KR102565924B1 - Alloy, alloy powder and alloy coated body having antimicrobial activity - Google Patents

Abstract

An alloy composition according to an aspect of the present invention is an alloy composition having antibacterial activity, comprising: a first component composed of Fe and Ni; A second component consisting of at least one or more selected from the group consisting of Cr, Co, Mo and Cu; and a third component consisting of at least one selected from the group consisting of Si, B and P.

Description

Alloy, alloy powder and alloy coated body having antimicrobial activity {Alloy, alloy powder and alloy coated body having antimicrobial activity}

The present invention relates to alloys, alloy powders, and alloy-coated bodies, and more particularly, to alloys, alloy powders, and alloy-coated bodies having antibacterial or bactericidal effects.

Recently, interest and demand for disinfection and sterilization are rapidly increasing worldwide in the global pandemic of COVID-19, and in addition to masks and hand sanitizers, elevator buttons that various people come into contact with in daily life Antibacterial films and the like are provided, but it is practically impossible to provide them in many fields requiring antibacterial functions, and the uncertainty of antibacterial activity and high price are obstacles to commercialization of antibacterial materials.

In general, there are silver and copper as metals well known to have antibacterial effects. Copper or silver and alloys containing them can be used to treat human infections, including bacteria such as Listeria monocytogenes, salmonella, and methacillin-resistant Staphyl lococcus aureus (MRSA). It is known to kill pathogens.

The US Environmental Protection Agency has declared that alloys containing 65% or more copper have inherent antibacterial activity, but silver and copper are not widely used as common living materials despite these excellent antibacterial properties. can't In particular, it is difficult to find applications for copper despite its relatively low price compared to silver.

In addition to the price problem, copper is difficult to commercialize because it is easily discolored by moisture or salt in parts that come into contact with air, moisture, or the human body, and a difference in color tone occurs in parts that do not.

In the case of an alloy material containing copper, discoloration is caused by oxidation (elution) of an alloying element that imparts color, and may additionally be caused by the formation of a metal oxide on the surface of the metal.

Metal materials as living materials are generally preferred in the form of alloys in which each metal is properly mixed rather than pure metal. Stainless steel, aluminum alloy, and titanium alloy, which are known to have excellent discoloration and corrosion resistance, are representative It is being used.

Recently, materials having a bacterial propagation inhibitory effect by using a surface coating on stainless steel having excellent corrosion resistance have been proposed. For example, antibacterial stainless steel sheets and coated steel sheets coated with silver (Ag) or copper (Cu) on metal using physical vapor deposition (PVD) or chemical vapor deposition (CVD) is being proposed

However, PVD and CVD processes require a very long time to form a plating layer, resulting in poor economic feasibility, and there are restrictions on the shape of a part due to the size of a vacuum chamber. In addition, these materials have a problem in that the antibacterial property is not permanently maintained because the thickness of the antibacterial layer is very thin and the mechanical properties are low, so that the antibacterial effect cannot be expected in the loss area when the coating layer is lost due to external force.

Among copper alloy materials, when Ni is 35% or more in the Cu-Ni system, discoloration resistance is improved, but it is impossible to realize various colors, and the raw material price is too high, so there is a limit to use as a living material. In addition, since Ni may cause an allergic reaction in the human body and a problem of elution of heavy metals may occur, development of an alloy capable of replacing the Cu-Ni alloy is required.

Republic of Korea Patent No. 10-0914858 (2009.08.25. Notice)

One aspect of the present invention relates to alloys, alloy powders, and alloy coatings having antibacterial activity, and provides efficient alloys, alloy powders, and alloy coatings having excellent antibacterial activity while limiting the addition of expensive metals such as silver and copper. Its purpose is to provide

An object of the present invention is to provide an antibacterial material having excellent oxidation resistance and corrosion resistance and excellent abrasion resistance, so that the durability of the antibacterial effect and long life when applied to everyday life or industrial products is provided.

One aspect of the present invention is an object of the present invention to provide an alloy that has excellent hardness and can be used in various ways such as home appliances, filters, hospitals, public place handles, household goods, etc. according to the processing method, and alloy powder and alloy coated body using the same .

An object of the present invention is to provide an alloy-coated body including an alloy-coated layer that has a metal-based color and is less repulsive to general users and can be applied to various types of base materials.

The alloy according to one aspect of the present invention,

a first component composed of Fe and Ni;

A second component consisting of at least one or more selected from the group consisting of Cr, Co, Mo and Cu; and

A third component consisting of at least one or more selected from the group consisting of Si, B and P; including,

With respect to 100 parts by weight of the first component,

The second component is included in 90 to 110 parts by weight,

The third component includes 5 to 15 parts, and the weight ratio of the Fe to 100 parts by weight of the first component may be 1.3 to 2.0 times the weight ratio of the Ni to 100 parts by weight of the first component.

The second component includes Cr and may further include at least one selected from Co, Mo, and Cu.

The weight ratio of the Cr to 100 parts by weight of the first component may be 0.63 to 1.39 times the weight ratio of the Fe to 100 parts by weight of the first component.

The second component is composed of Cr, Co, Mo and Cu,

The third component may be composed of Si and B.

Alloy powder according to an aspect of the present invention may be obtained by melting the alloy, spraying a fluid to atomize the molten alloy, and then cooling the atomized alloy with a refrigerant.

The alloy powder includes an amorphous phase and may have defects formed on its surface.

The alloy powder may have a reduction rate of E. coli measured by the KSM 0146 test method of 99.9% or more after 24 hours.

The alloy powder may have a reduction rate of E. coli measured by the KSM 0146 test method of 80% or more after 1 hour.

The alloy coated body according to one aspect of the present invention,

parent material; and

An alloy coating layer provided on the base material; Including,

The alloy coating layer,

A first component composed of Fe and Ni;

A second component consisting of at least one or more selected from the group consisting of Cr, Co, Mo, and Cu;

Including a third component consisting of at least one or more selected from the group consisting of Si, B and P,

With respect to 100 parts by weight of the first component,

The second component is included in 90 to 110 parts by weight,

The third component includes 5 to 15,

The weight ratio of the Fe of the first component to 100 parts by weight of the first component may be 1.3 to 2.0 times the weight ratio of the Ni to 100 parts by weight of the first component.

The thickness of the alloy coating layer may be 10 ㎛ to 500 ㎛.

The porosity of the alloy coating layer may be 5.0% or less.

The alloy coating layer may have a reduction rate of E. coli measured by the test method of JIS Z 2801 of 99.9% or more after 24 hours.

Alloys, alloy powders, and alloy coated bodies according to one aspect of the present invention have excellent antibacterial activity against Escherichia coli, Staphylococcus aureus, and pneumonia, and are economically superior, so that they can be applied to a wide range of fields such as daily life.

When the alloy according to one aspect of the present invention is manufactured as an alloy powder, it has a very excellent antibacterial effect against bacteria for a short time and has a higher sterilization and antibacterial effect than copper metal, so it can substantially provide a more improved antibacterial effect than copper metal. there is.

The alloy coating layer according to one aspect of the present invention may be prepared using alloy powder, and even after being prepared as a coating layer, the antibacterial activity against Escherichia coli, Staphylococcus aureus, and Pneumococcus does not decrease and may have the same or superior antibacterial activity as copper metal. there is.

Since the alloy powder and the alloy coating layer according to one aspect of the present invention include an amorphous phase due to the amorphous forming ability of the alloy, corrosion resistance and oxidation resistance are excellent. Therefore, problems such as decrease in antibacterial effect, discoloration, and corrosion do not occur over time, so it has high efficiency and a long lifespan, and it has excellent physical properties such as hardness of powder and coating layer, so it is diverse depending on the use. can make use of it.

The alloy according to one aspect of the present invention has very high surface energy and surface activity because additive elements are very uniformly and evenly distributed and has a short range ordered structure and microstructural defects. , it is difficult for bacteria to attach and proliferate on the surface of the amorphous alloy, so it can have excellent antibacterial activity.

The alloy powder and the alloy coating layer according to one aspect of the present invention have high metal ion activity on the surface due to a trace action due to the amorphous structure of the alloy, and copper, nickel, and cobalt are present on the surface due to the compositional characteristics of the alloy composition. It can cause micro-activation in the body, so it can have excellent antibacterial activity.

Since the alloy powder or alloy-coated body manufactured using the alloy according to one aspect of the present invention is less affected by moisture or moisture, it can be used even in a high-humidity environment where bacteria or fungi are likely to proliferate. Therefore, an excellent antibacterial effect can be obtained, and it can be applied to toilets and sewers, where antibacterial materials or processed products have been difficult to apply in the past, as well as medical instruments, building handles, and ambulance interiors that need to reduce the risk of infection and require excellent wear resistance. It can be used for parts, stretchers, etc. In addition, it has excellent resistance to external contamination and antifouling properties, so its utilization is high.

Even if the alloy powder according to one aspect of the present invention is used to form a thermal spray coating layer using a thermal spray coating method, etc., it has excellent amorphous forming ability and can form a coating layer containing an amorphous phase, and the hardness, corrosion resistance, oxidation resistance, etc. of the formed alloy coating layer are further improved. can be improved

Since the alloy composition according to one aspect of the present invention includes an amorphous phase while containing copper known to have antibacterial activity in a low weight of 4 wt% or less, excellent antibacterial activity and economic feasibility can be secured.

The present invention relates to an alloy, an alloy powder, and an alloy coated body, and hereinafter, preferred embodiments of the present invention will be described. Embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. These embodiments are provided to those skilled in the art to further elaborate the present invention.

When the term antibacterial is used in this specification, it can be interpreted in a broad sense that includes all of inhibiting, inhibiting, sterilizing, or sterilizing the growth of required microorganisms, wherein sterilization Means killing at least some of the microorganisms in the target material, and sterilization may mean removing or killing all microorganisms from the inside, surface or space of the target material.

In addition, antibacterial activity means a property of resisting microorganisms such as bacteria or fungi, and more specifically, may mean a property of inhibiting the growth or proliferation of bacteria. When the expression having antibacterial activity is used, it is understood to mean that the material or sample has an effect or activity such as antibacterial or mold resistance measured by KS test method or overseas standard test method for specific bacteria or bacteria. It can be.

In this specification, the weight part of the elements included in the alloy composition can be understood as including the target composition calculated from the raw material alloy and the actual element composition of the manufactured alloy, preferably from the result of analyzing the components of the manufactured alloy. can be calculated.

Hereinafter, the alloy of the present invention will be described in more detail.

The alloy of the present invention includes a first component, a second component and a third component.

The first component is a component that can affect physical properties, productivity, and economy of the alloy. The first component may be included in a weight similar to or higher than the second or third component in the total weight of the alloy. The second component may be included in a higher weight than the third component in the total weight of the alloy. Preferably, the second component may be included in 90 to 110 parts by weight based on 100 parts by weight of the first component, and the third component may be included in 5 to 15 parts by weight based on 100 parts by weight of the first component.

The first component may be at least one selected from iron (Fe) and nickel (Ni), and may include a case in which both Fe and Ni are included.

When both Fe and Ni are included as the first component, the weight of Fe included may be higher than the weight of Ni, and the weight ratio of Fe and Ni (Fe/Ni) with respect to 100 parts by weight of the first component is 1.3 to 2.0. can be It may be preferably 1.5 to 1.8, more preferably 1.59 to 1.65.

If the ratio of Fe to Ni is out of the range or if only Ni is included without Fe as the first component, it is undesirable in terms of economic feasibility and may cause human body characteristics such as Ni allergy upon human contact, so Fe is the first component. It is preferable to be included in the component. In addition, if the Ni content does not fall within a certain range, high-temperature stability may decrease, which may cause oxidation of the powder, depletion of alloy elements in the coating layer, and peeling of the coating layer during the preparation of the coating layer. preferably included.

The second component may contribute to improving the amorphous formation ability of the alloy or improving physical and chemical properties such as hardness, corrosion resistance, and oxidation resistance of the alloy. The second component may be at least one selected from chromium (Cr), cobalt (Co), molybdenum (Mo), and copper (Cu). The second component may be any one or more selected from Cr, Co, Mo, and Cu, and may include all of Cr, Co, Mo, and Cu.

The second component may be included in an amount of 90 to 110 parts by weight based on 100 parts by weight of the first component. It may preferably be included in 95 to 105 parts by weight, more preferably 99 to 102 parts by weight.

In order to secure the antibacterial effect and anticorrosive properties, the second component is preferably added in the above-mentioned amount. If the content of the second component exceeds the corresponding range, it is not preferable from the viewpoint of economic efficiency, and damage due to external force may be caused due to increased brittleness of the coating layer, so that antibacterial properties of a desired level may not be secured.

The second component may essentially include Cr, and the content of Cr included in the second component may be higher than the total content of Co, Mo, and Cu. For example, when the second component includes Cr and additionally includes one or more of Mo, Co, and Cu, the weight ratios of Cr, Co, Mo, and Cu with respect to 100 parts by weight of the first component are a, b, When c and d, the ratio (A) of the weight ratio of Cr in the second component and the sum of the weight ratios of the components other than Cr can be calculated as a/(b+c+d), and the value is 1.5 to 2.5, Preferably it may be 1.7 to 2.2. It is preferable to limit the lower limit of the content ratio (A) to the level described above in order to secure antibacterial properties. On the other hand, when the content ratio (A) exceeds the above-mentioned level, it is not preferable in terms of economic efficiency, and surface discoloration may occur due to reduced corrosion resistance.

When the content of Cr included in the second component is compared with the content of Fe included in the first component, the weight ratio of Cr to 100 parts by weight of the first component is 0.63 times to the weight ratio of Fe to 100 parts by weight of the first component. It may be within 1.39 times. Preferably, the weight ratio of Cr to 100 parts by weight of the first component may satisfy the range of 0.99 to 1.20 times the weight ratio of Fe to 100 parts by weight of the first component.

If the content ratio of Cr and Fe is out of the range, the amorphous forming ability is lowered and the ratio of the amorphous phase included in the alloy is reduced, so the antibacterial effect or corrosion resistance may be lowered.

The content of Cu included in the second component is preferably smaller than the content of each of Co, Mo, and Cr. For example, when the second component includes Cu and additionally includes one or more of Mo, Co, and Cr, the weight ratios of Cr, Co, Mo, and Cu with respect to 100 parts by weight of the first component are a, b, When c and d, the ratio (B) of the sum of the weight ratio of Cu and the weight ratio of other components except Cu in the second component can be calculated as d/(a+b+c), and its value is 0.04 to 0.10, preferably 0.05 to 0.07.

If Cu is not included in the second component or the ratio of the content of the other components to the content of Cu is out of the corresponding range, antibacterial performance or corrosion resistance may be deteriorated, and thermal or electrical conductivity may be deteriorated.

Cu may be included in an amount of 0 to 9.0 parts by weight based on 100 parts by weight of the first component. It may preferably be included in 0.1 to 8.0 parts by weight, more preferably 4.5 to 7.5 parts by weight.

When the Cu content does not fall within the corresponding range, antibacterial activity may be reduced, and when the Cu content exceeds the corresponding range, economic deterioration due to increased production cost may be caused.

Co may be included in an amount of 0 to 25 parts by weight based on 100 parts by weight of the first component. Preferably it may be included in 19 to 25 parts by weight, more preferably it may be included in 20 to 24 parts by weight.

When the content of Co exceeds the corresponding range, economic deterioration due to increase in production cost may be a problem. On the other hand, when the Co content is lower than the corresponding range, the antibacterial activity may be lowered, the high-temperature safety may be lowered, the oxide fraction in the coating layer may increase, and the coating layer may be peeled off due to external force.

The third component may be included in a relatively small proportion to improve the amorphous forming ability of the alloy and impart special functions such as antibacterial activity.

The third component is at least one selected from the group consisting of silicon (Si), boron (B), and phosphorus (P), and may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the first component. It may preferably be included in 7 to 13 parts by weight, more preferably 9 to 12 parts by weight.

When the content of the third component is less than the corresponding range, the amorphous forming ability of the alloy may decrease, and thus corrosion resistance and hardness may decrease. When the content of the third component exceeds the corresponding range, the content of the first component or the second component is relatively reduced, so that not only the strength of the alloy is lowered, but also the antibacterial activity is lowered.

When both Si and B are included as the third component, the weight ratio of Si and B in the third component (weight ratio of B to 100 parts by weight of the first component / weight ratio of Si to 100 parts by weight of the first component) is It may range from 1.5 to 10. It may preferably range from 2.5 to 9.

If the content ratio of B and Si is out of the range, corrosion resistance, hardness and strength may be deteriorated, and antibacterial activity may be deteriorated.

The alloy according to one aspect of the present invention may include an additional component included in a small amount in addition to the above-described first to third components. Additional components include tungsten (W), yttrium (Y), manganese (Mn), aluminum (Al), zirconium (Zr), magnesium (Mg), niobium (Nb), sulfur (S), scandium (Sc) , cerium (Ce), silver (Ag), titanium (Ti), and at least one of carbon (C), and these additional components may be intentionally or unintentionally included in the alloy.

The total amount of the additional components may be less than 10 parts by weight based on 100 parts by weight of the first component. Preferably it may be less than 7.5 parts by weight, more preferably less than 5.0 parts by weight. The total amount of each additional component may be less than 5.0 parts by weight based on 100 parts by weight of the first component. It may preferably be less than 3.0 parts by weight, more preferably less than 1.0 parts by weight.

If the content of the additional component exceeds the corresponding range, the antibacterial function and mechanical properties may be deteriorated.

Alloy powder according to an aspect of the present invention is provided using the above-described alloy. Alloy powder according to an aspect of the present invention has an alloy composition corresponding to the above-described alloy, and may include an amorphous phase. Alloy powder may be manufactured into powder using a well-known method, for example, an atomizing (or atomization) method.

In the atomizing method, the alloy in a molten state flows down by pressure or gravity, and a fluid such as gas or water is sprayed on the flowing molten alloy to atomize it in the form of fine droplets or droplets, and then the split droplets are separated into inert gas or It is a method of producing alloy powder by rapid cooling using a refrigerant such as water. Since the atomizing method is a well-known technique for producing metal powder, a detailed description thereof will be omitted.

In order to produce amorphous powder in the atomizing method, the split droplets must be rapidly cooled, because the molten alloy is solidified without giving time to crystallize, so it is advantageous to become amorphous.

Therefore, in order to manufacture an alloy powder having a higher proportion of the amorphous phase, it is more advantageous to have a special cooling facility capable of increasing the cooling rate.

However, the alloy according to one aspect of the present invention has excellent amorphous forming ability, so that even if a conventional atomizing method is used, an alloy powder having a high amorphous phase ratio can be produced.

In the case of a normal atomizing method without a special cooling facility, an amorphous phase powder can be produced from the alloy according to one aspect of the present invention even under a cooling rate of 10 ² to 10 ³ or 10 ¹ to 10 ⁴ (degree/sec). . At this time, 10 ^{1 ~ 2} (degree / sec) is a cooling rate substantially close to air cooling, which is a cooling rate when the alloy solution is ejected into the air.

On the other hand, the alloy powder or alloy coating layer including the amorphous phase may have a very uniform distribution of additive elements, a short range ordered structure, and at the same time have microstructural defects.

A defect refers to an irregular atomic arrangement or bonding structure that appears in the microscopic aspect, such as the atomic structure of a material. Point defects, which are 0-dimensional defects, and line defects, which are lattice distortions concentrated around imaginary lines, are 1-dimensional defects. It can be understood as a concept including a line defect or dislocation, a plane defect that occurs two-dimensionally and includes an external surface, grain boundary, stacking defect, slip band, etc. .

Due to these microscopic defects of the alloy powder or alloy coating layer including the amorphous phase, the amorphous alloy powder and the amorphous alloy coating layer may have very high surface energy and activity compared to crystalline alloys.

At this time, the uniform distribution of added elements, high surface energy and activity make it difficult for bacteria, bacteria and fungi to adhere to or proliferate on the surface of the amorphous alloy powder or amorphous alloy coating layer, and have an excellent antibacterial effect compared to crystalline metal materials can be obtained.

Antibacterial activity in the alloy, alloy powder, and alloy coating layer according to one aspect of the present invention is also interpreted as having excellent antibacterial activity due to the combination of these factors, and even if the specific mechanism is not revealed, it is made of a specific alloy composition and has an amorphous phase The fact that the alloy powder and the alloy coated body having an advantageous antibacterial activity can be inferred through examples and experimental examples described below.

Regarding the antibacterial activity of the alloy powder and the alloy coating layer of the present invention, an oligodynamic action can be seen as another mechanism of antibacterial activity.

Oligodynamic action is a phenomenon in which trace amounts of metal ions hinder the growth or death of organisms, and is known as a mechanism to explain the antibacterial action of phosphorus copper, one of the representative antibacterial metals.

Specifically, this microscopic action is observed in metals such as silver, gold, platinum, mercury, nickel, lead, and cobalt in addition to copper, and microorganisms such as bacteria recognize metal ions as essential nutrients and absorb them into cells, but absorption Metal ions (including copper ions) pierce cell membranes, inhibit metabolism, and attract active oxygen to reduce the survival time of bacteria and kill them. The antibacterial activity of alloys can be explained by the mechanism of destroying and destroying dielectric materials.

According to such a microscopic action, the alloy, amorphous alloy powder, and amorphous alloy coating layer according to the aspect of the present invention include the corresponding composition ratio and amorphous phase, so that the effect of the microscopic copper action on the surface is superior to that of other alloys or pure copper metal. It can be exerted to have a good antibacterial effect.

For example, since components other than copper, nickel, and cobalt are included on the surface of an alloy containing copper, nickel, and cobalt, the binding force, surface energy, and ionization rate of each metal atom are different from those of crystalline metals or crystalline alloys in amorphous alloys. The release rate will be faster, and since various types of metal ions are released and absorbed by bacteria, the absorption rate, and the effect on bacteria can be different, it is expected to have excellent antibacterial activity targeting a wide range of microorganisms. expected

In particular, in the case of an amorphous alloy, metal atoms do not form a certain metal bond in a crystalline structure, and additive elements are very uniformly distributed, so that fine metal atoms or metal ions in the atomic unit that can act as trace amounts of copper are easily released. Depending on the composition of the alloy, the amount, speed, and type of metal ions released from the surface are different, and at the same time, several types of metal ions are released in a complex way, which can show significant quantitative effects.

On the other hand, since the diameter of the alloy powder affects the surface area and is related to the antibacterial activity of the alloy powder, the particle size of the alloy powder can be controlled to obtain appropriate antibacterial activity.

The diameter of the alloy powder to be produced is not limited, but may be 1 to 150 μm as a non-limiting example, and more preferably 1 to 54 μm.

If the particle diameter of the alloy powder is larger than the corresponding range, the appropriate surface area may decrease and the efficiency of antibacterial activity may decrease. Powder having a particle diameter smaller than the corresponding range may be difficult to manufacture and expensive, and may not exhibit sufficient antibacterial effect.

The manufactured alloy powder may be manufactured in a shape close to a sphere. The hardness (Vickers hardness) of the alloy powder is not limited and may vary depending on the purpose of the powder and the field to be applied. It may have a hardness of 550 to 1500 Hv without limitation, and may preferably have a hardness of 800 to 1200 Hv.

If the hardness of the alloy powder is out of the range, it may not have wear resistance or be applied to antibacterial products for wear resistance.

Alloy powder according to an aspect of the present invention may have excellent antibacterial activity. The type and characteristics of bacteria exhibiting an antibacterial effect are not limited, but may mean excellent antibacterial activity against strains such as Escherichia coli, Staphylococcus aureus, and Pneumococcus.

Antibacterial activity can be obtained with different test methods and results depending on the purpose of the sample, shape, material, etc., and in the case of alloy powder, for example, it can be tested by methods such as KSM 0146.

In general, if there is an effect of reducing the number of bacteria by 99.9% or more based on 24-hour culture, it is often recognized that there is an antibacterial effect. In the case of the alloy powder according to one aspect of the present invention, the effect of reducing the number of bacteria after 24 hours may be similar to or higher than that of a copper metal sample known to have excellent antibacterial effect. The bacterial count reduction rate after 1 hour may be 80% or more.

In the alloy coated body according to one aspect of the present invention, an alloy coating layer formed from the alloy powder described above may be formed on a base material to form a coated body.

The base material from which the alloy coating body is formed is not limited, and the material, component, size, use, etc. are not limited.

The method and coating method for forming the alloy coating layer according to the embodiment are not limited, but a thermal spray coating method capable of producing an alloy coating layer using the alloy powder described above, for example, high velocity flame spraying (HVOF, High velocity Oxygen Fuel spray), plasma spraying, twin wire arc spraying (TWAS), cold spraying, vacuum plasma spraying, low-pressure plasma spraying, etc. or cladding, such as laser cladding, etc. It is preferred that this is used.

The raw material used for the coating is not limited as long as it is a molded form of the above-described alloy composition, and alloy powder, alloy wire, fluxed cored wire, and the like may be used.

On the other hand, the thickness of the alloy coating layer formed on the base material is not limited, and may vary depending on the type of base material on which the coating layer is formed, the thickness of the base material, usage purpose, use environment, etc., and preferably has a thickness of 10 μm to 500 μm, more Preferably it may be 50 to 300 μm.

The antibacterial activity of the alloy coating layer can be measured by various test methods depending on the shape and conditions of the sample, and for example, the antimicrobial activity of the alloy coating layer can be evaluated through methods such as JIS Z 2801 or FC-TM-20.

In general, when there is an effect of reducing the number of bacteria by 99.9% or more based on 24-hour culture, it is often recognized that the alloy coating layer has an antibacterial effect. In the case of the alloy coating layer according to one aspect of the present invention, the effect of reducing the number of bacteria after 24 hours may be similar to or greater than that of a copper metal sample known to have excellent antibacterial effect. The reduction rate of bacteria after 1 hour may be 80% or more.

The alloy coating layer according to one aspect of the present invention may be an amorphous alloy coating layer including an amorphous phase, and since the alloy coating layer includes an amorphous phase, it may have excellent physical properties of the amorphous alloy.

For example, the alloy coating layer may have a Vickers hardness of 550 to 1500 Hv, preferably 800 to 1200 Hv.

When the hardness of the alloy coating layer is lower than the corresponding range, wear resistance is lowered, and surface damage, denting, or scratches may occur, and when the hardness is higher than the corresponding range, cracking, cracking, or surface damage due to brittleness may occur.

In addition, since the alloy coating layer according to one aspect of the present invention has excellent corrosion resistance, wear resistance and oxidation resistance, peeling off or corrosion of the coating layer occurs less when used, not only the lifespan of the coating layer is improved, but also the antibacterial activity of the alloy coating layer is not lowered. and can be maintained for a long time.

In addition, the porosity of the alloy coating layer according to an aspect of the present invention may vary depending on the particle diameter of the powder used for coating, the coating method, and the coating conditions. The lower the porosity of the alloy coating layer, the more preferable, and specifically, may be within 5.0%, preferably within 1.0%.

If the porosity exceeds the range, a decrease in hardness or wear resistance may occur due to a decrease in the quality of the alloy coating layer, and problems such as deterioration in corrosion resistance due to easy penetration of corrosive substances may occur. In addition, attachment or proliferation of bacteria may be facilitated.

The application fields of the alloy powder and alloy-coated body according to the present invention are not limited, and can be used in various fields such as medical, sanitary, household goods, and home appliances where antibacterial activity can be utilized.

Hereinafter, the present invention will be described in detail through examples. It should be noted that the following examples are only for understanding of the present invention, and are not intended to specify the scope of the present invention. The scope of the present invention may be determined by the matters described in the claims and the matters reasonably inferred therefrom.

(Example)

Examples 1 to 7 - Preparation of alloy powder

An alloy powder containing an amorphous phase was prepared by melting an alloy prepared with a composition having components and parts by weight as shown in Table 1 below, atomizing using an atomizer under an inert gas atmosphere, and then cooling. The average particle diameter of the prepared powder was measured using a laser particle size analyzer, and the results are shown in Table 1 together.

Furtherance 1st ingredient
(parts by weight) Second Component
(parts by weight) 3rd ingredient
(parts by weight) average
particle size
(D50)
(μm) Fe Ni Cr Co Mo Cu B Si Example 1 61.7 38.3 65.96 21.28 8.51 5.32 8.51 3.19 30 Example 2 61.39 38.61 72.81 21 4.22 3.93 10.8 1.2 35 Example 3 62.26 37.74 59.4 21.55 9.05 9.0 6.43 2.57 30 Example 4 60.0 40.0 72.18 20.8 7.01 5.0 7.8 5.2 40 Example 5 64.29 35.71 59.84 20.49 8.49 6.22 6.36 0.64 30 Example 6 56.53 43.47 78.5 27.16 0 4.24 13.5 1.5 20 Example 7 66.66 33.34 54.2 0 27.82 7.98 3.58 1.42 25

Examples 8 to 14 - Preparation of alloy coated bodies

Using the alloy powder prepared in Examples 1 to 7, oxygen and propane gas were used as fuel using ultra high speed flame spraying equipment (Oerlikon Metco Diamond Jet series HVOF gas fuel spray system), and spraying distance was 30 cm, and ultra high speed flame spraying (HVOF, high velocity oxygen fuel spray) method to form an alloy coating on the base material. The equipment and conditions used at this time are described in detail below.

- DJ Gun HVOF -

[Conditions] Gun type: Hybrid, Air cap: 2701, LPG Flow 160 SCFH, LPG Pressure 90 PSI, Oxygen flow 550 SCFH, Oxygen Pressure 150 PSI, Air flow 900 SCFH, Air Pressure 100 PSI, Nitrogen flow 28 SCFH, Nitrogen Pressure 150 PSI, Gun speed: 100 m/min, Gun pitch: 3.0mm, Feeder rate 45 g/min, Stand-off distance: 250mm

(Comparative example)

Comparative Examples 1 to 6 - Preparation of alloy powder

After preparing an alloy satisfying the component composition of Table 2, alloy powder including a crystalline metal powder and an amorphous phase was prepared in the same manner as in Examples 1 to 7. The particle diameter of the prepared powder was measured using a laser particle size analyzer, and the results are shown in Table 2 together. The amorphous phase fraction of each powder was measured using EBSD (Electron backscatter diffraction), and the results are shown in Table 2 together. In the presence or absence of amorphous, the mark “○” means that the fraction of the amorphous phase is 10 vol% or more, and the mark of “X” in the inclusion or absence of amorphous means the fraction of the amorphous phase is less than 10 vol%.

Furtherance 1st ingredient
(parts by weight) Second Component
(parts by weight) 3rd ingredient
(parts by weight) particle size
(μm) amorphous
include
Whether Fe Ni Cr Co Mo Cu B Si C Comparative Example 1 0 0 0 0 0 100 0 0 0 25 X Comparative Example 2 100 0 29.2 0 50.2 0 2.3 0 7.0 35 ○ Comparative Example 3 67.74 32.26 83.92 10.00 1.91 19.17 0 4 0 30 ○ Comparative Example 4 52.38 47.62 40 20.60 17.07 2.33 0 16 0 35 ○ Comparative Example 5 100 0 91.67 0 0 0 13.64 4.17 0 35 ○ Comparative Example 6 100 0 72.86 21.00 4.22 3.92 0 0 0 35 X

Comparative Examples 7 to 10 - Preparation of alloy coated body

The alloy powders of Comparative Examples 1 to 4 were coated on the base material under the same equipment and conditions as in Examples 8 to 14 to obtain an alloy coated body having an alloy coating layer.

(experimental example)

Experimental Example 1 - Composition analysis of prepared alloy powder

As a result of analyzing the alloy powders of Examples 1 to 7 using ICP (Inductively Coupled Plasma Spectrometer), the alloy component content of the alloy used in the manufacture of the alloy powder and the alloy powder manufactured using the same was the same, and there was a slight difference. It was confirmed that even if there was, it was within the manufacturing error range.

Experimental Example 2 - Antibacterial activity test of alloy powder

In order to evaluate the antibacterial activity of the alloy powders of Examples 1 to 7 and Comparative Examples 1 to 6, a shake flask method was performed based on the test method presented in KSM 0146 (2003), a Korean industrial standard. Cultures of Escherichia coli, Staphylococcus aureus, and Pneumococcus were used to prepare the final concentration of the culture medium to be 1-5×10 5 CFU/ml, and then a sample was added thereto at a rate of 0.09 g/ml.

1 g of the alloy powder of Examples 1 to 7 and Comparative Examples 1 to 6 was added, and the flask was cultured at 37 ± 1 ° C. for 24 hours with shaking at 120 rpm, and then the number of viable cells before and after culture of each group was measured.

As for the antibacterial activity, the results of Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Table 3 below by calculating the bacterial reduction rate expressed as a percentage of the number of bacteria observed after 24 hours compared to the initial number of bacteria.

division Escherichia coli Staphylococcus aureus pneumococci Early result decrease rate
(%) Early result decrease rate
(%) thatch result decrease rate
(%) Example 1 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 Example 2 2.2X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 2.2X10 ⁵ <30 99.9 Example 3 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 2.3X10 ⁵ <30 99.9 Example 4 2.2X10 ⁵ <10 ² 99.9 2.3X10 ⁵ <10 ² 99.9 2.2X10 ⁵ <10 ² 99.9 Example 5 2.2X10 ⁵ <10 ² 99.9 2.3X10 ⁵ <10 ² 99.9 2.1X10 ⁵ <10 ² 99.9 Example 6 2.2X10 ⁵ 1.5X10 ³ 99.3 2.2X10 ⁵ 2.1X10 ³ 99.0 2.1X10 ⁵ 1.2X10 ³ 99.4 Example 7 2.1X10 ⁵ 1.7X10 ³ 99.2 2.2X10 ⁵ 1.7X10 ³ 99.2 2.1X10 ⁵ 1.4X10 ³ 99.3 Comparative Example 1 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ <30 99.9 Comparative Example 2 2.4X10 ⁵ 3.7X10 ³ 97.2 2.1X10 ⁵ <30 99.9 2.1X10 ⁵ 1.9X10 ⁴ 85.4 Comparative Example 3 2.2X10 ⁵ 8.7X10 ³ 60.5 2.1X10 ⁵ 3.9X10 ⁴ 81.4 2.1X10 ⁵ 1.3X10 ⁵ 38.1 Comparative Example 4 2.2X10 ⁵ 5.2X10 ³ 76.4 2.1X10 ⁵ 1.1X10 ⁴ 94.8 2.1X10 ⁵ 7.9X10 ⁴ 62.4 Comparative Example 5 2.4X10 ⁵ 3.5X10 ³ 73.1 2.1X10 ⁵ 3.9X10 ⁴ 97.0 2.1X10 ⁵ 1.8X10 ⁵ 14.2 Comparative Example 6 2.4X10 ⁵ 6.2X10 ³ 74.2 2.1X10 ⁵ 8.1X10 ⁴ 61.4 2.1X10 ⁵ 9.5X10 ⁴ 54.8

Example 1 and Comparative Example 1 showed a reduction rate of 99.9% or more for all of Escherichia coli, Staphylococcus aureus and Pneumococcus, showing excellent antibacterial activity, and Comparative Examples 2 to 6 showed antibacterial activity against coliform, Staphylococcus aureus and Pneumococcus. It can be seen that the activity is relatively low.

Experimental Example 3 - Antibacterial activity test of alloy coating layer

In order to evaluate the antibacterial activity of the alloy coated body of Example 8, an antimicrobial activity test was performed by a film adhesion method based on the test method presented in JIS Z 2801.

The test conditions were temperature 37 ~ 38 ℃, time 23 ~ 24 hr, the sample size was 50 mm in length and width, and the coating body was used. With the pieces in contact with the medium, the test bacterial solution was cultured for 24 hours at 35 ± 1 ° C and 90% relative humidity, and then the number of bacteria was measured, and the reduction rate was shown in Table 4 below.

division Example 8 Escherichia coli Early 1.4X10 ⁴ result <0.63 Decrease rate (%) 99.9% Staphylococcus aureus Early 1.4X10 ⁴ result <0.63 Decrease rate (%) 99.9% pneumococci Early 1.7X10 ⁴ result <0.63 Decrease rate (%) 99.9%

The alloy coated body of Example 8 also showed a reduction rate of 99.9% or more for all of Escherichia coli, Staphylococcus aureus and Pneumococcus, indicating excellent antibacterial activity. It was also confirmed that the sieve had antibacterial activity similar to that of the powder.

Experimental Example 4 - 1 hour antibacterial effect test of alloy powder

The experiment was conducted in the same manner as in Experimental Example 2, except that the shaking incubation time for the powders of Example 1 and Comparative Example 1 was 1 hour instead of 24 hours, and the results are shown in Table 5 below.

division Example 1 Comparative Example 1 Escherichia coli Early 2.5X10 ⁵ 2.4X10 ⁵ result 3.1X10 ⁴ 1.5X10 ⁵ Decrease rate (%) 87.6% 37.5% Staphylococcus aureus Early 2.1X10 ⁵ 2.1X10 ⁵ result 1.9X10 ⁵ 1.7X10 ⁵ Decrease rate (%) 9.5% 19.0% pneumococci Early 2.1X10 ⁵ 2.5X10 ⁵ result 1.9X10 ⁵ 1.0X10 ⁵ Decrease rate (%) 9.5% 60.0%

As a result, it was confirmed that the powder of Example 1 had an antibacterial activity twice or more than that of the copper powder, as the reduction rate of Escherichia coli for 1 hour was 2 to 3 times that of the copper powder of Comparative Example 1.

Experimental Example 5 - Evaluation of antibacterial durability according to repeated inoculation of amorphous alloy-coated specimens and evaluation of antibacterial properties under harsh conditions

[Evaluation of antibacterial durability according to repeated inoculation]

After preparing stainless steel (STS) specimens having a size of 2 cm * 2 cm, an amorphous alloy coating layer was formed on the surfaces of some of the specimens using the alloy powder of Example 1. At this time, the amorphous alloy coating layer was prepared by applying the same method as in Examples 8 to 14.

The surfaces of the prepared uncoated specimen and the amorphous alloy coated specimen were washed with 70% ethanol and then dried in a clean bench for about 15 hours. A mixture of Escherichia coli, Staphylococcus aureus, and Klebsiella pneumonia was repeatedly inoculated 5 times in an amount of 10 ⁵ cfu/ml to a specimen dried using 1/500 NB medium. , After inoculation, it was covered with a UV sterilized cover glass (18mm*18mm) and cultured in a constant temperature and humidity chamber maintained at 36°C and 90% RH. At 2 hours after each round of inoculation, bacteria were recovered by vortexing each specimen in 10 ml of letheen medium. After diluting the number of bacteria to a identifiable concentration, it was poured into TSA medium, and after incubation at 36 ° C. for 24 hours, the number of bacteria was confirmed and the reduction rate of the number of bacteria was described in Table 6.

division number of repeat doses 1 time Episode 2 3rd time 4 times 5 times Amorphous alloy coated specimen >99.9% >99.9% >99.9% >99.9% >99.9% uncoated specimen 98.6% 98.3% 97.6% 95.7% 75.0%

As shown in Table 6, it can be seen that the antibacterial activity of the amorphous alloy-coated specimen is maintained even when repeatedly inoculated 5 times, while the antibacterial activity of the uncoated specimen is lost under the same conditions.

[Evaluation of antibacterial properties under harsh conditions]

The same specimens as the specimens used in the antibacterial durability evaluation according to repeated inoculation were prepared.

The surfaces of the prepared uncoated specimen and the amorphous alloy coated specimen were washed with 70% ethanol and then dried in a clean bench for about 15 hours. A mixture of Escherichia coli, Staphylococcus aureus, and Klebsiella pneumonia was inoculated once in an amount of 10 ⁷ cfu / ml to a specimen dried using 1/500 NB medium, After inoculation, it was covered with a UV sterilized cover glass (18mm*18mm) and cultured in a constant temperature and humidity chamber maintained at 36° C. and 90% RH. At 1 hour, 2 hours, 3 hours, 9 hours and 18 hours after inoculation, each specimen was suspended (vortexing) in 10 ml of letheen medium to recover bacteria. After diluting the number of bacteria to a concentration that can be confirmed, it was poured into TSA medium, and after incubation at 36 ° C. for 24 hours, the number of bacteria was confirmed and the reduction rate of the bacteria was listed in Table 7.

division elapsed time 1hr 2hr 3hr 6hr 9hr 18 hours Amorphous alloy coated specimen TNTC TNTC TNTC TNTC >99.9% >99.9% uncoated specimen TNTC TNTC TNTC TNTC TNTC TNTC ※ TNTC (Too Numerous to Count): Unable to measure the number of bacteria due to excessive number of bacteria

As shown in Table 7, the antibacterial activity of the amorphous alloy coated specimen is confirmed after 9 hours, but the antibacterial activity of the uncoated specimen is not confirmed even after 18 hours have elapsed.

Although the present invention has been described in detail through examples above, other types of embodiments are also possible. Therefore, the spirit and scope of the claims set forth below are not limited to the embodiments.

Claims (12)

a first component composed of Fe and Ni;
A second component consisting of three or more selected from the group consisting of Cr, Co, Mo, and Cu; and
a third component composed of Si and B; including,
With respect to 100 parts by weight of the first component,
The second component is included in 90 to 110 parts by weight,
The third component is included in 5 to 15 parts by weight,
The weight ratio of the Fe to 100 parts by weight of the first component is 1.3 to 2.0 times the weight ratio of Ni to 100 parts by weight of the first component. According to claim 1,
The second component includes Cr,
An alloy further comprising at least one selected from Co, Mo, and Cu. According to claim 2,
The weight ratio of the Cr to 100 parts by weight of the first component is 0.63 to 1.39 times the weight ratio of the Fe to 100 parts by weight of the first component. According to claim 1,
The second component is composed of Cr, Co, Mo and Cu,
The third component is an alloy consisting of Si and B. An alloy powder obtained by melting the alloy according to any one of claims 1 to 4, spraying a fluid to the molten alloy to atomize the alloy, and then cooling the atomized alloy with a refrigerant. According to claim 5,
The alloy powder includes an amorphous phase and has a defect formed on the surface. According to claim 5,
The alloy powder is an alloy powder in which the reduction rate of E. coli measured by the KSM 0146 test method is 99.9% or more after 24 hours. According to claim 6,
The alloy powder is an alloy powder in which the reduction rate of E. coli measured by the KSM 0146 test method is 80% or more after 1 hour. parent material; and
An alloy coating layer provided on the base material; Including,
The alloy coating layer,
a first component composed of Fe and Ni;
A second component consisting of three or more selected from the group consisting of Cr, Co, Mo, and Cu; and
a third component composed of Si and B; including,
With respect to 100 parts by weight of the first component,
The second component is included in 90 to 110 parts by weight,
The third component is included in 5 to 15 parts by weight, and the weight ratio of the Fe to 100 parts by weight of the first component is 1.3 to 2.0 times the weight ratio of the Ni to 100 parts by weight of the first component. Alloy coated body. According to claim 9,
The alloy coating body having a thickness of 10 μm to 500 μm of the alloy coating layer. According to claim 9,
The porosity of the alloy coating layer is 5.0% or less of the alloy coated body. According to claim 9,
The alloy coating layer is an alloy coating body in which the reduction rate of E. coli measured by the test method of JIS Z 2801 is 99.9% or more after 24 hours.