WO2018047994A1

WO2018047994A1 - High-flowability spray powder and method for producing same

Info

Publication number: WO2018047994A1
Application number: PCT/KR2016/010071
Authority: WO
Inventors: 문흥수; 신평우; 이훈철
Original assignee: (주)세원하드페이싱
Priority date: 2016-09-08
Filing date: 2016-09-08
Publication date: 2018-03-15
Also published as: JP2019512611A; JP6659872B2; KR102085258B1; KR20180061385A

Abstract

Disclosed are a high-flowability powder that improves the flow characteristic of a spray powder to be introduced into a spray gun to improve the quality of a spray coating film, and a coating method using the same. The flow characteristic of the spray powder can be significantly improved by coating an organic monomer on the surface of a granulated spray powder, a heat-treated spray powder or a plasma surface-treated spray powder. Further, the improved flow characteristic of the spray powder coated with the organic monomer can increase the cost competitiveness of the spray powder because the coating yield, the quality of a coating layer, and the duration of use of the spray gun are extended.

Description

High flow sprayed powder and preparation method thereof

The present invention relates to a high flow sprayed powder and a method for producing the same, and more particularly, to a high flow sprayed powder coated with an organic monomer and a method for producing the same.

Ceramic spray coating technology using thermal spray powder is applied to various fields. By industry, it is most actively applied to general machinery, semiconductor, liquid crystal, steel and printing. With the expansion of market sizes in China, Korea, and Singapore, Asia's market size is a very promising technology that is growing to the same level as the US and EU.

Spray coating methods using thermal spray powders include arc spraying, flame spraying, high speed flame spraying, plasma spraying, cold spray (CS), suspension plasma spray, and SPPS (Solution precursor plasma spray). .

In terms of thermal spraying materials, we are actively developing and selling stabilized zirconia (YSZ) used for thermal barrier coating, Al ₂ O ₃ as insulation material, and TiO ₂ for photocatalyst. Avatar is also being developed for application as a high value-added thermal spray coating material. Tungsten (W) is also an important material as a high-temperature material for shielding radiation or plasma bulkheads in nuclear fusion reactors, and thermal spray coatings are being developed for its application.

Ceramic spray coating technology has been applied to a variety of wear-resistant coatings to improve the wear resistance, the wear-resistant coating by the thermal spray coating has a sufficient mechanical strength. Thermal spray coatings provide a significant level of thermal spray coating material for ceramic powders to provide control over friction and abrasion to withstand contact with other structural surfaces that come in contact in the form of sliding, rolling or impact. Used as Such ceramic coatings enable effective control of wear and friction as described above, and thus applications in industrial fields are continuously expanding.

In the thermal spray coating method, the greatest influence on the quality of the thermal spray coating film is to maintain the discharge rate of the thermal spray powder discharged from the thermal spray powder supply portion. If the velocity of the thermal sprayed powder is not kept constant during the thermal spray coating, the uniformity of the thermal sprayed coating film and the rate of generation of pores are out of the design value, or have a disadvantageous effect such as the strength of the thermal sprayed coating.

In addition, when the sprayed powder is discharged from the nozzle to the plasma or flame of the sprayed gun at the supply portion of the sprayed powder of the spray gun, clogging occurs. Like the phenomenon that occurs in an hourglass, it is a common problem that occurs when the powder is discharged at a defined inlet.

When the powder used for the spray coating is produced in a slurry, and the slurry is used by discharging, the clogging phenomenon may be suppressed, and a discharge amount may be generated according to a predetermined pressure.

However, the powder discharge using the slurry is caused to deteriorate the quality of the thermal spray coating due to the organic impurities contained in the slurry production.

In addition, the spray powder produced through spray drying, the quality of the thermal spray coating occurs due to the shape of the granules, the surface roughness of the granules.

Most of the thermal spray powders currently applied are sphericalized by spray drying to reduce friction between powders and control the center of gravity of the powders by spherical centers, thereby reducing clogging and applying to the thermal spray coatings.

However, the cost of producing the powder by adjusting the center of gravity of the powder to the center of the sphere has a large and difficult problem.

In addition, the flow characteristic value of the powder is low, resulting in a decrease in the spray coating quality.

In the Republic of Korea Patent No. 10-0669819 (filed August 19, 2003), when the slurry is produced, the powder is dispersed using a non-aqueous solvent, and the slurry is spray-dried Y ₂ O ₃ system, Al ₂ O ₃ system, TiO ₂ -based, AlN-based and nitride-based granulated powders are prepared. The granulated powder is then sintered to complete ceramic powder production. In particular, the flow rate of the conventional Y ₂ O ₃ raw material powder is an unmeasurable state, and it is reported that the powder has a flow characteristic of 0.19 g / sec when the powder is prepared by spray drying.

However, there is a limit to improving the flowability of the powder through the change of the powder manufacturing method, and still does not significantly improve the quality of the sprayed coating film.

In Republic of Korea Patent No. 10-0863697 (application date December 31, 2007), the spray coating powder and the sealing organic powder is sprayed together to form a spray coating film to seal the spray coating film without any additional process.

In addition, the spray coating powder is obtained by forming a sealing film on the outer surface of the ceramic powder and surrounding it, and heat treating the sealing organic substance powder in the state surrounding the outer surface. The particle diameter ratio of the ceramic powder and the said organic substance powder is 1: 0.1-0.3, The range is narrowed further, The thermal spraying powder whose content ratio of the ceramic powder and the organic substance powder was adjusted to 1: 0.2-0.5 is disclosed.

However, the prior art is to form a sealing film of the thermal spray coating at the time of forming the thermal spray coating, there is a problem that the quality, such as uniformity of the thermal spray coating film is degraded due to the aggregation of the thermal spray powder because a large amount of organic material is coated on the ceramic powder. .

In addition, there is a problem in that the powder discharge due to the clogging phenomenon generated during the discharge of the thermal spray powder is delayed and the quality of the thermal spray coating is deteriorated.

The first technical problem to be achieved by the present invention is to provide a high flow powder with improved flow characteristics during powder discharge.

In addition, the second technical problem to be achieved by the present invention is to provide a method for producing a high-flow sprayed powder for achieving the first technical problem.

The present invention for achieving the above-described first technical problem, to provide a high flow spray powder characterized in that it comprises a granulated powder and an organic monomer attached to the surface of the granulated powder.

The granular powder may have any one selected from the group consisting of ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , AlN, HfO ₂ , TiO ₂ and stabilized zirconia.

The granulated powder is characterized in that the high flow sprayed powder, which is a powder produced through a granulation process.

The granulated powder is characterized in that the high flow sprayed powder which is a powder surface-treated by plasma.

It is characterized in that the high flow sprayed powder of which the surface roughness of the granulated powder surface-treated by the plasma is reduced.

The surface of the granule powder is melted by the plasma, characterized in that the high-flow sprayed powder of which the surface density of the granule powder is increased.

The granular powder is characterized in that the high fluid spray powder is stabilized zirconia.

The content of the organic monomer is characterized in that the high fluid spray powder in the range of 0.05 wt% to 5.0wt% relative to the weight of the granule powder.

The organic monomer is characterized in that the high flow sprayed powder occupying 5% to 100% of the surface area of the granule powder.

The organic monomer may have any one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

The organic monomer is palmitic acid, tetraethyl orthosilicate, hexamethyldsiloxane, acrylic, styrene ethylene, acrylamide, methacrylic acid, acrylate, vinyl carboxylic acid, acrylonitrile, propylene oxide, butyl acrylate, stearic acid (C ₁₇ H ₃₅ COOH), oleic acid (CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ COOH), eicosanic acid (C ₁₉ H ₃₉ COOH) and docosanoic acid (C ₂₁ H ₄₃ COOH) have.

The present invention for achieving the above-described second technical problem, preparing a granulated powder prepared through a granulation process, preparing an organic monomer solution by adding an organic monomer to a solvent, the granules in the organic monomer solution It is to provide a method for producing a high flow sprayed powder comprising the step of adding a powder, mixing and coating the organic monomer on the surface of the granule powder while evaporating the solvent.

The granulated powder is ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , AlN, HfO ₂ , TiO ₂ and a method of producing a high flow spray powder, characterized in that any one selected from the group consisting of stabilized zirconia.

After the step of preparing the sprayed powder prepared by the granulation process, the method of producing a high flow sprayed powder characterized in that it further comprises the step of plasma-treated the sprayed powder.

The surface of the granule powder is melted by the plasma surface treatment, so that the surface density of the granule powder is increased, and the surface roughness is reduced.

The granulated powder is a method for producing a high flow sprayed powder, characterized in that the stabilizing zirconia.

According to the present invention described above, there is an effect of forming an organic coating layer on the surface of the sprayed powder, inducing a certain amount of static electricity (repulsive force) generation on the surface of the sprayed powder to prevent agglomeration between the powders.

In addition, the flow characteristics of the powder during the thermal spray coating of the organic coating powder is improved, there is an effect that the clogging phenomenon in the spray nozzle is suppressed.

In addition, by improving the flow characteristics of the powder during thermal spray coating has an effect of increasing the thickness uniformity and surface roughness of the thermal spray coating film.

In addition, the use of the powder with improved flow characteristics has the effect of prolonging the continuous use time of the plasma spray gun for the spray coating.

In addition, by using the powder with improved flow characteristics, there is an effect of removing the nozzle clogging phenomenon of the powder injector portion of the spray gun.

1 is a flowchart illustrating a process of coating an organic monomer on a sprayed powder surface according to an embodiment of the present invention.

Figure 2 is a 300 times electron microscope image of the granule powder in the range of 5 ㎛ to 25 ㎛ in accordance with a preferred embodiment of the present invention.

Figure 3 is a 1000 times electron microscope image of the granule powder in the range of 5 ㎛ to 25 ㎛ in accordance with a preferred embodiment of the present invention.

Figure 4 is a 300 times electron microscope image of the granule powder in the range of 15 ㎛ to 45 ㎛ in accordance with a preferred embodiment of the present invention.

5 is a 1000-fold electron microscope image of granule powder in the range of 5 μm to 25 μm in accordance with a preferred embodiment of the present invention.

6 is an electron microscope image of 300 times the powder of the plasma surface treatment of the granule powder in the range of 15 ㎛ to 45 ㎛ according to an embodiment of the present invention.

Figure 7 is an electron microscope image of 1000 times the powder of the plasma surface treatment of the granule powder in the range of 15 ㎛ to 45 ㎛ in accordance with a preferred embodiment of the present invention.

8 is a schematic view of a cross section of a granular powder coated with an organic monomer according to an embodiment of the present invention.

9 is a schematic view of a cross section of the plasma surface-treated granulated powder coated with an organic monomer according to an embodiment of the present invention.

10 is a schematic diagram of an experimental apparatus for measuring the flow rate of the sprayed powder according to an embodiment of the present invention.

11 is a cross-sectional image of a coating layer formed of a thermal spray coating using the thermal spray powder according to an embodiment of the present invention.

12 is a cross-sectional image of the coating layer measured by enlarging the dash circle area of FIG. 11 according to an exemplary embodiment of the present invention.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the drawings, similar reference numerals are used for similar elements.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention.

1 is a flowchart illustrating a process of coating an organic monomer on a sprayed powder surface according to an exemplary embodiment of the present invention.

Referring to Figure 1, the sprayed powder is manufactured by the spray drying method which is a conventional method. The powder produced by spray drying is a powder in the form of granules, which is a powder in the form of an aggregate of fine powder.

Usually, the granular powder is calcined or calcined to be used as a sprayed powder. The calcination process is 4 hours or less at 1200 ° C., and the firing process is then 4 hours or less at 1600 ° C., but the heat treatment step is performed according to the required properties of the thermal sprayed powder. This process can be carried out to prepare a sprayed powder.

In the present invention, after preparing the granulated powder prepared through a calcination process or a calcination process, the granulated powder is added to the solution in which the organic monomer is dissolved. After the granular powder is charged, the solution is stirred and the granular powder is allowed to sufficiently disperse in the solution.

When the granular powder is sufficiently dispersed in the solution, the solution is heated to evaporate the solvent. Subsequently, the coating of the organic monomer on the surface of the thermal spray powder is completed so that the organic monomer is coated on the surface of the thermal spray powder. Solvent evaporation does not occur at a high rate and is heated in a bath in order to uniformly heat the entire solution. The solvent evaporation rate varies depending on the total amount, but is controlled by process optimization.

After all of the solvent has evaporated, the thermal sprayed powder is in an apparent aggregated state. This can resolve the coagulation state through a sieving process or a simple disintegration process.

The amount of the organic monomer coating on the surface of the granular powder may be determined by adjusting the amount of the organic monomer added during preparation of the initial solution or the amount of the sprayed powder introduced into the solution.

When the thermal spray coating process using the granular powder is carried out, the discharge of the granular powder does not occur. Therefore, the powder density is increased through the calcining process or the calcination process of the granulated powder, the surface roughness is reduced, and the spray powder can be used for the spraying process. However, there is still a problem of the powder discharge for the spray coating has a great effect on the quality of the thermal spray coating film. Each spray coating company has powder treatment know-how and the specification of spray powder for spray coating is decided. However, problems such as the delayed ejection of powder during spray coating always exist.

Referring to FIG. 2, it is an electron microscope image of the granulated powder prepared by the spray drying method, and the granular powder has a size distribution in the range of 5 μm to 25 μm.

Referring to FIG. 3, when looking at the surface of the granular powder, it is indirectly predicted that the surface roughness of the granular powder will have a large value, and the granular powder is produced through calcination and firing processes.

In addition, the image on the electron microscope can be seen that there is a considerable level of internal pores, the surface area of the powder is large, it can be expected that the amount of static electricity due to friction between the powders. Electrostatic charges are generated due to excessive charge on the surface of the granular powder, and the frequency of contact between the powders is increased within a predetermined space so that the agglomeration of the granular powder is easily generated.

For this reason, when the granulated powder prepared by spray drying is injected into a spray gun for spray coating, the aggregated powder is easily clogged. Therefore, since the ejection of the granulated powder does not occur normally with a limited discharge hole, the normal spray coating does not occur.

Usually, the powder is optimized for the thermal spray coating by using a powder whose change in powder surface state or powder distribution is optimized by the firing process of the granulated powder, but the quality or coating efficiency of the thermal spray coating is not improved.

Referring to FIG. 4, it is an electron microscope image of the granulated powder prepared by the spray drying method, and the granular powder has a size distribution in the range of 15 μm to 45 μm.

5 is a 1000-fold electron microscope image of granule powder in the range of 15 μm to 45 μm in accordance with one preferred embodiment of the present invention.

Referring to FIG. 5, although the size distribution of the granular powder is upward, the surface roughness of the granular powder is not reduced, and pores are present in the granular powder.

Even when the size distribution of the granular powder is raised and the thermal spray coating is performed, the ejection of the granular powder hardly occurs. That is, even when the spray powder size distribution is upward, the charge state generated on the surface of the powder is generated due to the tendency of the powder to aggregate.

Referring to Figure 6, it is an electron microscope image of the powder surface-treated powder of the granulated powder prepared by the spray drying method, the size distribution of the sprayed powder plasma surface treatment is a spray powder in the range of 15 ㎛ to 45 ㎛.

Referring to FIG. 7, it can be predicted that the surface of the plasma surface treated granular powder is considerably smoother and the surface density is improved, and pores on the image are hardly visible.

8 to 9, this structure is a form in which the surfactant is adsorbed on the surface of the granulated powder in a micelle structure. The micelle structure is a structure of an organic monomer adsorbed on the surface of the powder in which the part which is bonded to the surface of the powder is a hydrophobic part and the part which is in contact with air is a hydrophilic part. When water is used as a solvent to dissolve the organic monomer, and the thermal spray powder is added, the organic monomer adheres to the surface of the thermal spray powder. At this time, the portion of the organic monomer in contact with water is negatively charged, and the hydrophobic material such as oil forms an micelle structure in which the organic monomer is in contact with the powder surface.

When the granular powder is added to the solution in which the organic monomer is dissolved, the organic monomer is bonded to the surface of the granular powder. When the solvent is water, the surface of the granule powder adheres to the organic monomer of the lipophilic portion, and the hydrophilic portion is located toward the solvent. In this state, the granulated powder is dispersed in the solvent.

The sprayed powder is dispersed in the solution containing the organic monomer, and the solvent is slowly evaporated to obtain the sprayed powder coated with the organic monomer, thereby obtaining the sprayed powder coated with the organic monomer.

The surface of the granular powder coated with the organic monomer is not significantly reduced in the surface roughness, but the friction force between the granular powders is reduced due to the coating formed with the organic monomer, and due to the proper amount of electrostatic charge generated in the coating formed with the organic monomer, Agglomeration is in a controlled state.

Even in the case of the plasma surface treated granular powder, when a film is formed of an organic monomer, aggregation between the powders is controlled by reducing friction between the granular powders.

Referring to FIG. 10, it is a schematic diagram of a powder flow measurement apparatus including a sample cup 70 including a measuring funnel 100 loaded with powder and a specific gravity cup 60 containing free falling powder. The sample cup 70 and the specific gravity cup 60 have a distance 80 between cups of 48 mm, and the internal volume of the specific gravity cup 60 is about 100 cc.

Standard measurement methods for fluidity characteristics are specified in KS L 1618-4. This standard is the result of the research of enactment of the KS standard for abrasive materials and special ceramic products, which is part of the standardized academic research service project conducted in 2002.

Most granular powders made of ceramics are made into granules due to handling problems, and are manufactured by spray drying granulation, etc., and the characteristics of granule diameter, bulk density, drying loss, flow rate, etc. are confirmed by standard methods.

Since the diameter range of the granular powder of ceramic material is mostly 20 micrometers to 500 micrometers, this range is limited to tens to hundreds of micrometers, and most ceramic granules will be included in the diameter range of this granular powder.

The measurement procedure for measuring the flow rate of the powder is as follows. After filling the measurement funnel 100 with the measurement sample which is the thermal spray powder, the filling sample falls freely into the specific gravity cup 60 through the powder discharge port 90. The time for free fall of the powder is measured, and it is calculated by averaging three times in total.

The flow rate F is calculated to three decimal places according to the following equation, and after three measurements, the arithmetic average of the three measurement results is calculated.

Where F is the flow rate (g / s), w ₁ is the mass (g) of the specific gravity cup (60), w ₂ is the mass (g) of the sum of the samples dropped in the specific gravity cup (60) and the specific gravity cup (60). , t is the time it takes for the sample to fall (s, second). That is, w ₂ -w ₁ is the mass of the sample free falling into the specific gravity cup 60.

Example 1

The solution is prepared using palmitic acid as an organic monomer material. 0.2g of palmitic acid is prepared, and the mixture is put into a beaker containing 200 ml of ethanol and dissolved by stirring for a sufficient time of about 0.5 hr. Note that the amount of ethanol is not excessively reduced during the dissolution of palmitic acid.

10 g of stabilized zirconia granule powder is added into the ethanol solution in which palmitic acid is dissolved, and the mixture is stirred while stirring until the total amount of granule powder is 100 g. The granule powder was coated with palmitic acid using a size ranging from 5 μm to 25 μm. For a sufficient time of at least 1 hour, stirring was continued until the granular powder could be dispersed in solution.

Subsequently, while stirring and heating the solution containing the granular powder, ethanol used as the solvent was evaporated, leaving only the granular powder coated with palmitic acid. The granitic powder coated with palmitic acid is left in a weakly aggregated state. In order to disintegrate it, disintegration was performed using a sieving process.

The size distribution of the powder produced by the above-described method was little different from the size distribution of the granulated powder initially introduced. Since the weight content of palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH) is 0.2 wt% relative to the granular powder, the size of the granular powder is hardly increased.

The flow characteristics of the granitic powder coated with palmitic acid prepared as described above were measured. In the case of stabilized zirconia granule powder before palmitic acid coating, the measured value is almost zero with very low flow characteristics. In contrast, the granitic powder coated with palmitic acid significantly increased the flow characteristics, and the flow characteristics were measured as 1.0912 g / sec.

Electron microscopic images of the granitic powder coated with palmitic acid show an image similar to that of FIGS. 2 to 5. The coating thickness of 0.2 wt% palmitic acid is very small, which is difficult to see by electron microscopy.

The surface roughness of the granular powder was measured to be 20 nm or more, and the surface roughness of the palmitic acid-coated granular powder was measured to be less than 20 nm. As a result, the coating of palmitic acid on the granular powder surface can be indirectly confirmed.

The coating amount of palmitic acid is preferably 0.01 wt% to 5.0 wt%, but is not limited thereto.

Comparative Example 1

0.2g of polymer polystyrene (polystylene) is prepared and introduced into a beaker containing 200 ml of ethanol, and agitation is performed for a sufficient time of about 0.5hr to dissolve the polystyrene (polystylene).

Polystyrene coating was performed on 100 g of stabilized zirconia granule powder in the same manner as in Example 1. The flow characteristics of the prepared polystyrene-coated stabilized zirconia granule powder were carried out. The flow characteristic value of the polystyrene coated stabilized zirconia granule powder was determined to be 0.4453 g / sec.

Using the thermal spray powder prepared as described above was loaded on the plasma gun, and the thermal spray powder was discharged to prepare a thermal spray coating film. The produced thermal spray coating film had an uneven surface, and a sharp protrusion was also observed. It is presumed that the quality of the thermal spray coating has occurred due to the clogging phenomenon or the partial aggregation of the thermal spray powder when the thermal spray powder is discharged. In order to improve the quality of a thermal sprayed coating, the flow characteristic of a thermal sprayed powder needs to be improved.

In addition, when producing a sprayed coating using the polymer-coated granule powder, an increase in the amount of carbon remaining in the sprayed coating can be brought about, thereby degrading the quality of the sprayed coating.

Comparative Example 2

0.2g of trimeric glycolic acid, which is an oligomer polymerized with a small number of molecules, is prepared and introduced into a beaker containing 200 ml of ethanol, followed by a sufficient time of about 0.5hr to dissolve.

In the same manner as in Example 1, trimeric glycolic acid coating was performed on 100 g of stabilized zirconia granule powder. In addition, the flow characteristics of trimeric glycolic acid coated stabilized zirconia granules were measured. The flow characteristic value of the polystyrene coated stabilized zirconia granule powder was determined to be 0.6521 g / sec.

The flow characteristics were improved to a small level compared to the polymer coated granule powder, and showed good results as a spray powder applied to the thermal spray coating.

Example 2

0.2g of palmitic acid is prepared and added into a beaker containing 200 ml of ethanol, followed by a sufficient time of about 0.5hr to dissolve. Take care to maintain the amount of ethanol in the process of dissolving palmitic acid.

10 g of stabilized zirconia granule powder is added into the ethanol solution in which palmitic acid is dissolved, and the mixture is stirred while stirring until the total amount of granule powder is 100 g. The granule powder was coated with palmitic acid using a size ranging from 15 μm to 45 μm. For a sufficient time of at least 1 hour, stirring was continued until the granular powder could be dispersed in solution.

The flow characteristics of the granitic powder coated with palmitic acid prepared as described above were measured. In the case of stabilized zirconia granule powder before palmitc acid coating, the measured value is almost zero with very low flow characteristics. In contrast, the granitic powder coated with palmitic acid significantly increased the flow characteristics, and the flow characteristics were measured as 1.9084 g / sec.

By increasing the size distribution of the granular powder, it can be seen that the flow characteristics have been improved to a significant level in the case of the granitic powder coated with palmitic acid. This is presumably due to the fact that the amount of static electricity on the surface of the coated powder is small relative to the volume of the powder, making it easier to maintain the separation state between the powders.

The spray coating process was performed using the granitic powder coated with palmitic acid prepared as described above.

The coating amount of palmitic acid is preferably 0.01 wt% to 2.0 wt% relative to the isolated powder, but is not limited thereto.

11 to 12, an image of a sample in which a thermal spray coating is manufactured using the thermal spray powder prepared in Example 2 is illustrated. FIG. 12 is an enlarged image of the coating area 110. It can be seen that there is very little). When the pore content of the thermal sprayed coating layer using the granular powder in Example 2 was measured using an image analysis system, the pore content of about 5% was measured.

The thermal sprayed coating was prepared using the prepared thermal spray powder of Example 1, and the pore content of the thermal sprayed coating was measured to be 6% or more. This shows that the properties of the thermal sprayed coating can be controlled by controlling the flow characteristics of the thermal sprayed powder.

Example 3

10 g each of the stabilized stabilized zirconia granulated powder was plasma-treated into the ethanol solution in which palmitic acid was dissolved, and the mixture was stirred while stirring until the total powder was 100 g. Plasma surface-treated stabilized zirconia granule powder was coated with palmitic acid using a size ranging from 15 μm to 45 μm. For a sufficient time of at least 1 hour, stirring was performed until the powder could be dispersed in solution.

The flow characteristics of the granitic powder coated with palmitic acid prepared as described above were measured. Plasma surface-treated stabilized zirconia granules powder before palmitc acid was coated with very low flow characteristics, resulting in nearly zero measurements. In contrast, the plasma surface-treated stabilized zirconia granule powder coated with palmitic acid significantly increased the flow characteristics, and the flow characteristics were measured as 2.0152 g / sec.

The spray coating process was performed using the granitic powder coated with palmitic acid prepared as described above. When the thermal spray coating was performed using the powder prepared as described above, and the thermal spray coating film was evaluated, the pore internal content, which is the same level as the thermal spray coating prepared in Example 2, was measured to a value within 5%.

It can be seen that the organic monomer is coated on the surface of the granulated powder treated with plasma surface, and its flow characteristics are improved. This is due to the improved uniformity of the organic monomers coated on the powder surface.

In the case of using a sprayed powder having improved flow characteristics, the spray gun can be used for a longer time, and the quality of the sprayed coating can be improved. In addition, it becomes easier to control the properties of the thermal spray coating.

Comparative Example 3

0.2g of polystyrene is prepared and introduced into a beaker containing 200 ml of ethanol, followed by a sufficient time of about 0.5hr to dissolve.

Polystyrene coating was performed on 100 g of the stabilized zirconia granule powder subjected to the plasma surface treatment as in Example 1. In addition, the flow characteristics of the polystyrene-coated stabilized zirconia granule powder were measured. The flow characteristic value of the polystyrene coated stabilized zirconia granule powder was determined to be 0.4128 g / sec.

It can be seen that it is not significantly different from the course of Comparative Example 1, which is that the selection of the coating material has a great influence on the flow characteristics of the sprayed powder.

In addition to the organic monomer materials as described above, Tetraethyl orthosilicate (TEOS) or Hexamethyldisiloxane may be used to coat the granular powder surface. In this case as well, it shows improved flow characteristics.

In addition, at least one selected from the group consisting of styrene, acrylic, ethylene, acrylamide, methacrylic acid, acrylate, vinylcarboxylic acid, AN, PROPYLENE OXIDE, silicone macro and butyl acrylate as the organic monomer (monomer) granules The surface of the powder can be coated.

In addition, organic monomers include stearic acid (C ₁₇ H ₃₅ COOH), oleic acid (CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ COOH), eicosanic acid (C ₁₉ H ₃₉ COOH) and docosanoic At least one selected from the group consisting of acid (C ₂₁ H ₄₃ COOH) may be used to coat the surface of the granular powder.

The granulated powder surface-coated with the organic monomer is loaded into the spray gun, and the sprayed spray process is performed by discharging the powder into the flame from the spray gun. That is, the powder for thermal spray coating is a thermal spray powder, and the thermal spray powder may be a granulated powder coated with an organic monomer or a granulated powder coated with a plasma.

(Explanation of the sign)

10: organic monomer 20: surface of granule powder

30: granulated powder 40: plasma treated granulated powder surface

50: plasma treated granule powder

60: specific gravity cup 70: sample cup

80: distance between cups 90: powder discharge port

100: measuring funnel 110: coating area

Claims

Granulated powder; And

A high flow sprayed powder comprising an organic monomer attached to the surface of the granular powder.
The method of claim 1,

The granular powder is ZrO 2 , Y 2 O 3 , Al 2 O 3 , AlN, HfO 2 , TiO 2 and a high fluid spray powder, characterized in that any one selected from the group consisting of stabilized zirconia.
The method of claim 2,

The granulated powder is a high fluid spray powder, characterized in that the powder produced through a granulation process.
The method of claim 3,

The granular powder is a high flow spray powder, characterized in that the powder surface-treated by plasma.
The method of claim 4, wherein

The high fluid spray powder, characterized in that the surface roughness of the granulated powder surface-treated by the plasma is reduced.
The method of claim 4, wherein

The surface of the granular powder is melted by the plasma to increase the surface density of the granulated powder, characterized in that the high-flow sprayed powder.
The method of claim 6,

The granular powder is a high fluid spray powder, characterized in that the stabilizing zirconia.
The method of claim 1,

The high molecular weight spray powder, characterized in that the content of the organic monomer is in the range of 0.05 wt% to 5.0wt% relative to the weight of the granule powder.
The method of claim 1,

The organic monomer is a high fluid spray powder, characterized in that occupies 5% to 100% of the surface area of the granule powder.
The method of claim 1,

The organic monomer is a high fluid spray powder, characterized in that any one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.
The method of claim 1,

The organic monomer is palmitic acid, tetraethyl orthosilicate, hexamethyldsiloxane, acrylic, styrene ethylene, acrylamide, methacrylic acid, acrylate, vinyl carboxylic acid, acrylonitrile, propylene oxide, butyl acrylate, stearic acid (C 17 H 35 COOH), oleic acid (CH 3 (CH 2 ) 7 CH = CH (CH 2 ) 7 COOH), eicosanic acid (C 19 H 39 COOH) and docosanoic acid (C 21 H 43 COOH) High thermal spray powder.
Preparing a granulated powder prepared through a granulation process;

Preparing an organic monomer solution by adding an organic monomer to a solvent;

Injecting the granular powder into the organic monomer solution and mixing; And

Coating the organic monomer on the surface of the granule powder while evaporating the solvent.
The method of claim 12,

The granular powder is ZrO 2 , Y 2 O 3 , Al 2 O 3 , AlN, HfO 2 , TiO 2 and a method for producing a high flow sprayed powder comprising any one selected from the group consisting of stabilized zirconia.
The method of claim 12,

After the step of preparing the sprayed powder prepared by the granulation process,

Plasma surface treatment of the sprayed powder further comprising the step of producing a high flow sprayed powder.
The method of claim 14,

The surface of the granule powder is melted by the plasma surface treatment to increase the surface density of the granule powder, the surface roughness manufacturing method of high flow sprayed powder.
The method of claim 15,

The granular powder is a method of producing a high flow sprayed powder is stabilized zirconia.