂ (Comparative Example 1) has a pale pink coating of 5R9 / 1, The DS value is 11. On the other hand, Er ₂ O ₃ and Al ₂
What added SiO ₂ and MnO ₂ to O ₃ (Example 1)
10RP7 / 6, a pin that is darker than (Comparative Example 1)
And exhibit a higher wear resistance than (Comparative Example 2).
The thermal spray material to which P ₂ O ₅ was further added (Example 2) was 7.5.
It has a dark pink color of RP8 / 6 and a DS value of 25 .
Abrasion resistance is improved.

Further , Er ₂ O ₃ and Al ₂ O ₃ have SiO ₂ , M
at least one of nO ₂ and P ₂ O ₅
The sprayed material obtained by sintering is 7.5 RP8 / 6 (implemented
Example 3) 10RP7 / 6 (Example 4), 7.5RP7 /
6 (Example 5), each having a coating showing a deep pink color.
And the DS value of the film is 33-42, which is remarkably abrasion resistant
Was improved.

[0022]

By using the ceramic sprayed material of the present invention, the density which is much higher in saturation than in the prior art, which is excellent in wear resistance, is obtained.
Pink, that is, the hue is nRP (where 0 <n ≦ 10)
It is possible to form a thermal spray coating having a pink color tone represented by a range of chroma of 6 or more and lightness of 8 or less . Further, since the thermal sprayed coating of the present invention has corrosion resistance and heat resistance, by spraying onto a manhole iron cover, various metal base material surfaces, concrete surfaces, and the like, a beautiful material having wear resistance, corrosion resistance, and heat resistance is provided. It is possible to form a thermal spray coating of various colors.

Continuation of front page (56) References JP-A-1-316446 (JP, A) JP-A-4-246159 (JP, A) JP-A-7-90535 (JP, A) JP-A-7-18404 (JP) , A) JP-A-51-95414 (JP, A) Dictionary of Chemistry, 1st edition, 1st printing, (Hei 1-10-20), Tokyo Chemical Industry Co., Ltd., p.

Claims (2)

(57) [Claims] An erbium oxide in an amount of 10 to 30% by weight,
Mina 60-80% by weight, silica, manganese dioxide, pentaacid
A thermal spray material comprising 1 to 10% by weight of at least one phosphorus hydride. 2. An erbium oxide of 10 to 30% by weight,
Mina 60-80% by weight, silica, manganese dioxide, pentaacid
Containing at least one type of phosphorus hydride in an amount of 1 to 10% by weight
Sprayed material obtained by firing at a temperature of 1400 ° C. or more .