KR102197178B1 - Mineral material composition from basalt source and anti-wear coating layers and anti-wear shaped articles manufactured by using the same - Google Patents

Abstract

The present invention is a powdered mineral composition after melting and extraction of basalt, and has a scratch strength of at least 9.0H and a Mohs hardness of at least 7.3 when direct melt coating on the surface of a metal base material, and has a temperature of 500°C and a temperature of -70°C, respectively. It provides a basalt-derived abrasion-resistant mineral material composition capable of forming a coating film without peeling and breaking under temperature. The mineral material composition may be further processed into various shapes such as pellets, coating films, molded bodies, etc. and used.

Description

A mineral material composition derived from basalt, and an abrasion-resistant coating film and abrasion-resistant molded body manufactured using the same

The present technology is a technology in the field of ceramic materials using minerals, and more specifically, relates to a new material technology based on minerals that are remarkably improved in terms of physical properties such as wear resistance.

With the development of the ceramic material field, various inorganic materials have been developed. Various inorganic materials based on minerals extracted from ore, from artificial ceramic materials that undergo chemical processes, are used for various purposes throughout the industry.

In particular, mineral materials are eco-friendly materials and have various advantages because they can utilize the unique physicochemical properties of minerals. These mineral-based ceramic materials have recently been used in the coating field to protect the basic base material and to enhance physical properties.

However, conventional ceramic coating materials are fundamentally difficult to avoid degradation of durability over time because a coating film is formed through physical bonding by forming a binder layer at the interface to improve coating bonding. For example, in the case of Teflon coating, multiple binder layers are introduced to improve adhesion between Teflon and the base material. In addition, the conventional coating film has a problem such as generation of cracks due to a number of pores present at the interface between the base material and the coating film. Furthermore, conventional ceramic coating materials have fundamental limitations in being used in precision fields requiring perfect wear resistance or under poor weather or environmental conditions. Therefore, it can be said that there has been a steady demand for the development of new materials and breakthrough changes to conventional mineral-based materials.

The present invention is an invention completed by developing a new material capable of causing a breakthrough in physical properties of a conventional mineral-based ceramic material, and the present invention causes a breakthrough in physical properties such as wear resistance, corrosion resistance, high temperature and low temperature stability. It is an object to provide a wear-resistant mineral material composition derived from basalt.

In addition, the present invention is a pellet manufactured by molding the mineral material composition, it is an object of the invention to provide a wear-resistant pellet that can be applied to various applications and processed and maximized convenience.

In addition, an object of the present invention is to provide a method of forming a coating film exhibiting remarkably excellent physical properties without a binder on a base material such as a metal by using the above-described pellet or mineral material composition.

In addition, an object of the present invention is to provide a wear-resistant coating film derived from basalt produced by the method of forming the coating film.

Furthermore, an object of the present invention is to provide a basalt-derived abrasion-resistant molded article molded using the mineral material composition and having excellent mechanical properties.

The abrasion-resistant mineral material composition derived from basalt according to an embodiment of the present invention is a powdered mineral composition after melting and extraction of basalt, and has a scratch strength of at least 9.0H and a Mohs hardness of at least 7.3 when direct melt coating on the surface of the metal base material. It has, and it is possible to form a coating film without peeling and breaking phenomena under a temperature of 500 ℃ and -70 ℃ respectively. The mineral composition, SiO ₂ 100 parts by weight; Al ₂ O ₃ 25 to 32 parts by weight; CaO 18 to 22 parts by weight; MgO 18 to 22 parts by weight; Fe ₂ O ₃ 18 to 22 parts by weight; And 0.1 to 2 parts by weight of at least one metal component selected from the group consisting of Ti, Y, La, Ce, and Nd.

The wear-resistant pellets derived from basalt according to an embodiment of the present invention may be formed by sintering and molding the composition into a pellet shape, and due to the convenience of a pellet type, it may be introduced into various applications and processed efficiently.

As a result of the analysis of the Korea Institute of Materials Research, it was confirmed that the pellet contains ball (CaFeMg)Si ₂ O ₆ as a constituent component.

A method of forming a wear-resistant coating film derived from basalt according to an embodiment of the present invention comprises the steps of preparing a coating composition by melting the above-described pellets at a temperature of 800 to 900°C; Cleaning and drying the surface of the base material; And directly coating the coating composition on the surface of the base material without a binder.

The abrasion-resistant coating film derived from basalt according to an embodiment of the present invention is a coating film formed by the above-described method, and pores are not formed at the interface with the base material, and the amount of Si element decreases as the base material approaches The amount has a tendency to increase.

At least one region of the coating film may be chemically adsorbed on the surface of the base material.

On the other hand, the composition of the coating film was found to contain the same (CaFeMg)Si ₂ O ₆ composition as the pellet as a result of analysis by the Korea Institute of Materials Research.

The wear-resistant molded article derived from basalt according to an embodiment of the present invention may be melted, fired, and molded from the above-described mineral material composition or the above-described pellet.

The molded body may function as a kind of new alloy by further including a separate metal component supplied from the outside in addition to the metal component contained in the mineral material composition.

The mineral material composition according to the present invention is an eco-friendly inorganic material derived from basalt, and can be used in various applications in industrial fields requiring excellent physical properties and mechanical properties by being made of various molded articles manufactured by molding a coating agent or the material itself. This is a very excellent material.

In addition, the mineral material composition may be provided as a pellet by melting the material in the form of a powder for the first time, so that the convenience of distribution and the convenience of operation can be maximized.

In particular, while conventional ceramics are fundamentally not well bonded to metals, the mineral material composition according to the present invention exhibits perfect bonding properties to the base material as a coating film.

The basalt long mineral material of the present invention basically has the following physical and mechanical properties.

-It has high-strength abrasion resistance that can withstand extreme wear environments such as sand oil mining, which is the same as sapphire or diamond almond (Mohs hardness is 7.3 level)

-It is possible to form a coating film with high quality corrosion resistance and heat resistance applied to semiconductor processing equipment.

-Excellent antibacterial properties due to basic acid resistance and minerals themselves

-No peeling or destruction occurs under poor temperature environment (500℃ and ??70℃)

Furthermore, the mineral material of the present invention not only forms a perfect coating film on the base material with only one coating without a separate binder, but also increases the strength of the base material itself, and has very excellent economics in terms of workability and process.

The mineral material according to the present invention can be used in various industrial fields, such as high-tech materials, bridges, shipbuilding fields, steel structures, natural gas pipelines, and semiconductor processing equipment, so that the technology has a very large impact.

1 is a photograph showing a powder shape of a mineral material composition derived from basalt according to an embodiment of the present invention.
2 is a photograph showing a state of pellets according to an embodiment of the present invention and a state of coating coated on a base material by melting them.
3 is an optical microscope photograph of an interface after cutting the pellet-coated stainless steel using a cutter.
4 is a photograph of observation of the coated surface and the interface of the pellet-coated stainless steel with a scanning electron microscope.
5 is a scanning electron microscope photograph of an interface between a pellet-coated stainless steel and a coating portion observed by magnification.
6 is a scanning electron microscope photograph showing the location of an interface, which is a hardness measurement site, and a graph showing a result of measuring the surface hardness of each site.
7 is a graph and table showing the results of EDS analysis on the surface of the coating layer in order to analyze the components of the coating layer.
8 is a graph and table showing the results of EDS analysis of the interface between the coating film and stainless steel.
9 is a graph showing the results of X-ray diffraction of the coating film coated by the pellet.
10 to 15 are scanning electron micrographs illustrating an initial surface state of a casting according to an embodiment of the present invention.

Hereinafter, the mineral material composition of the present invention, and various pellets, coating films, molded articles, etc. using the same will be described in detail with reference to the accompanying experimental drawings. However, the following descriptions are exemplary descriptions to aid understanding of the present invention, and the technical idea of the present invention is not limited by the following descriptions. The technical idea of the present invention may be interpreted or limited only by the following claims.

The mineral material composition is extracted from basalt. The basalt is crushed to remove impurities, and the crushed basalt powder is melted in a relatively low temperature environment of 800 to 1000°C instead of 1400°C or higher, which is a normal complete melting temperature, and cooled to room temperature to extract mineral components. In the melting step, sulfur, an acidic solution, etc. may be added. The cooling body of the melt may be powdered to be manufactured as a mineral material.

Whether or not the melting temperature condition or the additive is added may be variably made so that the mineral material composition has the following composition. The mineral material composition, SiO ₂ 100 parts by weight; Al ₂ O ₃ 25 to 32 parts by weight; CaO 18 to 22 parts by weight; MgO 18 to 22 parts by weight; Fe ₂ O ₃ 18 to 22 parts by weight; And metal components such as Ti, Y, La, Ce, and Nd.

1 is a photograph showing a powder shape of a mineral material composition derived from basalt according to an embodiment of the present invention. In addition, Table 1 below illustrates the composition of the mineral material powder extracted from basalt. The following composition was requested and received from the Korea Institute of Materials Research.

SiO ₂ Al ₂ O ₃ CaO MgO Fe ₂ O ₃ Ti Y La Ce Nd bal 15.33 10.19 10.07 10.18 1.19 0.0043 0.0095 0.0131 0.0071

The mineral material composition has a scratch strength of at least 9.0H and a Mohs hardness of at least 7.3 when hot-dip coating on the surface of the base material, and can form a coating film without peeling and breakage at a temperature of 500°C and -70°C, respectively. have.

The mineral material composition can be processed into abrasion-resistant pellets derived from basalt with maximized operation convenience by sintering the material in the form of powder and molding it into a pellet shape. It may be general that a subsequent process is conducted using the pellet as a raw material rather than a powder type.

The pellets may be melted to form a coating film or mixed with other additives to form a molded body in the form of an alloy.

Hereinafter, an example in which the pellet is used as a coating film of a metal base material will be described in detail. In this embodiment, a metal base material is exemplified as the base material, but various materials other than metal may be used as the base material. As described above, when the surface of the metal base material is coated by using the pellets, it is determined that the strength of the metal is significantly increased. On the other hand, when the pellet is melted at a temperature of 800 to 900°C and coated on the surface of a metal base material that has undergone cleaning and drying processes, it forms a coating film that is chemically completely combined with the metal base material with only one process without a binder or additional process. can do.

Coating film analysis

After coating the pellets melted at 830° C. on stainless steel, various interfaces and surface phenomena were analyzed. The coating thickness was 1.5 mm. 2 is a photograph showing a state of a pellet according to an embodiment of the present invention and a state of coating coated on a metal base material by melting and melting the same. Referring to Figure 2, the pellet according to an embodiment of the present invention has a black oval or bead shape.

Experiment method

(1) Observation of interface shape

After cutting the sample using a high-speed cutter of PRESI's model name MECATOME T300, grinding and micro-polishing the interface, and then etching stainless steel with 30 ml of HCl, 20 ml of glycerol and 10 ml of HNO ₃ , using an optical microscope and JEOL's model name. The interface was observed using a scanning electron microscope of this JSM-5800.

(2) Surface and interface hardness test

The surface of the SAM coated on stainless steel was measured using a Vickers hardness tester with the model name HM-211 of Mituhoyo for 10 seconds under a load of 0.1Kg, and the hardness was measured in the same way from stainless steel to the coated part. The hardness change was observed.

(3) Surface and interface EDS analysis

For the component analysis of the pellet, EDS analysis was performed on the surface of the pellet coated on stainless steel and the coating interface using a scanning electron microscope with the model name JSM-5800 of JEOL.

(4) XRD analysis

X-ray diffraction analysis was performed using PANalytical's X'pert-PRO MRD to confirm the state of the constituent elements of the pellet.

Experiment result

(1) Observation of interface shape

3 is an optical microscope photograph of an interface after cutting the pellet-coated stainless steel with a cutter. Referring to FIG. 3, as a result of observation, it was confirmed that the interface was very smooth and adsorption was well performed without the part where the coating part was separated by the cutter. As a result of observing the interface with an optical microscope, the pellets are coated with a thickness of about 105㎛, consist of polygons of different sizes and contain pores, and no microcracks or pores were observed at the interface between stainless steel and pellets. It was found that the adsorption was well performed.

4 is a photograph of observation of the coated surface and the interface of the pellet-coated stainless steel with a scanning electron microscope. 5 is a scanning electron microscope photograph of an interface between a pellet-coated stainless steel and a coating portion observed by magnification. Referring to FIGS. 4 and 5, as a result of observation at high magnification, it can be seen that the coating interface is composed of microcracks, and although the boundary is clear, pores between the interfaces are not observed and are closely adsorbed. It was determined that the micro-cracks at the coating interface occurred due to the stress received during the interface cutting of the stainless steel.

(2) Surface and interface hardness test

The surface coated on the stainless steel by the pellet was maintained for 10 seconds under a load of 0.1Kg using a Vickers hardness tester with the model name HM-211 of Mitutoyo, and the surface hardness was measured and the results are shown in Table 2. 6 is a scanning electron microscope photograph showing the location of an interface, which is a hardness measurement site, and a graph showing a result of measuring the surface hardness of each site. Referring to Table 2 and FIG. 6, it was found that the hardness of the surface of the coating was about 591 Hv, which was considerably light, and it was confirmed that the hardness value decreased as the interface became closer to the base material.

One 2 3 4 5 6 7 8 9 10 Average Hv 547.7 516.4 575.5 588.6 582.0 664.9 630.5 559.8 595.3 649.3 591.0

(3) Surface and interface EDS analysis

In order to analyze the composition of the coating film by the pellet, the surface of the coating film coated on stainless steel was subjected to EDS analysis using a scanning electron microscope with the model name JSM-5800 of JEOL. 7 is a graph and table showing the results of EDS analysis on the surface of the coating layer in order to analyze the components of the coating layer. Referring to FIG. 7, in EDS analysis using a scanning electron microscope, since O was not properly analyzed, the remaining components excluding O were analyzed as a reference. As a result of the analysis, Si was the highest, followed by Ca, Na, Al, and Fe. Based on this, it was determined that the pellet or coating film was composed of SiO ₂ , Al ₂ O ₃ , CaO, and the like.

8 is a graph and table showing the results of EDS analysis of the interface between the coating film and stainless steel. Referring to FIG. 8, it was confirmed that the amount of Si decreased while the amount of Fe increased as the coating portion got closer to the stainless steel, and the composition of the stainless steel was compromised at the position 5, indicating that adsorption was well performed. I could confirm.

(4) XRD analysis result

9 is a graph showing X-ray diffraction results of a coating film coated by a pellet. Referring to FIG. 9, it was determined that the pellet or coating film is a material made of (CaFeMg)Si ₂ O ₆ as a constituent element.

(5) Summary

Looking at the experimental results as a whole, it was confirmed that the abrasion-resistant pellet or coating film derived from basalt according to the present invention is a material containing (CaFeMg)Si ₂ O ₆ as a component. In addition, almost no pores were found in the coating film and the metal base material (stainless steel), and it was confirmed that the coating film component was almost completely adsorbed to the metal base material. In addition, specifically, the coating film showed a tendency of decreasing the amount of Si element and increasing the amount of Fe element as it approaches the metal base material.

In the above, the characteristics of the coating film melt-coated by pellets have been mainly described, but the mineral material composition according to the present invention is formed into pellets, and then subjected to processes such as melting, firing, and molding using the pellet itself as a source. It is possible to directly manufacture a molded article having. On the other hand, when the molded article is manufactured, by adding a separate metal component, the molded article may exhibit excellent mechanical and physical properties such as remarkably enhanced abrasion resistance that can function as a kind of new alloy.

Evaluation of molded body properties

The above-described pellets were melted and formed into a square column shape to evaluate the physical properties of the formed body. The molded article may be manufactured through a sintering and molding process of a powdered mineral material composition without using pellets, and a method of manufacturing the molded article is not particularly limited.

(1) cutting experiment

As a result of cutting the molded body of the same shape using the same cutter, cutting time of about 6 hours was required for the steel, while the cutting time of about 108 hours was required for the molded body according to the present embodiment. Through this, it was confirmed that the molded body exhibited high hardness almost similar to that of titanium carbon and tungsten carbon.

(2) as-cast structure

In order to confirm the initial casting structure of the molded body, the state of the initial surface of the cast in the shape of a square column was observed using a scanning electron microscope.

10 to 15 are scanning electron micrographs illustrating an initial surface state of a casting product according to an embodiment of the present invention.

As a result of analyzing the pictures, the peculiar point was that the cooling coefficient and the thermal conductivity coefficient of each side (6 sides) of the square column shape were different from each other. Further, referring to FIG. 14, a porous structure was also observed, and in FIG. 15, a dendritic structure was also shown. Overall, it shows a monolithic structure. As such, the molded article of the present invention is expected to be able to develop a variety of applications utilizing this because the surface condition and physical properties of each surface are observed differently and have high hardness.

Claims (10)

As a powdered mineral composition after melting and extracting basalt,
It has a scratch strength of at least 9.0H and a Mohs hardness of at least 7.3 when direct melt coating on the surface of the base material of the metal, and can form a coating film without delamination and fracture phenomena at a temperature of 500°C and -70°C, respectively,
SiO ₂ 100 parts by weight; Al ₂ O ₃ 25 to 32 parts by weight; CaO 18 to 22 parts by weight; MgO 18 to 22 parts by weight; Fe ₂ O ₃ 18 to 22 parts by weight; And 0.1 to 2 parts by weight of at least one metal component selected from the group consisting of Ti, Y, La, Ce and Nd,
Abrasion-resistant mineral material composition derived from basalt.
delete Abrasion-resistant pellets derived from basalt formed by firing and molding the composition of claim 1 into a pellet shape.
The method of claim 3,
(CaFeMg) Si ₂ O ₆ Basalt-derived wear-resistant pellets, characterized in that it contains as a constituent component.
Preparing a coating composition by melting the pellets of claim 4 under a temperature of 800 to 900°C;
Cleaning and drying the surface of the base material; And
Method of forming a wear-resistant coating film derived from basalt comprising the step of directly coating the coating composition without a binder on the surface of the base material.
As a coating film formed by the method of claim 5,
No pores are formed at the interface with the base material,
Abrasion-resistant coating film derived from basalt that tends to decrease the amount of Si element and increase the amount of Fe element as it approaches the base material.
The method of claim 6,
At least one region of the coating film is abrasion resistant coating film derived from basalt, characterized in that adsorbed on the surface of the base material.
The method of claim 6,
The coating film is a wear-resistant coating film derived from basalt, characterized in that it contains (CaFeMg)Si ₂ O ₆ as a constituent component.
Abrasion-resistant molded article derived from basalt formed by melting, firing, and molding the mineral material composition of claim 1 or the pellet of claim 3.
The method of claim 9,
The molded article is a wear-resistant molded article derived from basalt, characterized in that it further comprises a separate metal component supplied from the outside.

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