JPH0790535A - Thermal spraying material - Google Patents

Abstract

PURPOSE:To obtain a thermal spraying material capable of forming a deep pink sprayed coating improved in wear resistance by adding silica into an alumina-manganese dioxide base thermal-spraying material. CONSTITUTION:The thermal spraying material consists of alumina, a manganese compound and silica, or is made by firing these materials. Or, the thermal spraying material consists of alumina, the manganese compound, silica and phosphorus pentaoxide, or is made by firing these materials. For instance, the thermal spraying material is made by sufficiently mixing, by weight, 94%, Al2O3, 3% MnO2, and 3% SiO2 in a ball-mill. Or, the thermal-spraying material is made by firing a mixture, which is obtained by sufficiently mixing, by weight, 79% Al2O3, 7% MnO2, 7% SiO2, and 7% P2O5 and pulverizing the fired material.

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 which forms a thermal spray coating having a pinkish color tone.

[0002]

2. Description of the Related Art Conventionally, as a method for coloring and coating a surface of a base material, there are an enamel method, a plating method, an alumite processing method, a method of applying an organic paint, and the like. Of these, the enamel method,
In the plating method and the alumite processing method, the color tone is easy to control, and although the colored coating layer is relatively strong, the enamel method requires heating the base material, and the wood and concrete base materials cannot be applied. There is a drawback that you cannot do it. The colored coating layer formed by the plating method or the alumite processing method has a drawback that the environment of use is particularly severe and that it may be scratched or peeled off when it is used for a long period of time.

In addition, particularly in the method of applying an organic paint, since the color is vivid and has many color tones, the base material can be colored with vivid colors, but the manhole iron lid, outer wall material, concrete It does not have sufficient durability for long-term outdoor use such as buildings,
Significant fading and discoloration. Also, because it has poor wear resistance,
For example, when it is applied to a manhole iron cover, not only the application surface is peeled off due to walking or passing of a vehicle, but the manhole iron cover becomes a temperature of 90 ° C. or higher in the hot weather in summer, and therefore the manhole iron cover is discolored or discolored in a short period of time. Furthermore, the coating surface is slippery when it rains, which is dangerous for walking and vehicle traffic.

As a technique for improving the above-mentioned drawbacks, application of thermal spraying of ceramics can be considered. That is, a ceramic sprayed material is sprayed on various base materials to form a sprayed coating, and heat resistance, corrosion resistance, wear resistance, and friction resistance can be imparted. However, most of the currently used thermal spray materials place importance on the above-mentioned respective performances, and the color tone of the thermal spray coating is hardly considered at present. For example, white alumina exhibiting a white color tone, alumina-titania system exhibiting a black color tone,
There are only alumina-cobalt type which exhibits a blue color tone and calcium silicate-chromia type which exhibits a green color tone.

Recently, an alumina-manganese dioxide-based thermal spray material has been proposed as a thermal spray material for forming a pink thermal spray coating, and a coating that develops a pink color tone when sprayed on a substrate such as metal or concrete is formed. it can. However, this is a very pale pink color, and since the abrasion resistance of the film is inferior, development of a deep pink color and improvement of abrasion resistance have been demanded.

[0006]

DISCLOSURE OF THE INVENTION The present invention is an improvement over the conventional alumina-manganese dioxide-based thermal spray material exhibiting a light pink color, which forms a deep pink thermal spray coating with improved wear resistance. To provide a thermal spray material.

[0007]

As a result of various researches by the present inventors, (1) when a thermal spray material in which a manganese compound is mixed with alumina and silica is further sprayed on a base material, wear resistance is improved. A sprayed coating that improves and has a deep pink color is obtained. (2) When a sprayed material obtained by blending alumina and a manganese compound and further blended silica and phosphorus pentoxide is sprayed on a base material, a sprayed coating having high wear resistance and a deep pink color is obtained. thing. (3) By spraying a thermal spray material obtained by firing the composition of (1) or (2) above onto a base material, a sprayed coating exhibiting a deep pink color with excellent abrasion resistance can be obtained. It was found that the present invention has been completed.

That is, the first invention is a thermal spray material composed of alumina, a manganese compound and silica.
The third invention is a thermal spray material consisting of alumina, manganese compound, silica and phosphorus pentoxide, the third invention is a thermal spray material obtained by firing alumina, manganese compound and silica, and the fourth invention is alumina. A thermal spray material obtained by firing a manganese compound, silica, and phosphorus pentoxide.

[0009]

The raw materials of alumina, manganese compound, silica and phosphorus pentoxide all preferably have a purity of 90% or more in order to improve the controllability of the color tone of the sprayed coating and the vividness of the color tone. As alumina, coarse-grained alumina, fine-grained alumina, fused alumina, activated alumina, low soda alumina, ultrafine-grained alumina, or the like can be used. As the manganese compound, manganese oxide, chloride, borate, sulfate or the like can be used.

Alumina and a manganese compound are components that control the thermal spray coating in a pink color tone, silica is a component that improves the wear resistance of the thermal spray coating, and phosphorus pentoxide is a component that enhances the darkening of the pink color. It is a component to control.

The blending ratio of the thermal spray material of the first invention is
Alumina: 70 to 98% by weight, manganese compound: MnO
_It is preferably 1 to 20% by weight in terms of ₂ and silica: 1 to 10% by weight. The blending ratio of the thermal spray material of the second invention is as follows: alumina: 60 to 97.9 wt%, manganese compound: 1 to 20 wt% in terms of MnO ₂ , silica: 1 to 10
% By weight, phosphorus pentoxide: 0.1 to 10% by weight is preferable.

The thermal spraying materials of the first and second inventions each have an average particle size of 5 to 100 μm, preferably 20 to 40 μm, because of the flowability of the thermal spraying material and the meltability of the material during coating formation. Good to do. Also, when using a spray dryer or the like to make granules, the particle diameter of each raw material should be 0.05 to 100 μm in order to make them as spherical as possible.
m, preferably 0.1 to 30 μm, methyl cellulose, polyvinyl alcohol, etc., 0.5 to 5
Granule size 5 to 500 μm, preferably 10
It is better to adjust to -100 μm.

The blending ratio of the thermal spray material of the third invention is
This is similar to that of the thermal spray material of the first invention. The blending ratio of the thermal spraying material of the fourth invention is the same as the blending ratio of the thermal spraying material of the second invention. The thermal spray materials of the third and fourth inventions can be obtained by firing the raw material mixture in a known firing furnace such as an electric furnace or a rotary kiln. If the firing temperature is lower than 1000 ° C., the sintering is difficult to proceed, which is not preferable. If the firing temperature is 1400 ° C. or higher, sintering proceeds, and the film is darkened and the wear resistance is improved during thermal spraying. Therefore, firing at 1400 ° C. or higher is particularly preferable. After pulverizing the calcinated product obtained at the above calcination temperature with a crusher such as a ball mill, the grain size is adjusted to the same particle size as in the thermal spray material of the first and second inventions,
Alternatively, it is made into a granular form and prepared as a thermal spray material.

Incidentally, as shown in Examples 5 and 6 described later, a mixture of the thermal spray material of the first and second inventions and the thermal spray material of the third and fourth inventions is sprayed. It can also be used as a material. The coating obtained by thermal spraying of these exhibits a hue between light and dark in a pink color tone and exhibits relatively excellent characteristics in abrasion resistance.

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

[0016]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. Fine-grained alumina (Al ₂ O ₃ ) having a purity of 98% as a starting material, and a purity of 91% as a manganese compound
Manganese dioxide (MnO ₂ ), silica with a purity of 98% (SiO ₂ ), and phosphorus pentoxide (P ₂ O ₅ ) with a purity of 94% were used. These were sufficiently mixed with a ball mill according to the composition of Table 1 so as to have an average particle size of 30 μm,
Used as a thermal spray material. Further, in accordance with the blending composition of each raw material, a sufficiently mixed mixture was fired at a predetermined temperature, pulverized and grained to prepare an average particle size of 30 μm to obtain a thermal spray material. Further, the above mixture or the calcined product was further pulverized into fine powder, and spray granulated with a spray dryer to prepare granules having an average particle size of 30 μm to obtain a thermal spray material. Plasma coating was performed under the following conditions on a SUS substrate on which a Ni—Al system was plasma sprayed using these thermal spray materials as an undercoat material in advance to form a coating.

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

The color tone of the thermal spray coating formed was examined using a Munsell color chart. In addition, in order to check wear resistance characteristics, JIS
A film of 1 mg in accordance with the reciprocating motion wear test method of H8503
The abrasion resistance was measured by measuring the number of reciprocations (DS / mg) of the abrasion paper required for the abrasion loss. The results are shown in Table 1.

[0019]

[Table 1]

As can be seen from Table 1, Al ₂ O ₃ : 70
The thermal spray material (Comparative Example 1) composed of 30% by weight of MnO ₂ and 30% by weight of MnO ₂ exhibits a light pink film of 5R9 / 1, but has a low DS value of 11. On the other hand, Al ₂ O ₃ : 94 wt%, MnO ₂ : 30 wt% and S
Thermal spray material composed of 3% by weight of io ₂ (Example 1 ...
The first invention product) is a film showing a pink color of 5R9 / 2, and the DS value is as high as 19 and the abrasion resistance is improved.

Thermal spraying material composed of Al ₂ O ₃ : 91% by weight, MnO ₂ : 3% by weight, SiO ₂ : 3% by weight and P ₂ O ₅ : 3% by weight (Example 2 ... Second invention product) Is a dark pink film showing 10RP8 / 4 and has a DS value of 2
It shows a high value of 0 and the wear resistance is improved. Al
_The thermal spray material (Comparative Example 2) obtained by firing a mixture of 70% by weight of ₂ O ₃ and 30% by weight of MnO ₂ at 1630 ° C. has a pink 5R9 / 2 coating, but a DS The value shows a low value of 14.

Al ₂ O ₃ : 80% by weight, MnO ₂ : 43
% By weight and SiO ₂ : 5% by weight.
The thermal spray material obtained by firing at 0 ° C. and crushing (Example 3 ... Third invention product) was a film showing 5R8 / 4 in a deep pink color, and a DS value of 35 was a very high value. Wearability is improved. A sprayed material obtained by firing and pulverizing a mixture of Al ₂ O ₃ : 79 wt%, MnO ₂ : 17 wt%, SiO ₂ : 7 wt% and P ₂ O ₅ : 7 wt% at 1600 ° C. Example 4 ... Fourth invention) is a deep pink 10R7
The film showed a value of / 6 and the DS value was as high as 37. Further, as shown in Examples 5 and 6, when the respective Example products were appropriately mixed, a film having a color tone and a DS value according to the mixing ratio was obtained.

[0023]

By using the ceramics thermal spray material of the present invention, it is possible to form a thermal spray coating having a pinkish color tone which is excellent in abrasion resistance. Further, since the thermal spray coating of the present invention has corrosion resistance and heat resistance, by spraying on a manhole iron lid, various metal substrate surfaces, concrete surface, etc., wear resistant, corrosion resistant, heat resistant pink type It is possible to form a thermal sprayed coating.

Claims (4)

[Claims] 1. A thermal spray material comprising alumina, a manganese compound and silica. 2. A thermal spray material comprising alumina, a manganese compound, silica and phosphorus pentoxide. 3. A thermal spray material obtained by firing alumina, a manganese compound and silica. 4. A thermal spray material obtained by firing alumina, a manganese compound, silica and phosphorus pentoxide.