WO2018016772A1

WO2018016772A1 - Method for manufacturing multilayer-structure metal by using composite surface treatment method and multilayer-structure metal manufactured thereby

Info

Publication number: WO2018016772A1
Application number: PCT/KR2017/007076
Authority: WO
Inventors: 한종수; 오종훈; 이원준
Original assignee: 전남대학교산학협력단
Priority date: 2016-07-19
Filing date: 2017-07-04
Publication date: 2018-01-25
Also published as: KR101841471B1; KR20180011895A

Abstract

The present invention relates to a multilayer-structure metal manufacturing method using a composite surface treatment method. A multilayer-structure metal manufacturing method using a composite surface treatment method according to the present invention comprises the steps of: treating a surface of a base layer; forming a protective layer on the surface of the surface-treated base layer; and attaching a solid particle to a surface of the protective layer.

Description

Method for manufacturing multilayered metal using composite surface treatment method and multilayered metal produced thereby

The present invention relates to a method for manufacturing a multi-layered metal and a multi-layered metal produced thereby, and more particularly, to a method for manufacturing a multi-layered metal using a composite surface treatment method for improving frictional resistance of a surface of a base layer and a multi-layer manufactured thereby A structural metal.

The titanium surface forms a surface layer because of its own components or because of its chemical activity. If the molar volume of the resulting surface layer is greater or less than the molar volume of the original base surface, cracks occur in the resulting surface layer and the surface reaction continues. On the other hand, when the molar volume of the resulting surface layer is similar to the molar volume of the original base surface, the change is stopped at the extent to which a thin film is formed on the surface. These surface reactions can occur not only in the simple chemical reaction of the underlying solid surface and surrounding chemicals, but also in electrochemical reactions and forced collisions of energetic species.

When the titanium surface and the titanium surface are in contact with each other, the kinetic energy applied during the contact through friction is converted into thermal energy, and the two surfaces are worn out by the contact. Friction is derived from the forces between the atomic molecules of the two surfaces in contact, rather than the properties of the surface itself, but it is impossible to establish a theory by physical inference.

This titanium surface friction is represented by the so-called Law of dry friction. The experimental law obtained in the 15th-18th centuries states that Amontons' 1st law that frictional force is proportional to the applied load, Amontton's 2nd law that frictional force is not related to the apparent area of contact, and kinetic frictional force Not a function is summed up by Coulomb's law.

Microscopically, friction can be attributed to the mechanical engagement of the surfaces in contact and the physical attraction between two surface atoms (eg, van der Waals forces), which are called mechanical friction and physical friction, respectively. Ideally, the attraction between surface molecules will be proportional to the contact area in proportion to the number of surface atoms in contact with the interaction between surface atoms, and the resistance due to mechanical engagement will increase the degree of engagement under load, regardless of the area of contact. It can be expressed as an experimental result such as Amontong's first and second law observed macroscopically. Mechanical friction will be related to the surface curvature, and in general, as the curvature increases, the coefficient of friction increases, lowering surface curvature to reduce friction. Usually, the bending height of the surface can be lowered by using a general abrasive having a high hardness up to the micrometer area. However, when the height of the bend is in the region of 1 to 1000 nm, polishing with mechanical polishing and chemical reaction is necessary.

A method of reducing friction in large sized parts is to use fluid bearings such as ball bearings, roller bearings and air cushions. In this case, many plastic materials such as nylon, high density polyethylene (HDPE), and polytetrafluoroethylene (PTFE) are used. For smaller, non-bearing parts, the usual way to reduce friction is to use a lubricant that sandwiches oil, water, grease, and layered solids between the two surfaces.

However, the method of using a lubricant has a disadvantage in that a surface component and a different material are put between two surfaces in contact and the concentration is maintained to some extent. And since the other layer is formed by interaction of the surface and the molecule | numerator contained in a lubricant when a junction area is unit of nm, the action pattern is not certain. In particular, if the lubricant cannot be used for various reasons, there is no way to lower the friction.

An object of the present invention is to provide a multi-layer metal manufacturing method using a complex surface treatment method that can reduce the frictional resistance of the surface of the base layer, without the use of lubricants in the small size parts.

The present invention comprises the steps of treating the surface of the base layer; Forming a protective layer on the surface of the base layer surface-treated; And

Affixing solid particles on the surface of the protective layer; is achieved by providing a multi-layer metal manufacturing method using a composite surface treatment method comprising a.

In the above, the solid particles are characterized by having a size in the range of 10nm ~ 10㎛ diameter.

The solid particles are formed of a metal.

The solid particles are characterized by being spherical of uniform size.

Attaching the solid particles on the surface of the protective layer is characterized in that it is carried out by a method of producing the solid particles directly on the surface of the protective layer.

The method for producing solid particles directly on the surface of the protective layer is characterized by using an electroless plating method.

The step of attaching the solid particles on the surface of the protective layer is characterized in that it is carried out by producing solid particles first, and then connecting the resulting solid particles to the surface of the protective layer.

The step of attaching the solid particles on the surface of the protective layer is characterized by physical or chemical bonding by having functional groups in affinity with both the surface of the protective layer and the surface of the solid particles at both ends of the compound serving as a bridge.

The step of treating the surface of the base layer includes polishing the base layer using physical polishing so that the surface curvature is 10 nm to 10 μm, and chemically treating the surface of the ground base layer. It is done.

Chemically treating the surface of the ground substrate layer is performed by any one selected from a mixed solution of an acid, a base, and an organic solvent.

In the chemical treatment of the polished base layer surface, the compound layer formed on the base layer surface is removed.

The base layer or the protective layer is characterized in that formed of a metal.

The metal of the base layer is characterized in that titanium.

In the multi-layered metal manufacturing method using the composite surface treatment method according to the present invention, the solid particles attached to the surface may act as a ball bearing to reduce the surface friction, thereby reducing the tightening torque mainly during surface contact. In order to improve the tightness of the fine screw (screw), it is possible to improve the adhesion and airtightness between the two surfaces when bonding.

1 is a flowchart illustrating a method of manufacturing a multilayer structure metal using the composite surface treatment method according to the present invention.

Figure 2 is a graph showing the results of microscopic analysis of the surface of the Ti specimen used in the present invention.

Figure 3 is an electron micrograph of the Pt / Ti specimen used in the present invention. (x 5,000)

Figure 4 is an electron micrograph of the Pt / Ti specimen used in the present invention. (x 200,000)

5 is an AFM image of the surface of the Pt / Ti specimen used in the present invention.

6 is an R-LFM image of the surface of the Pt / Ti specimen used in the present invention.

7 is an L-LFM image of the surface of the Pt / Ti specimen used in the present invention.

8 is a scanning electron micrograph of Au nanoparticles produced in the connecting molecule solution according to Example 1 of the present invention.

9 is a scanning electron micrograph of the Au / Pt / Ti specimen according to Example 1 of the present invention.

10 is an AFM image of the Au / Pt / Ti specimen surface according to Example 1 of the present invention.

FIG. 11 is an R-LFM image of the Au / Pt / Ti specimen surface according to Example 1 of the present invention. FIG.

12 is an L-LFM image of the Au / Pt / Ti specimen surface according to Example 1 of the present invention.

13 is an electron micrograph of the surface of the Au / Pt / Ti specimen according to Example 2 of the present invention.

14 shows EDX measurement results on the surface of the Au / Pt / Ti specimens according to Example 2 of the present invention.

FIG. 15 is a graph showing ESCA measurement results of the Au / Pt / Ti specimen surface according to Example 2 of the present invention. FIG. 16 is an AFM image of the Au / Pt / Ti specimen surface according to Example 2 of the present invention.

17 is an L-LFM image of the Au / Pt / Ti specimen surface according to Example 2 of the present invention.

18 is an R-LFM image of the Au / Pt / Ti specimen surface according to Example 2 of the present invention.

19 is a scanning electron micrograph of the surface of the Au / Pt / Ti specimen in accordance with Example 3 of the present invention. (x10,000)

20 is a scanning electron micrograph of the surface of the Au / Pt / Ti specimen in accordance with Example 3 of the present invention. (x50,000)

21 is an AFM image of an Au / Pt / Ti specimen according to Example 3 of the present invention. (20 μm x 20 μm)

FIG. 22 is an L-LFM image of an Au / Pt / Ti specimen according to Example 3 of the present invention. FIG.

FIG. 23 is an R-LFM image of an Au / Pt / Ti specimen according to Example 3 of the present invention. FIG.

The size of the solid particles deposited on the surface of the protective layer may be in the range of diameter micro (μm) or nano (nm), preferably in the range of 10 nm to 10 μm in diameter. In this range, the surface frictional resistance improving effect is excellent, and beyond this range, sufficient frictional resistance improving effect cannot be expected.

From the viewpoint of improving the surface friction resistance, the solid particles are preferably spherical, and more preferably uniform in size.

If the size of the solid particles is uniform, it is possible to substitute the properties of the uniform film without being affected by the surface irregularities.

Such solid particles may be formed of a metal, and may be preferably formed of gold (Au) having excellent adhesion (bondability).

In addition, the solid particles may be formed using a soft material, in which case the two surfaces may be deformed upon fixation to increase airtightness.

The surface of the multi-layered metal produced by the composite surface treatment method having such a structure reduces friction when the particles attached to the protective layer surface act as a ball bearing in the surface contact in small size parts. This reduction in surface frictional resistance can reduce the tightening torque of the screw, particularly when the base layer of titanium is a threaded component, thereby improving the tightening of fine screws, ie male and female threads, I can improve a feel.

In addition, the surface of the multi-layered metal produced by the composite surface treatment method of such a configuration improves the adhesion and airtightness between the surfaces formed when two surfaces are joined.

Advantages and features of the present invention, and methods for achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Hereinafter, with reference to the accompanying drawings it will be described in detail with respect to a multi-layer metal manufacturing method using a composite surface treatment method according to the present invention.

Referring to Figure 1, the multi-layer metal manufacturing method using the composite surface treatment method according to the invention, the base layer surface treatment step (S110), the protective layer forming step (S120) and the protective layer surface particle attachment step (S130) Include.

In the base layer surface treatment step (S110), after polishing the surface of the base layer, the compound layer formed on the base layer surface is removed by appropriate chemical treatment to chemically activate the base layer surface.

The base layer may be formed of a metal, and may be formed of titanium (Titanium), which is preferably light and strong in biocompatibility. At this time, the base layer has a bend height of approximately 1 ~ 1000nm.

Surface polishing of such a base layer can be performed using at least one of physical polishing or chemical polishing, thereby lowering the degree of curvature of the base layer surface.

Physical polishing which lowers the degree of curvature of the base layer surface can be carried out so that the degree of curvature of the surface of the base layer is 10 nm to 10 탆 using mechanical polishing usually using an abrasive. At this time, if the curvature of the base layer surface is less than 10nm it may be difficult to implement the process, if it exceeds 10㎛ it may be difficult to expect sufficient surface adhesion or airtightness between the two surfaces in contact.

The size of the abrasive is in the size of [mu] m and in particular cases tens of nm sized particles can be used. The type of abrasive grain is determined according to the mechanical strength of the base layer surface.

In the polishing of the base layer surface, part of the compound layer formed on the surface of the base layer, for example, an oxide layer, is partially removed.

Titanium easily reacts with oxygen in air to form a nanometer (nm) titanium oxide (TiO ₂ ) film on the surface, which causes a problem of poor adhesion when coating other materials on the titanium surface.

According to the present invention, since the oxide layer on the surface of the base layer is partially removed during the base layer surface polishing process, even if the base layer is formed of titanium, it is possible to prevent a decrease in adhesion due to the coating of the base layer.

The ground surface of the ground layer is washed several times with distilled water or an organic solvent, and then chemically treated with a mixed solution of acid, base or organic solvent in consideration of the material of the base layer. Most base layer surfaces are chemically treated with appropriate compounds to bring about surface activation.

The protective layer forming step (S120) may form a protective layer that may dry or wet the base layer surface and bind particles on the surface-treated base layer surface.

The protective layer can be formed of a metal with low chemical activity.

The protective layer may be formed using any one selected from physical, chemical and electrochemical methods. For example, the physical method may be vacuum deposition, and the electrochemical method may be electroplating, but is not particularly limited thereto.

For example, the protective layer may be formed of a platinum plating layer coated with platinum (Pt) having low reactivity by a conventional electroplating method. In this case, platinum plating may be performed using a conventional H ₂ PtCl ₆ plating solution.

Protective layer surface particle attachment step (S130) attaches a certain size of solid particles on the surface of the protective layer.

The particle attachment method of the present invention is characterized by attaching a particle lubricating substance of a prescribed size, ie, solid particles, on the surface of the protective layer, as opposed to forming a conventional solid lubricating substance as a film on the surface of the protective layer.

In this case, the particles attached on the surface of the protective layer act as a ball bearing upon surface contact, thereby reducing the adhesive frictional force on the surface of the base layer. This is because the mechanical friction due to the engagement of the protrusions with the protrusions and the physical friction due to the physical attraction of the surface atoms are reduced compared to the surface before treatment.

Specifically, the particle attachment method of the present invention may be a method of producing solid particles directly on the surface of the protective layer, or may be a method of first generating particles of a required size and then attaching the generated particles to the surface of the protective layer.

These particle attachment methods have physical or chemical bonds at both ends of a compound serving as a bridge to have a functional group that has affinity with the protective layer surface and the particle surface.

In one example, the former particle attachment method is a method of growing solid particles on the surface of a protective layer and bonding solid particles to the surface of a protective layer.

This electron particle attachment method may be composed of a linking molecule bonding process, a washing process, and a solid particle growth and linking process.

The linking molecule binding process deposits a base layer having a protective layer surface in the linking molecule ligand solution to bind the protective layer surface and the connecting molecule. In this case, the linking molecule ligand solution is a ligand solution including an organic molecule having a functional group having affinity with the protective layer surface and the particle surface.

The washing process may be performed by washing the base layer in which the linking molecule is bound to the protective layer surface to remove the linking molecule not bound to the protective layer surface, for example, by ultrasonic washing with distilled water and ethanol.

The solid particle growth and ligation process grows solid particles on the surface of the protective layer by depositing the connecting molecular binding base layer washed in the solid particle precursor compound-ligand solution, then adding a reducing agent and optionally stirring. In this process, the grown solid particles are combined with the linking molecules bonded to the protective layer surface, and as a result, the solid particles are connected (bonded, attached or bonded) to the protective layer surface.

In this case, the solid particle precursor compound-ligand aqueous solution may be prepared by mixing the solid particle precursor compound solution and the linking molecule ligand solution at a constant molar ratio and then stirring the mixture at room temperature for a predetermined time.

Another example of the former particle adhesion method is an electrolessplating method using an electroless solution. This method is useful for forming metal nanoparticles on solid substrate surfaces. In this method, since the surface of the protective layer and the produced nanoparticles are not chemically connected, the bonding strength is weak, the size of the attached particles is microscopically irregular, and the plating solution may be toxic to the human body. However, this method does not require useful and precise control when the size of the adhesion particles is several hundred nm to tens of micrometers.

In the latter method of particle attachment, a reducing agent is added to the linking molecule solution to produce solid particles first in the linking molecule solution, and then a base layer having a protective layer surface is deposited in the linking molecule solution containing the produced solid particles and optionally stirred. To connect (bond, adhere or bond) the solid particles to the surface of the protective layer.

In this case, the linking molecule solution may be a mixture of the linking molecule ligand solution and the solid particle-containing aqueous solution at a constant molar ratio.

Meanwhile, the linking molecule solution, the ligand solution, and the like may be appropriately selected depending on the material of the protective layer and the solid particles, and conventionally known materials may be used without limitation.

On the other hand, if the solid particles are a soft material, the deformed during mechanical bonding or fixing the two surfaces to act as a kind of gasket (gasket) to increase the airtightness between the two surfaces.

The most suitable example of the multi-layer metal using the composite surface treatment method of the present invention is a dental implant, a metal fixation system used in surgery, gaskets to improve the airtightness using soft particles.

Although not shown, The multi-layered metal produced by the composite surface treatment method of the present invention comprises a surface-treated base layer, a protective layer formed on the surface of the base layer, and solid particles attached on the surface of the protective layer.

In this case, the solid particles may have a size ranging from 10 nm to 10 μm in diameter, and may be bonded to the surface of the protective layer by a connecting molecule. The rest of the configuration is the same as described above and will be omitted.

실시예Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

1. 시편의 제조1. Preparation of Specimen

Ti specimen used in this example

As the metal of the base layer, Ti and light bioadhesives were used.

First, the surface was ground with sandpaper (# 100, # 200, # 400, # 800, # 1000, # 2000) and powder (1 μm, 3 μm) in order to reduce the degree of curvature of the Ti metal surface.

Subsequently, the surface polished Ti metal was immersed in 10% hydrochloric acid to remove various impurities adhering to the Ti surface, and then washed using ultrasonic waves.

Thereafter, the washed Ti metal was immersed in a mixed aqueous solution of 20% nitric acid and 2% hydrofluoric acid for 30 seconds in a volume ratio, followed by washing to obtain Ti pieces.

An optical micrograph analysis result of the surface of the Ti specimen is shown in FIG. 2, and as shown in FIG. 2, the roughness of the surface of the Ti specimen was about 100 nm.

보호층으로서의 Pt 층 형성 시편Pt layered specimen as protective layer

Since the Ti surface from which the oxide film was removed is unstable due to its high reactivity, Pt was coated by electroplating to obtain a Pt / Ti specimen to form a protective layer on the surface of the Ti specimen.

For the Pt plating, a 0.05 mol / LH ₂ PtCl ₆ plating solution was used. The electroplating conditions were 0.1 Adm ^-2 , 318K, pH 1.5, and the plating rate was 0.05 micrometermin ^-1 .

<실험예> SEM 사진 측정 Experimental Example

3 and 4 show scanning electron micrographs of the prepared Pt / Ti specimens.

<실험예> AFM 영상 측정 Experimental Example AFM Image Measurement

The frictional resistance is expressed as being proportional to the contact surface, but in the sample where Au particles are chemically attached to the surface of Pt / Ti, the circular curvature of the sample is about 100 nm and the size of the attached particles is several tens of nm, so that one measurement area is several tens of nm. Should be less than

As a measuring method that satisfies these conditions, there is an LFM that measures the degree of warpage caused by friction between the syringe probe and the surface in the AFM. The LFM measurement of a surface consists of an AFM image showing the curvature of the surface, and two LFM images showing the frictional force, that is, the degree of deflection of the probe, according to the direction of the probe.

5 to 7 show AFM images, R-LFM images and L-LFM images of the prepared Pt / Ti specimen surface.

실시예 1Example 1

Au nanoparticles were first formed in the connecting molecule solution, and then Pt / Ti specimens were deposited on the connecting molecule solution containing the produced Au nanoparticles to connect the Au nanoparticles to the Pt surface. The method is as follows.

first, A Au nanoparticle was first produced by adding a reducing agent to the Au gold compound-ligand aqueous solution of Example 1 in which a C ₃ H ₆ O ₂ S ligand solution and an aqueous Au solution were mixed in a molar ratio.

Subsequently, the Pt / Ti specimen was deposited in an aqueous Au compound-ligand solution containing the produced Au nanoparticles, followed by stirring for 1 hour while maintaining the temperature at 95 ° C., where Au nanoparticles were attached to the Pt surface. A / Pt / Ti specimen was obtained.

<< 실험예Experimental Example > > SEMSEM 사진 측정 Photo measurement

8 is a scanning electron micrograph of the Au nanoparticles produced in the solution according to Example 1 of the present invention, Figure 9 is a scanning electron micrograph of the Au / Pt / Ti specimen according to Example 1 of the present invention .

<< 실험예Experimental Example > > AFMAFM 영상 측정 Image measurement

10 to 12 are AFM images, R-LFM images, and L-LFM images of the Au / Pt / Ti specimen surfaces according to Example 1, respectively.

In FIG. 10, it can be seen from the AFM that tens of nanoparticles are present on the Pt surface of the Au / Pt / Ti specimen according to Example 1, which can be confirmed by the two LFM images shown in FIGS. 11 and 12.

The spreading degree of the frictional resistance of FIG. 11 is 200 mV at the peak half height. On the other hand, in the LFM image of FIG. 6 to which Au nanoparticles are not attached, the spread from the peak half height is about 500 mV.

When Au nanoparticles are attached to the platinum surface, it is impossible to find the same surface before and after the treatment, so the LFM image of the Pt surface (Figs. 5 to 7) and the Pt / LFMs of Ti surfaces (Figs. 10-12) were compared. Compared with FIGS. 5 to 7, it was found that the Au / Pt / Ti specimen prepared in Example 1 of the present invention reduced the overall frictional force by the adhesion of Au nanoparticles.

실시예 2Example 2

Organic molecules containing sulfur (S) C ₃ H ₆ O ₂ S [3-Mercaptopropionic acid, ALDRICH] (ligand) are used to grow Au nanoparticles on the Pt surface as a protective layer and to connect Au to the Pt surface. It was. The method is as follows.

First, the Pt / Ti specimen was deposited on an aqueous solution of C ₃ H ₆ O ₂ S [3-Mercaptopropionic acid] ligand to combine the Pt surface with the organic molecules. Thereafter, ultrasonic waves were washed with distilled water and ethanol to remove organic molecules not bound to the Pt surface.

Subsequently, 72 mL of 880 mM NaBH ₄ [Sodium borohydride] was added as a reducing agent while the washed organic molecule-bound Pt / Ti specimen was deposited in an aqueous Au compound-ligand solution to grow Au particles on the Pt surface. An attached Au / Pt / Ti specimen was obtained.

Here, Au compound-ligand aqueous solution is a mixture of HAuCl ₄ · 3H ₂ O [Gold (lll) chloride trihydrate] 20.3 mM (5.08 × 10 ^-4 mol) and C ₃ H ₆ O ₂ S solution, C ₃ H ₆ The molar ratio of O ₂ S and HAuCl ₄ 3H ₂ O was 1: 25,000, and the two solutions were mixed and stirred at room temperature for 1 hour.

<실험예> SEM 사진 측정 Experimental Example

Scanning electron microscope (SEM) images of the Au / Pt / Ti specimen surfaces prepared according to Example 2 were measured and the results are shown in FIG. 13.

Referring to FIG. 13, the size of the Au particles attached to the Au / Pt / Ti specimens of Example 2, which was grown after Au particles were grown on the Pt surface, was about 50 nm.

<실험예> EDX 측정 Experimental Example EDX Measurement

Table 1 and Figure 14 below shows the EDX measurement results of the Au / Pt / Ti specimen surface according to Example 2 of the present invention.

구분division	원소element	무게%weight%	원자%atom%
실시예1Example 1	CC	9.369.36	60.8160.81
	TiTi	2.492.49	4.064.06
	PtPt	53.2853.28	21.3121.31
	AuAu	34.8734.87	13.8213.82
	합계Sum	100.00100.00	100.00100.00

Referring to Table 1 and FIG. 14, the Au / Pt / Ti specimens of Example 2 consisted of about 4%, 21%, 14%, and 61% of Ti, Pt, Au, and C in atomic percent, respectively, as a result of EDX analysis. Could confirm.

<실험예> ESCA 측정 Experimental Example ESCA Measurement

Table 2 and Figure 15 shows the ESCA measurement results of the Au / Pt / Ti specimen surface according to Example 2 of the present invention.

구분division	피크 이름Peak name	Pt4f7Pt4f7	Au4fAu4f	S2pS2p	C1sC1s	O1sO1s
실시예 1Example 1	결합에너지(eV)Binding energy (eV)	73.9173.91	84.3284.32	162.97162.97	284.99284.99	532.05532.05
	피크 면적(N)Peak area (N)	3748.663748.66	14660.0514660.05	6095.086095.08	59276.1159276.11	21914.3321914.33
	원자 %Atomic%	3.553.55	13.8713.87	5.775.77	56.0856.08	20.7320.73

Referring to Table 2 and FIG. 15, the Au / Pt / Ti specimens of Example 2 were obtained by ESCA analysis, wherein Ti, Pt, Au, and C were about 0%, 4%, 14%, 56%, and sulfur in atomic percentages, respectively. And oxygen were about 6% and 21%, respectively.

Here, the Ti seen in the EDX is not seen in the ESCA or the Pt decreases because the analysis penetration depth of the EDX is several hundred nm while the ESCA is several nm.

Taken together, in the case of the Au / Pt / Ti specimen of Example 2, it can be seen that Ti is almost covered by Pt, Au nanoparticles are present on some surface of Pt.

On the other hand, the analysis of oxygen and sulfur in ESCA, which did not appear in EDX, is interpreted that the molecules composed of oxygen and sulfur connect the Au nanoparticles with the Pt surface.

<< 실험예Experimental Example >> AFMAFM 영상 측정 Image measurement

16 to 18 are AFM images, L-LFM images, and R-LFM images of the Au / Pt / Ti specimens prepared in Example 2 above.

In FIG. 16, it can be seen in the AFM that tens of nanoparticles exist on the Pt surface of the Au / Pt / Ti specimen according to Example 2 as shown in the SEM photograph of FIG. 14, which is represented by L shown in FIGS. 17 and 18. It could be confirmed again by -LFM image and R-LFM image.

실시예 3Example 3

The Pt / Ti specimen was deposited on an Au plating solution, and electroless Au plating was performed while maintaining 95 ° C. and a hydrogen ion concentration of 4.6.

Subsequently, the Pt / Ti specimens in which the electroless Au plating process is completed are washed three times with pure water, and then washed with ethyl alcohol (CH ₃ CH ₂ OH) and dried at 80 ° C., where Au particles are attached to the Pt surface. A / Pt / Ti specimen was obtained.

Here, the Au plating solution contained potassium cyanide (KAu (CN) ₂ ) as a source of Au, and the concentration of Au in the Au plating solution was 2.5 g / l.

19 and 20 are scanning electron micrographs at x10,000 and x50,000 magnifications of Au / Pt / Ti specimen surfaces according to Example 3 of the present invention.

19 and 20, on the platinum surface of the Au / Pt / Ti specimen according to Example 3, particles having a diameter of about 60 nm and clusters of 1 μm were formed. This is different from the shape of the separated nanoparticles that can be seen in the SEM photographs of Examples 1 and 2 in which the nanoparticles are bonded to the Pt surface through a ligand.

<< 실험예Experimental Example > > EDXEDX 측정 Measure

Table 3 shows the EDX measurement results of the Au / Pt / Ti specimen surface according to Example 3 of the present invention.

	원소element	질량%mass%	원자 %Atomic%
실시예 3Example 3	CuCu	6.686.68	18.0818.08
	PtPt	52.4452.44	46.2346.23
	AuAu	40.8840.88	35.7035.70
	합계Sum	100.00100.00	100.00100.00

Referring to Table 3, the Au / Pt / Ti specimen of Example 3 did not show a peak of Ti as a result of EDX analysis, which means that the average Au layer is thicker than that of Examples 1 and 2.

In addition, the Au / Pt / Ti specimen of Example 3 showed a peak of copper, indicating that Cu contained in the electroless plating solution was also precipitated.

<< 실험예Experimental Example > > AFMAFM 사진 측정 Photo measurement

AFM images of the Au / Pt / Ti specimen surface according to Example 3 of the present invention were measured.

21 to 23, it can be seen that the peak half height spread is about 200 mV, which is smaller than the surface to which the Au particles of FIG. 6 are not attached.

Taken together, it can be seen that the particle generation method by the electroless plating method has a thicker particle layer and deposits impurities in the plating solution than the nanoparticle binding method by the ligand, but the frictional force is similar to that of the nanoparticle binding method by the ligand. have.

Preferred embodiments of the present invention described above are disclosed for the purpose of illustration, and various substitutions, modifications, and changes within the scope without departing from the spirit of the present invention for those skilled in the art to which the present invention pertains. It will be possible, but such substitutions, changes and the like should be regarded as belonging to the following claims.

Claims

Treating the surface of the base layer;

Forming a protective layer on the surface of the base layer surface-treated; And

Attaching solid particles on the surface of the protective layer; a multi-layer metal manufacturing method using a composite surface treatment method comprising a.
The method of claim 1,

The solid particles are

Method for producing a multilayer structure metal using a composite surface treatment method having a size in the range of 10nm ~ 10㎛ diameter.
The method of claim 1,

Attaching the solid particles on the surface of the protective layer,

Method for producing a multi-layered metal using a composite surface treatment method performed by the method of producing the solid particles directly on the surface of the protective layer.
The method of claim 1,

Attaching the solid particles on the surface of the protective layer,

Method for producing a multi-layered metal using a composite surface treatment method which is produced by first producing the solid particles, and then connecting the generated solid particles to the surface of the protective layer.
The method according to claim 3 or 4,

Attaching the solid particles on the surface of the protective layer,

Method of producing a multi-layer metal structure using a composite surface treatment method to have a physical or chemical bond by having a functional group having affinity with the surface of the protective layer and the surface of the solid particles at both ends of the compound acting as a bridge.
The method of claim 3,

The method for producing the solid particles directly on the surface of the protective layer

Method for producing a multilayer structure metal using a composite surface treatment method using an electroless plating method.
The method of claim 1,

The solid particles are

Method for producing a multi-layer metal using a composite surface treatment method of forming a metal.
The method of claim 1,

The solid particles are

Method for producing a multilayer structure metal using a composite surface treatment method that is a spherical shape of uniform size.
The method of claim 1,

Treating the surface of the base layer is

Polishing the base layer using physical polishing so that surface curvature is 10 nm to 10 μm,

A method of producing a multilayer structure metal using a composite surface treatment method comprising the step of chemically treating the surface of the ground layer polished.
The method of claim 9,

Chemically treating the surface of the ground base layer

Method for producing a multilayer structure metal using a composite surface treatment method performed by any one selected from a mixed solution of acid, base and organic solvent.
The method of claim 9,

In chemical treatment of the ground surface of the ground,

Method for producing a multi-layered metal using a composite surface treatment method in which the compound layer formed on the surface of the base layer is removed.
The method of claim 1,

The base layer is

Method for producing a multi-layer metal using a composite surface treatment method of forming a metal.
The method of claim 12,

The metal of the base layer is

Method for producing a multilayer structure metal using a composite surface treatment method that is titanium.
The method of claim 1,

The protective layer

Method for producing a multi-layer metal using a composite surface treatment method of forming a metal.