KR20110063962A - One-time usable products - Google Patents

Abstract

PURPOSE: A biodegrading disposable product is provided to be bio-degraded in a short time using a biodegradable magnesium alloy, and to secure the light weight of the product. CONSTITUTION: A biodegrading disposable product contains a biodegradable magnesium alloy. The biodegradable magnesium alloy contains magnesium, and an impurity selected from manganese, iron, nickel, or a compound of the iron and the nickel. The biodegradable magnesium alloy is marked with chemical formula 1.

Description

Disposable products {ONE-TIME USABLE PRODUCTS}

The present invention relates to a disposable article comprising a biodegradable magnesium alloy.

With the development of the industry, the consumption of instant foods is increasing due to the change of dietary life with the increase of income level. At present, there is a need for cheap disposable products such as food containers, packaging materials, cutlery, etc., which are hygienic, convenient and productive, which are suitable for such instant foods. Accordingly, disposable products are used in large quantities in fast food stores, convenience stores and vending machines, and these disposable products are collected and recycled after being discarded after use.

Such disposable containers have increased year by year due to a number of excellent advantages, environmental pollution due to the increased use of these containers. There is a method of disposal of disposable containers, such as landfills, which are hardly decomposed by transition metals or microorganisms present in the soil. In addition, when incineration is used, it is known that a large amount of toxic gases (dioxin, carbon monoxide, etc.) are generated to have a global warming and harmful effects on the human body.

In order to overcome such environmental problems, biodegradable resins that are similar in nature to conventional synthetic resins and easily decomposed by microorganisms and / or ultraviolet rays have been studied. For example, Japanese Patent Laid-Open No. 2005-264159 discloses a biodegradable resin composition having excellent strength of a molded article and having an antistatic function. In addition, Japanese Patent No. 4058683 discloses a resin composition comprising a metal containing magnesium hydroxide in a biodegradable resin. In addition, US Patent Publication No. 20070257239 discloses a biodegradable resin composition that reduces the generation of toxic substances when the resin is burned using a metal hydroxide as a flame retardant additive.

However, the above-described biodegradable resins are difficult to realize the appropriate strength and heat resistance according to the use and difficult to have an appropriate decomposition rate.

It is an object of the present invention to provide a disposable product which is biodegradable, lightweight, high strength and high heat resistance in a short time in a natural state.

The present invention provides a disposable article comprising a biodegradable magnesium alloy.

The present invention provides a packaging material comprising a biodegradable magnesium alloy.

Disposable article of the present invention is biodegradable in a short time in the natural state, light weight, high strength and high heat resistance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Ⅰ. Disposable

Disposable article according to an embodiment of the present invention comprises a biodegradable magnesium alloy. The biodegradable magnesium alloy provides strength and heat resistance to the disposable product, and enables biodegradation in a short time in a natural state. Here, strength and heat resistance can be adjusted by the amount of the biodegradable magnesium alloy included in the disposable product of the present invention.

The biodegradable magnesium alloy may be represented by the following formula (1).

<Formula 1>

Mg _a Ca _b X _c

In Chemical Formula 1,

a, b, and c are molar ratios of the components, a + b + c = 1, 0.5 ≦ a <1, 0 ≦ b ≦ 0.4, 0 ≦ c ≦ 0.4, provided that at least one of b and c is 0 And c is 0, the content of Ca is included in the range of 5 to 33% by weight based on the total weight of the biodegradable magnesium alloy, X is zirconium (Zr), molybdenum (Mo), niobium (Nb), tantalum Choose from (Ta), titanium (Ti), strontium (Sr), chromium (Cr), manganese (Mn), zinc (Zn), silicon (Si), phosphorus (P), nickel (Ni), and iron (Fe) It is 1 type or 2 or more types.

Even if said X is 2 or more types, the molar ratio of the sum total of X satisfy | fills the range of said c. As the content of Ca and X increases, the strength of the magnesium alloy increases, and at the same time the rate of biodegradation increases. Therefore, the disposable article of the present invention can determine the amount of Ca and X within the above-described range in consideration of the required strength and the rate of extinction of the filling metal.

When X contains nickel (Ni). Nickel reduces the toxicity of disposable products and facilitates the control of corrosion rate. At this time, the content of nickel is preferably 100ppm or less, more preferably 50ppm or less. In addition, when iron (Fe) is included in X, since iron has a great influence on the increase in corrosion rate of magnesium alloy, the iron content is preferably 1,000 ppm or less, and more preferably 500 ppm or less. At this time, if the iron content is included in the above range, the iron is not dissolved in magnesium and exists as an independent factor to increase the corrosion rate of magnesium.

The biodegradable magnesium alloy is magnesium (Mg); Manganese (Mn) as an impurity; Including iron (Fe), nickel (Ni) and one selected from the group consisting of a mixture of iron (Fe) and nickel (Ni), the impurity content is greater than 0 to 1 part by weight based on 100 parts by weight of the magnesium It may be less than, {1 type selected from the group consisting of a mixture of iron (Fe), nickel (Ni), iron (Fe) and nickel (Ni) / manganese (Mn) = more than 5 or less.

It is preferable that {the 1 kind chosen from the group which consists of a mixture of iron (Fe), nickel (Ni), iron (Fe), and nickel (Ni)} / manganese (Mn) = more than 0.2 or less. When the {one kind selected from the group consisting of a mixture of iron (Fe), nickel (Ni), iron (Fe) and nickel (Ni)} / manganese (Mn) satisfies the above-mentioned range, the decomposition rate is extremely Low control improves corrosion resistance.

When the impurities include nickel (Ni) and manganese (Mn). Increase the corrosion rate of net Mg.

In addition, the biodegradable magnesium alloy preferably further includes aluminum (Al) as an impurity.

The biodegradable magnesium alloy is represented by the following formula (2), relative to the total weight, Ca is greater than 0 to 23% by weight; Y is greater than 0 and less than or equal to 10 weight percent; And Mg may be a magnesium alloy including the remaining amount.

<Formula 2>

Mg-Ca-Y

In Formula 2, Y is Mn or Zn.

When the biodegradable magnesium alloy represented by the formula (2) satisfies the above-described range, it is possible to provide a disposable product in which mechanical properties and corrosion resistance are improved at the same time, and brittle fracture does not occur.

In addition, the magnesium alloy represented by the formula (2) is preferably based on the total weight, Ca is more than 0 to 23% by weight, Y is 0.1 to 5% by weight and Mg is the remaining amount, more preferably the Ca is more than 0 and 23 wt% or less, X is 0.1 to 3 wt% and Mg is the balance. The reason is that when the same corrosion rate is implemented in consideration of possible side effects of impurities, it is advantageous that the content of impurities is small.

The biodegradable magnesium alloy may be applied by ultrasonic.

Disposable article according to another embodiment of the present invention may be filled with the biodegradable magnesium alloy in a porous structure.

The pore size of the porous structure can be adjusted according to the field used using a conventional method in the art, it is preferably 200 to 500㎛. If the pore size satisfies the above-mentioned range, biodegradation is easy in a natural state.

The porosity of the porous structure is preferably 5-95%. Here, the porosity refers to the volume ratio occupied by the pores in the total volume. The porosity may increase the strength of the porous structure by lowering the porosity when the required strength of the object to be applied is high.

The porous structure may be at least one selected from the group consisting of metals, ceramics, and polymers. When the porous structure is a metal, it is preferable that it is at least one member selected from the group consisting of titanium or a titanium alloy, cobalt-chromium alloy and stainless steel. When the porous structure is ceramic, it is preferably at least one selected from the group consisting of calcium phosphate (Calciu, Phosphate), alumina, zirconia and magnesia. When the porous structure is a polymer, it is preferably one or more selected from the group consisting of polyethylene, polylactic acids (PLA), polyglycolic acid (PGA), and copolymers thereof PLGA.

Disposable article according to another embodiment of the present invention may further comprise a biodegradable resin. The biodegradable resins facilitate the process when molded or processed for single use. In addition, compared to when the biodegradable magnesium alloy is included alone, it is possible to implement a lightweight.

The biodegradable resin is polylactic acid, polyglycolic acid, polycaprolactone, polybutylene succinate, polybutylene succinate o adipate copolymer, polyethylene succinate, polybutylene Adipate o terephthalate copolymer, polyethylene terephthalate o adipate copolymer, polyvinyl alcohol, polyurethane, polyester amide, polyaspartic acid, polyhydroxy butyrate, polyhydroxy butylate o burate copolymer , Polyhydroxy valeric acid (polyhydroxy valeric acid), starch (starch), chitin, chitosan, cellulose acetate and one or more selected from the group consisting of acetyl cellulose.

The disposable product of the present invention can be used as a disposable container or disposable cutlery.

II. Manufacturing method of disposable product

Method for producing a disposable article according to an embodiment of the present invention may include a) providing the biodegradable magnesium alloy, b) molding the provided biodegradable magnesium alloy.

Preferably, the step a) is a step of melting and providing the magnesium. In more detail, step a) may be a step of melting and providing the magnesium in an inert gas atmosphere or in a vacuum atmosphere such as argon (Ar) that does not react with magnesium. In the step a), the magnesium may be melted using various methods such as resistance heating, which generates heat by applying electricity to the resistor, induction heating by flowing a current through an induction coil, or by laser or focused light. It may be a step of providing. Here, the resistance heating method of the above-described melting method is the most economical. It is preferable to stir the molten alloy (hereinafter, molten metal) so that impurities can be mixed well when melting magnesium.

If the disposable product according to another embodiment of the present invention is filled with the biodegradable magnesium alloy in the pores of the porous structure, the step a) comprises the steps of a-1) preparing a porous structure; And a-2) filling pores of the porous structure with the biodegradable magnesium alloy.

In the step a-1), the porous structure may be one selected from the group consisting of metals, ceramics and polymers.

 When the porous structure is manufactured using only metal, step a-1) is as follows.

First, the metal is made of powder or wire. The metal produced from the powder or wire is prepared as a green preform. As the method for producing the preform, a sintering method and a method in which the sintering method is modified may be used.

The production method of the preform using the sintering method is as follows.

First, a metal made of the powder or wire is put in a container or pressed with an appropriate force of 100 MPa or less to have a weak strength, and the metal having such a weak strength is 2/10 to 9/10 of the melting point of the metal. Maintained at the temperature of the powder or wires to combine to prepare a preform having a mechanical strength.

In addition, the manufacturing method using a method in which the sintering method is modified is as follows.

The preform is manufactured by sintering the metal made of the powder or wire into a conductive container such as graphite and flowing a high current through the conductive container to generate heat instantaneously at the contact portion of the metal made of the powder or wire. .

When the porous structure is manufactured including a metal and a polymer, the step a-1) is as follows.

First, the metal is made of powder or wire. Subsequently, the polymer is mixed with the metal made of powder or wire, and the polymer is decomposed and extinguished at low temperature in the process of raising the temperature, and the metal made of powder or wire is sintered at high temperature to have a suitable mechanical strength. To prepare. At this time, the porosity and the strength of the sintered body are determined according to the sintering temperature, the pressing force, the mixing ratio of the polymer and the metal, and appropriate conditions can be selected as necessary. The sintering temperature depends on the type of material used to prepare the porous structure, and generally, about 1/2 to 9/10 of the melting point of the porous structure is preferable. Although sintering occurs even if no pressure is applied during sintering, the higher the pressure, the faster the sintering proceeds. However, as the pressing force is increased, additional costs such as device cost and mold cost are required, so it is better to select an appropriate pressure.

In addition, in addition to the above-described method, when the porous structure is prepared including a metal and a polymer, the step a-1) is as follows.

First, the polymer surface is plated with precious metals such as gold, platinum, and Pd. Thereafter, the polymer may be removed to prepare a metal porous structure having better biocompatibility.

When the porous structure is prepared using a water-soluble salt and a metal, the step a-1) is as follows.

First, a water-soluble salt and a metal powder are mixed and molded at high temperature to prepare a preform. Here, the water-soluble salt is preferably at least one selected from the group consisting of NaNO 2, KNO 2, NaNO 3, NaCl, CuCl, KNO 3, KCl, LiCl, KNO 3, PbCl 2, MgCl 2, CaCl 2 and BaCl 3. Subsequently, the preform is pressed at a temperature of 2/10 to 9/10 of the melting point of the metal powder. In the pressing process, the metal powders are bonded to each other by atomic transfer to form a structure, and form a composite material containing a water-soluble salt therein. When the composite material is immersed in water, only the water-soluble salt is dissolved to prepare a metal porous structure having pores. Furthermore, the metal porous structure may be manufactured by injecting a blowing agent that generates gas after completely melting the metal material.

When the porous structure is manufactured using an electrolyte solution containing a polymer and a metal ion, the step a-1) is as follows.

First, the surface of the porous polymer is plated with a metal using an electrolyte solution containing metal ions. In this case, the metal ion is not particularly limited, but is preferably at least one selected from the group consisting of Ti, Co, Cr, and Zr. Subsequently, when the temperature is removed to remove the polymer, a porous metal structure may be manufactured.

When the porous structure is manufactured using a ceramic, the step a-2) is as follows.

First, ceramic fine powder and binder polymer (polymer) are mixed. The mixture is coated on the surface of the skeleton structure of a foam material made of a removable material such as polyurethane and dried to form a porous structure. Then, when the temperature is increased, the polymer is burned and removed near the combustion temperature of the binder polymer, If the temperature is further increased, the remaining ceramics may be sintered with each other to produce a porous structure having mechanical strength.

Here, the ceramic fine powder is preferably at least one selected from the group consisting of hydroxyapatite (HA), zirconia and alumina.

Step a-1) may be a method of modifying or combining the above-described method of manufacturing a porous structure, or a method of manufacturing a porous structure in which the porosity of the inside and the outside is controlled by applying a part of a heterogeneous material. In the latter method, it is possible to produce a porous structure having high or low porosity on the inside and high porosity on the outside.

Step a-2), the method of immersing the porous structure in the melt of the biodegradable magnesium alloy, the method of fixing the porous structure and flowing the melt of magnesium to fill the pores, and the two methods from the outside One type selected from the group consisting of a method of applying the pressure of 1 atm or more to allow the molten biodegradable magnesium to be more easily filled between pores of the porous structure may be used. At this time, the molten biodegradable magnesium alloy may be heated so as not to solidify while filling the pores, or the various contaminants on the surface may be removed to induce the molten magnesium to easily fill the pores.

In addition, the step a-2) may be the following steps. In more detail, first, magnesium is vaporized by maintaining it at a high temperature, preferably at 700 ° C. or higher, and then magnesium vapor is deposited on the pore surface while passing between the pores of the porous structure, so that the pores of the porous structure are made of magnesium. It may be a filling step.

In addition, the step a-2) may be the following steps. In more detail, after dissolving a salt containing magnesium in a liquid, the magnesium may be adsorbed to the pore surface of the porous structure while passing the porous structure through the liquid.

In addition to the filling method as described above, in another modification, only some of the pores of the porous structure may be filled without completely filling the magnesium alloy. That is, after the molten magnesium is filled in the porous structure, if the high pressure gas is blown into the porous structure or the porous structure is rotated or shaken before the magnesium is completely solidified, the unsolidified magnesium is removed from the porous structure and only a part of the magnesium It can remain to produce a composite with magnesium impregnated in some of the pores. In this case, the magnesium filling rate for each position of the porous structure pores may be controlled differently.

On the other hand, in the case of a polymer having a lower melting point than magnesium, the porous structure is first formed, and when the pores are subsequently filled with molten magnesium, the polymer porous structure cannot maintain its shape. Therefore, the disposable product including the polymer and the biodegradable magnesium alloy is mixed with the biodegradable magnesium alloy powder and the polymer in the volume fraction of the range of 5:95 to 95: 5 and then heated to 150 to 500 ℃ Celsius range of 1 atm to 100 atm It is preferable to prepare a disposable product containing a biodegradable magnesium alloy by a method of pressurizing with. The above conditions are only preferable manufacturing conditions of the disposable article containing the polymer porous structure-biodegradable magnesium alloy, and even if the conditions deviated from the above conditions, the disposable article containing the polymer porous structure-biodegradable magnesium alloy is not molded. Modifications may not infringe the rights of the present invention.

Method for producing a metal, ceramic and polymer porous structure as described above, a method for filling the pores of the porous structure with a magnesium alloy, a method for producing a biodegradable disposables comprising a polymer filled with a biodegradable magnesium alloy to illustrate the present invention Only, the protection scope of the present invention is not limited thereto.

Step b) included in the method for producing a biodegradable magnesium alloy of the present invention may be a step of molding the molten biodegradable magnesium alloy into at least one selected from the group consisting of a cooling method, an extrusion method, and a metal processing method. have.

The said cooling method can be used for the purpose of improving the mechanical strength of a magnesium alloy. In more detail, if magnesium is melted in step a), a method of immersing the crucible containing molten magnesium in water may be used. In addition, a cooling method of spraying the molten magnesium using an inert gas such as argon may be used. The spraying cooling method can be cooled at a much higher rate to show very fine texture. However, care should be taken when casting magnesium to a smaller size, since a large number of pores (black portions) may be formed inside.

The extrusion method is used for the purpose of making the structure of magnesium uniform and improving mechanical performance. The extrusion method is preferably made at 300 to 450 ℃. In addition, the extrusion of the magnesium may be carried out within 10: 1 to 30: 1 reduction ratio (extrusion ratio) before and after extrusion. As the extrusion ratio increases, the microstructure of the extrusion material becomes uniform, and there is an advantage in that defects formed during casting are easily removed. In this case, it is preferable to increase the extrusion device capacity.

The metal processing method is not particularly limited as long as it is a metal processing method known in the art. For example, as described above, the molten magnesium is poured directly into a mold processed in a form close to the final product, which is manufactured from an intermediate material such as rod or plate, and then lathed or milled, and a large amount of magnesium alloy is applied. And pressurized forging to produce a final product shape.

In another embodiment of the present invention, if the disposable product includes a biodegradable magnesium alloy and a biodegradable resin, c) may further include coating a biodegradable resin on the biodegradable magnesium alloy.

Disposable article of the present invention is biodegradable in a short time in the natural state, light weight, high strength and high heat resistance.

III. Packing materials

The packaging material according to an embodiment of the present invention may include a biodegradable magnesium alloy. Since the description of the biodegradable magnesium alloy has been described above, it will be omitted.

The packaging material according to another embodiment of the present invention may be a biodegradable magnesium alloy is filled in the pores of the porous structure. Since the description of the porous structure has been described above, it will be omitted.

The packaging material according to another embodiment of the present invention may further include a biodegradable resin. Since the description of the biodegradable resin has been described above, it will be omitted.

Ⅳ. Manufacturing method of packaging material

The packaging material according to an embodiment of the present invention may include a) providing the biodegradable magnesium alloy, b) molding the provided biodegradable magnesium alloy.

If the packaging material according to another embodiment of the present invention is filled with the biodegradable magnesium alloy in the pores of the porous structure, the step a) comprises the steps of a-1) preparing a porous structure; And a-2) filling pores of the porous structure with the biodegradable magnesium alloy.

In another embodiment of the present invention, if the disposable product includes a biodegradable magnesium alloy and a biodegradable resin, c) may further include coating a biodegradable resin on the biodegradable magnesium alloy.

Description of each step is omitted because it has been described above.

Hereinafter, the production of a disposable or packaging material containing a biodegradable magnesium alloy will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention.

Examples 1-4: Preparation of Biodegradable Magnesium Alloys

Example 1

In Table 1, impurities (magnesium based) were mixed with magnesium (ultra purity: 99.9999% for reagents) and charged into a crucible having an internal diameter of 50 mm made of stainless steel (SUS 410). Subsequently, argon (Ar) gas was flowed around the crucible so that magnesium in the crucible did not come into contact with air, and the crucible temperature was raised from about 700 ° C. to 750 ° C. using a resistance furnace to melt magnesium. The crucible was shaken and stirred so that the molten magnesium and impurities could be mixed well. The molten magnesium was cooled to produce magnesium in the solid state. In addition, when cooling, the crucible was immersed in water for the purpose of improving the mechanical strength of the magnesium so that the molten magnesium is cooled rapidly.

Fe (ppm) Ni (ppm) Example 1-1 400 10 Example 1-2 70 5 Example 1-3 10 35

1 is a photograph taken by an optical microscope after polishing the cross section of the casting material of Example 1-1.

<Example 2>

The impurities (based on the Mg-Ca alloy) were mixed with Mg-Ca mixed with the composition shown in Table 2, and then charged into a crucible having an internal diameter of 50 mm made of stainless steel (SUS 410). Subsequently, argon (Ar) gas was flowed around the crucible so that the magnesium alloy in the crucible did not come into contact with air, and the crucible temperature was raised from about 700 ° C. to 1000 ° C. using a resistance furnace to melt the magnesium alloy. The fully molten magnesium alloy was cooled to produce a magnesium alloy in the solid state. The crucible was shaken and stirred so that the constituent elements of the molten magnesium alloy could be mixed well with each other. In addition, when cooling, the crucible was immersed in water for the purpose of improving the mechanical strength of the magnesium alloy to rapidly cool the molten magnesium alloy.

Mg (% by weight) Ca (% by weight) Fe (ppm) Ni (ppm) Example 2-1 99.2 0.8 10 35 Example 2-2 95 5 10 35 Example 2-3 89.5 10.5 10 35 Examples 2-4 77 23 10 35 Example 2-5 67 33 10 35

Mg: ultra-pure (99.9999%) magnesium for reagents

Figure 2 is a photograph of the appearance of the cast material produced in Example 2-5.

3 to 7 are polished cross sections of the cast materials prepared in Examples 2-1 to 2-5, respectively, and observed with an optical microscope.

3 to 7, in the cast material prepared in Examples 2-1 to 2-5, gray Mg occupies most of the area, and some dark gray Mg 2 Ca compounds and Mg mixed regions appear slightly. . As the amount of Ca increases, the area of the dark gray portion (called the mixed or process region of Mg 2 Ca compound and Mg) increases. In addition, it can be seen that all of the casting materials manufactured in Examples 2-1 to 2-5 were well manufactured without defects such as pores therein.

<Example 3>

A method of melting a magnesium alloy containing 67 wt% Mg and 33 wt% Ca with a heating furnace and then spraying a molten magnesium alloy with argon gas into a fine hole having a diameter of about 3 mm (also called gas blowing). By rapidly injecting and solidifying to prepare a rapidly cooled magnesium alloy material. When using this method, the magnesium alloy material is cooled at a much higher rate than that of Examples 1 and 2, showing very fine structure.

8 is a cross-sectional view of the Mg _0.67 Ca _0.33 alloy prepared by the above method with an optical microscope.

Referring to FIG. 8, it can be seen that the size of the constituent phase is very fine as compared with FIG. 7, which is a cross-sectional optical photograph of a magnesium alloy material manufactured by immersing the crucible in water and cooling.

<Example 4>

After mixing impurities (based on the Mg-Ca alloy) to the Mg-Ca alloy in the composition described in Table 3, it was prepared using the same method as in Example 1 described above, and then extruded. The extrusion temperature was varied depending on the Ca content and was increased as the Ca content was increased to facilitate the extrusion. Extrusion temperature was carried out in the range of at least 300 ℃, at a maximum 450 ℃, the cross-sectional area reduction ratio (extrusion ratio) before and after extrusion was fixed to 15: 1.

Mg (% by weight) Ca (% by weight) Fe (ppm) Ni (ppm) Example 4-1 100 0.0 10 35 Example 4-2 99.2 0.8 10 35 Example 4-3 95 5 10 35 Example 4-4 89.5 10.5 10 35 Example 4-5 77 23 10 35 Example 4-6 67 33 10 35

FIG. 9 shows the microstructure change according to the extrusion, and is a photograph obtained by observing the cross section of the longitudinal direction (left) and the horizontal direction (right) of Example 4-3 (extruded Mg0.95Ca0.05). It can be seen that the microstructure of the petal-shaped equipment visible in the casting material of Figure 4 is deformed during extrusion.

<Example 5>

After the alloys prepared in Examples 1 and 2 were processed into discs (targets) having a diameter of 3 inches and a thickness of 5 mm, magnesium was placed on the surface of the Ti alloy base material by sputtering by installing them inside a vacuum chamber and applying RF power. An alloy coating layer was formed.

FIG. 10 shows the biological material (Ti alloy) on which the coating film is formed by the method described above, and cuts the coating cross-section to reveal the coating cross section, and then observes the result by electron microscope. The thickness of the coating layer is about 5㎛, it can be seen that the coating film is grown in the vertical direction, it can be seen that irregularities are formed on the magnesium alloy coating surface.

FIG. 11 is a photograph of a magnesium alloy coating layer formed by Example 5 on a Ti 6 V 4 Al alloy with a diamond tip, and then observed with an electron microscope. FIG. In FIG. 16, the upper photograph is a specimen coated without surface cleaning, the intermediate photograph is a specimen coated after surface cleaning in a plasma atmosphere for about 1 minute, and the lower photograph is a specimen coated after surface cleaning in a plasma atmosphere for about 2 minutes. . In the case of coating without surface cleaning, the phenomenon that the coating film is slightly peeled off due to the external diamond tip occurred due to external stress. However, when the coating film is cleaned and then cleaned, the coating film is not peeled off by external stress.

Test Example 1 Evaluation of Properties of Magnesium Alloy

<Measurement test of magnesium alloy>

In order to test the strength of the magnesium alloy material of the present invention, the magnesium alloy materials prepared in Examples 1 and 2 were discharged and processed into a diameter of 3 mm and a length of 6 mm. The lower and upper surfaces of the discharged specimens were polished with 1000 times emery paper to level the surfaces. The machined test specimen was placed horizontally on a jig made of cemented carbide (tungsten carbide), and then a force was applied from the direction of the specimen using a head of a compression tester with a maximum load of 20 tons. At this time, the vertical descending speed of the head was set to 10-4 / s. During the test, the deformation amount and the compressive stress change amount were recorded in real time using an extensometer and a stress cell mounted on the compression tester. At this time, the size of the specimen was small, so that the strain gauge was mounted on the jig of the tester which pressed the specimen rather than the specimen, and was measured to be larger than the actual deformation of the specimen.

12 is a graph showing the results of strength measurement experiments on the magnesium alloy of the present invention prepared by varying the concentration of calcium in the magnesium alloy. According to the results of FIG. 12, it was confirmed that the strength of the alloy increases as the calcium content increases in the magnesium alloy. On the other hand, when the amount of Ca increases from 22% to 33%, it can be seen that the magnesium alloy is destroyed at a relatively low stress.

13 is a result of measuring the compressive strength after extruding the cast material. Although the yield strength (strength when bent in a straight line in a curve) of most Mg-Ca alloys was increased by extrusion, the yield strength rather decreased when the amount of Ca was 23%. The reason for this is that brittle Mg 2 Ca, which is largely distributed in the Mg matrix, is broken during extrusion or separated from the Mg matrix. When the amount of Ca is increased to 33%, the strength change is small before and after extrusion since almost all of the alloy material is composed of a brittle Mg 2 Ca phase.

Experiment on Corrosion Rate of Magnesium Alloy

Potentio Dynamic Test was used to evaluate the corrosion characteristics of magnesium alloys. First, the magnesium alloy material produced by the casting method was cut, and the surface was polished with 1000 emery paper. Except for the area of 1 cm2 on the polished magnesium alloy material surface was coated with an insulating material. Subsequently, a magnesium alloy was connected to the positive electrode, Pt and Ag-AgCl as a reference to the negative electrode, and the current was measured while gradually increasing the voltage after immersing the positive electrode and the negative electrode in the corrosion solution. The caustic solution was a mixture of the substances shown in Table 4 in 1 liter of water was used. The solution temperature was maintained at 37 ° C. during the test. The composition of the corrosion solution used in the corrosion test is based on a total volume of 1 liter.

Ingredient Name Weight (g) NaCl (Sodium Chloride) 8 KCl (Potassium Chloride) 0.4 NaHCO ₃ (Sodium Hydrogen Carbonate) 0.35 _{NaH 2 PO 4 · H 2 O} (A430846 420) 0.25 _{Na 2 HPO 4 · 2H 2 O} (K32618380 408) 0.06 MgCl ₂ (magnesium chloride) 0.19 MgSO ₄ 7H ₂ O (Magnesium Sulfate Heptahydrate) 0.06 Glucose One CaCl _{2 ·} 2H ₂ O (Calcium Chloride Dihydrate) 0.19

14 is a graph showing the results of the corrosion test of magnesium-calcium alloys prepared with various compositions. In FIG. 14, Cast is a cast specimen, Extruded is an extruded specimen, H is impurity Fe is 0.04%, Ni is 0.001%, M is impurity Fe is 0.07%, Ni is 0.0005%, L is impurity It means a material in which Fe is 0.001% and Ni is 0.0035%. As magnesium content increases, the corrosion rate of magnesium alloy increases, and in pure Mg, the concentration of impurity Fe is an important factor that determines the corrosion rate. As the amount of Fe increases, the corrosion rate also increases. In addition, it can be seen that the corrosion rate is greatly reduced by miniaturization and homogenization of the microstructure by extrusion. Therefore, it can be seen that the desired corrosion rate can be obtained by adjusting the processing, impurity concentration, and the amount of Ca as an additive element due to extrusion. For reference, the corrosion rates of AZ91 (Mg-9% Al-1% Zn) alloy castings and extruded materials developed and sold as corrosion resistant high strength materials are presented as comparative data. By impurity control, additive element control, and secondary processing (extrusion, etc.), it can be seen that a corrosion rate close to AZ91, which is a material excellent in corrosion resistance among known Mg alloys, can be obtained.

15 is a diagram showing the corrosion rate and strength of the Mg alloy at the same time. 13, the corrosion rate and the compressive strength can be controlled by secondary processing such as the concentration of impurities, the amount of Ca added to the Mg, and the extrusion, and the material can be selected according to the required characteristics according to the type of disposable products to be applied.

Examples 6 and 7: Preparation of porous structures filled with biodegradable magnesium alloys

<Example 6>

200 ml of ethanol as a solvent, 6 g of polyvinyl butyral-co-vinyl alcohol-co-vinyl acetate (PVB) as a binder, 99.8% 6 ml of triethyl phosphate as a dispersant, and alumina as a biocompatible ceramic Mix 50g and mix for 2 hours using a stirrer. After filling the solution and the zirconia ball and performing ball milling for about 24 hours, the polyurethane cut into the appropriate size and shape is immersed in the solution, taken out, and rotated at room temperature to prevent pores from being blocked by the solution. The next step is to dry in the air for about 5 minutes so that the highly concentrated alumina is buried in the polyurethane foam (foam) member. The process of immersion and drying in the solution as described above is repeated to form a 50-1000 ㎛ thick alumina mixture film in the skeleton structure of the polyurethane. In the next step, the dried foam material is dried in an oven at 60 ° C. for about 10 minutes and subjected to heat treatment. The heat treatment conditions were maintained for 3 hours after reaching 800 ° C (polyurethane vaporization) at a temperature increase of about 5 ° C per minute (polyurethane vaporization), and reaching for 1000 to 1500 ° C (sintering temperature depending on the powder) after reaching the same temperature rising condition.

16 is an external appearance of the alumina porous structure having a diameter of 3 cm and a height of 4 cm prepared as described above.

The alumina porous structure prepared by the above method was impregnated with magnesium in the following manner. First, 1 kg of magnesium (manufacturer: Timminco Metals, trade name: PURCH Mangnesium ASTM 99.98% INGOT) was charged into a resistance furnace installed in the vacuum chamber. A metal mold having a 3 cm diameter passage was installed below the furnace, and the prepared alumina porous structure was placed in an internal passage. After forming a vacuum atmosphere in the vacuum chamber to 10-4 torr or less, high purity argon of 99.99% or more was injected. In a high-purity argon atmosphere, the magnesium melt is heated to 700 ° C., the metal mold is heated to 500 ° C., and a stopper installed in the furnace is removed to remove molten magnesium into the alumina porous structure located in the metal mold. Alumina filled with pores with magnesium was prepared by flowing.

Fig. 17 shows the appearance of magnesium-filled alumina prepared by the above method. In addition, FIG. 18 shows an enlarged photograph of a cross section of magnesium-filled alumina. The gray impregnated magnesium metal, with the relatively dark gray portion representing the alumina porous structure.

Example 7

Ti-spherical powder with a diameter of 100-200㎛ is placed between the conductive electrodes, and then discharged by instantaneously discharging the voltage charged in the 450 ㎌ capacitor under the conditions of 1.0kJ and 1.5kJ using a high vacuum switch. A Ti porous structure manufactured by a rotating electrode method for sintering within a short time by controlling the voltage and current passed therein was used. A copper electrode rod was mounted below the quartz tube with an internal diameter of 4.0 mm, 0.7 g of the selected titanium powder was injected, and the powder and the powder were well packed using a vibrator. After applying a load of 10kg by the automatic loading device was connected to the upper powder, low vacuum discharge was carried out while maintaining a vacuum of about 2x10-3 torr in the chamber where the discharge is made. The voltage and current passed through the powder during discharge were measured in real time using a high voltage probe and a high current probe to control the structure of the porous body.

19 is an external view of a porous structure used for preparing a Ti structure filled with Mg metal.

In order to impregnate the pores of the Ti porous structure, the following process was performed. Magnesium (manufactured by Timminco Metals, trade name: PURCH Mangnesium ASTM 99.98% INGOT) was charged to a crucible with an internal diameter of 50 mm made of stainless steel (SUS 410). Subsequently, argon (Ar) gas was flowed around the crucible so that magnesium in the crucible did not come into contact with air, and the crucible temperature was raised from about 700 ° C. to 750 ° C. using a resistance furnace to melt magnesium. The crucible was shaken and stirred so that the molten magnesium could be mixed well with each other. After immersing the porous structure preheated to about 200 ℃ in the molten magnesium to maintain the immersion state for about 5 minutes, the crucible was taken out and cooled by water.

20 is a cross-sectional view taken after the specimen containing the porous structure is removed from the fully cooled crucible to deliver and polish the site where the porous structure is located. The dark gray part is titanium of the porous structure, and the relatively light gray part is magnesium with pores. As shown in FIG. 20, it can be seen that a structure filled with pores with magnesium can be easily manufactured by a method of immersing a porous structure in a molten magnesium alloy.

Test Example 2 Strength Measurement Experiment of Alumina Structure Impregnated with Mg Alloy

In order to evaluate the change in strength of the magnesium-filled structure of Example 6 according to the present invention, after compressing the surface of the magnesium-filled alumina material prepared in Example 6 with emery paper for 1000 times, a compression / tension tester Located in the bottom plate. Next, a tip having a diameter of 3 mm and a tip inclination of 45 degrees was attached to the moving head of the tensile / compression tester, and then lowered at a rate of 1 mm / minute to press the surface of the specimen. At this time, the movement distance of the tip was limited to a maximum of 2 mm.

Figure 21 is a schematic view of the scene and the tip of pressing the alumina foam surface prepared in the present invention with the tip for compression test described above.

FIG. 22 is a graph illustrating a result of measuring compressive strength of an alumina porous structure not filled with a magnesium-based alloy by the above method. A force of up to 2.2 N was applied to the test specimen, and the strength of the specimen changed irregularly as the porous structure was broken when the compression test tip was advanced.

FIG. 23 is a graph showing the results of measuring compressive strength of an alumina structure filled with a magnesium-based alloy. FIG. As the compression test tip penetrated deeply into the test specimen surface, the force applied to the test specimen increased to 1500N. This is about 680 times higher than the strength of the alumina foam material that does not fill pores with magnesium-based alloy.

Example 8, Example 9, and Comparative Example 1: The total impurity containing manganese (Mn), iron (Fe), and nickel (Ni) is greater than 0 and 1 part by weight or less, based on 100 parts by weight of magnesium, and {iron ( Preparation of Biodegradable Magnesium Alloys with Fe) + Nickel (Ni) / Manganese (Mn)> 0 and Below 5

Iron, nickel, aluminum, manganese and magnesium in the amounts shown in Table 5 were charged to a crucible having an internal diameter of 50 mm made of stainless steel (SUS 410). Subsequently, argon gas was flowed around the crucible so that iron, nickel, manganese, aluminum and magnesium in the crucible did not come into contact with the air, and the crucible temperature was raised using a resistance furnace to about 700 to 750 ° C. , Aluminum, manganese and magnesium were melted. The crucible was shaken and stirred so that the molten iron, nickel, aluminum, manganese and magnesium could be mixed well with each other. The molten magnesium alloy was cooled to prepare a magnesium alloy in the solid state. In addition, when cooling, the crucible was immersed in water for the purpose of improving the mechanical strength of magnesium, so that the molten magnesium alloy was rapidly cooled.

The solid magnesium alloy was extruded, the extrusion temperature was 400 ° C., and the ratio of cross-sectional area reduction (extrusion ratio) before and after extrusion was fixed at 15: 1.

Fe (part by weight) Ni (parts by weight) Al (part by weight) Mn (parts by weight) Mg (parts by weight) (Fe + Ni) / Mn Example 8 0.0014 0.0002 0.0021 0.0015 100 2.26 Example 9 0.0092 0.0027 0.0043 0.0380 100 0.313 Comparative Example 1 0.0214 0.0027 0.0053 0.0036 100 6.69

Test Example 3 Evaluation of Corrosion Rate of Biodegradable Magnesium

The biodegradable magnesium alloys of Example 8, Example 9 and Comparative Example 1 were immersed in the solution having the composition of Table 6, and the corrosion rate was evaluated by the amount of hydrogen generated according to the immersion time, and the results are shown in FIG. 24.

Molarity [mM / L] Mass [g] CaCl ₂ 2H ₂ O 1.26 0.185 KCl 5.37 0.400 KH ₂ PO ₄ 0.44 0.060 MgSO ₄ 7H ₂ O 0.81 0.200 NaCl 136.89 8.000 Na ₂ HPO ₄ 2H ₂ O 0.34 0.060 NaHCO ₃ 4.17 0.350 D-Glucose 5.55 1,000

Referring to FIG. 24, in Example 8, hydrogen is generated after 50 hours have elapsed, and in Example 9, hydrogen is hardly generated from the beginning of immersion until 200 hours, and corrosion of the biodegradable magnesium alloy is prevented. It can be seen that rarely occurs. On the other hand, in Comparative Example 1 it can be seen that hydrogen is generated from the initial immersion. According to these results, it can be seen that Examples 1 and 2 in which {iron (Fe) + nickel (Ni)} / manganese (Mn) are greater than 0 and 5 or less have the lowest decomposition rate of the biodegradable magnesium alloy.

Examples 10 to 18 and Comparative Examples 2 to 5: Preparation of Biodegradable Magnesium Alloys

Magnesium, calcium, manganese and zinc in the contents shown in Table 7 were charged to a crucible having an internal diameter of 50 mm made of stainless steel (SUS 410). Subsequently, argon gas was flowed around the crucible so that magnesium, calcium, manganese and zinc in the crucible did not come into contact with the air, and the crucible temperature was raised from about 700 ° C to 750 ° C using a resistance heating furnace. Was melted. The crucible was shaken and stirred so that the molten magnesium, calcium and manganese could be well mixed with each other. The molten magnesium alloy was cooled to prepare a magnesium alloy in the solid state. In addition, when cooling, the crucible was immersed in water for the purpose of improving the mechanical strength of magnesium, so that the molten magnesium alloy was rapidly cooled.

The solid magnesium alloy was extruded, the extrusion temperature was 400 ° C., and the ratio of cross-sectional area reduction (extrusion ratio) before and after extrusion was fixed at 15: 1.

Mg (% by weight) Ca (% by weight) Mn (% by weight) Zn (% by weight) Example 10 89 10 One - Example 11 88.98 9.99 - 1.03 Example 12 86.29 10.8 - 2.91 Example 13 84.42 10.7 - 4.88 Example 14 94.88 4.62 - 0.50 Example 15 94.52 4.72 - 0.76 Example 16 93.86 4.51 - 1.63 Example 17 92.44 4.56 - 3.00 Example 18 91.23 4.65 - 4.12 Comparative Example 2 95 5 - - Comparative Example 3 89.9 10.1 - - Comparative Example 4 A maker: Timinco company, purity 99.98% Mg Comparative Example 5 AZ91: Al: 8.5-9.5%, Zn: 0.45-9%, Mg

Test Example 3 Evaluation of Mechanical Strength of Biodegradable Magnesium Alloy

The mechanical strength evaluation result of the biodegradable magnesium alloy before extrusion is shown in FIG. 25, and the mechanical strength evaluation result of the biodegradable magnesium alloy after extrusion is shown in FIG.

25 and 26, it can be seen that Example 11 fell slightly from 220 MPa to 180 MPa in comparison with Comparative Example 3, and slightly dropped from 320 MPa to 280 MPa after extrusion. However, since 280 MPa is a value that is sufficiently applicable to a disposable product under load, there is no problem in applying the product at all. In addition, after extrusion, the elongation was increased from 12% to 16%, which means that the biodegradable magnesium alloy has excellent performance when subjected to strong impact from the outside.

In addition, in Example 10, the strength dropped from 220 MPa to 170 MPa, but was maintained at 320 MPa equivalent to Comparative Example 2 after extrusion. The elongation was also increased from 12% before extrusion to 17% after extrusion, maintaining mechanical equivalent or more than Comparative Example 3.

Test Example 4: Evaluation of Corrosion Rate of Biodegradable Magnesium Alloy

In general, the corrosion rate of biodegradable magnesium alloy is measured by the amount of hydrogen generated in the biological mother liquor. This is because hydrogen is generated when magnesium biodegrades.

The biodegradable magnesium alloys of Examples 10 to 18 and Comparative Examples 2 to 6 were immersed in the solution having the composition of Table 8, and the corrosion rate was evaluated by the amount of hydrogen generated according to the immersion time.

FIG. 27 shows the results of hydrogen generation according to the bedtimes of Examples 10, 11 and Comparative Example 3. FIG. 28 shows the results of hydrogen generation according to the bedtimes of Examples 11-13. FIG. 29 shows the results of hydrogen generation according to the needle times of Examples 14 to 18, Comparative Example 3, and Comparative Example 5. FIG. 30 shows the results of hydrogen generation according to the zinc content.

Molarity [mM / L] Mass [g] CaCl ₂ 2H ₂ O 1.26 0.185 KCl 5.37 0.400 KH ₂ PO ₄ 0.44 0.060 MgSO ₄ 7H ₂ O 0.81 0.200 NaCl 136.89 8.000 Na ₂ HPO ₄ 2H ₂ O 0.34 0.060 NaHCO ₃ 4.17 0.350 D-Glucose 5.55 1,000

Referring to FIG. 27, it can be seen that in Comparative Example 3, rapid decomposition starts after 5 hours, but in Example 10, rapid decomposition starts after 17 hours. In addition, in Example 10, even after 30 days of immersion, there was no sudden corrosion phenomenon. Therefore, it can be seen that the biodegradable magnesium alloy according to the present invention is excellent in corrosion resistance compared to Comparative Example 3.

28 and 29, the corrosion rate according to the Zn content can be seen, it can be seen that the corrosion rate increases as the zinc content increases.

Referring to FIG. 30, the corrosion rate according to the Zn content at the hydrogen generation amount of 0.5 ml / cm 2 was shown. In view of the corrosion rate, the optimum composition of the alloy is 0.1 to 5%, but preferably 0.1 to 3%. The reason is that the same section of corrosion rate exists, but considering the Zn side effects that may be unknown to the human body, the content of Zn should be small under the assumption that the same corrosion rate is achieved.

31 is an electron micrograph showing the surface of the biodegradable magnesium alloy specimen of Example 14 left in the solution of Table 8 for 61 hours, Figure 32 is an EDS of the biodegradable magnesium alloy specimen of Example 14 shown in FIG. The surface photograph analyzed. FIG. 33 is a photograph of a corrosive substance removed from the biodegradable magnesium alloy specimen of Example 14 illustrated in FIG. 31.

Referring to FIGS. 31 and 32, it can be seen that a corrosive material is formed on the surface. Analysis of the corrosive results of the components are shown in Table 9.

Component Mass (%) Atom (%) 0 33.076 52.0767 Mg 5.580 5.7816 P 19.398 15.7781 Ca 41.946 26.3635 Sum 100.000 100.0000

Referring to Table 9, oxygen was measured as a component of the corrosive, indicating that the biodegradable magnesium alloy specimen of Example 14 was oxidized, and it can be expected that phosphorus and calcium may be derived from the solution of Table 8.

FIG. 33 is a photograph showing that the corrosives shown in FIGS. 31 and 32 are removed. Table 10 shows the results of analyzing the biodegradable magnesium alloy specimen of Example 14 from which the corrosives were removed.

Component Mass (%) Atom (%) 0 7.749 11.4133 Mg 90.178 87.4252 P 0.521 0.3968 Ca 0.903 0.5305 Zn 0.649 0.2342 Sum 100.000 100.0000

Referring to Table 10, it can be seen that phosphorus and calcium remain after the corrosive is removed. This can be seen that the phosphorus and calcium derived from the solution of Table 8 is not easily removed.

34 is a cross-sectional view of the biodegradable magnesium alloy specimen of Example 14 left in the solution of Table 8 for 61 hours, FIG. 35 is an enlarged view of the photograph of FIG. 34, and FIG. 36 is left in Table 9 for 61 hours. The biodegradable magnesium alloy specimen of Example 14 was taken with a WDS (manufacturer: JEOL, product name: JXA-8500F).

34 to 36, it can be seen that a light line between magnesium is Mg 2 Ca, and a line like dark line is a corroded region. The black line slowly penetrates the magnesium, indicating that corrosion progresses.

FIG. 37 is a cross-sectional view of the biodegradable magnesium alloy specimen of Example 15 left in the solution of Table 8 for 61 hours.

38 is a photograph taken with WDS (manufacturer: JEOL, product name: JXA-8500F) of Example 15, which was left in Table 9 for 61 hours.

Referring to FIGS. 37 and 38, it can be seen that the compound of Mg-Ca-Zn surrounds Mg 2 Ca (Zn), and when zinc content is increased, zinc is further contained in Mg 2 Ca.

Test Example 5: Evaluation of Corrosion Rate of Biodegradable Magnesium Alloy

The yield strength, fracture strength and elongation of the biodegradable magnesium alloy specimens of Examples 14 to 18 and Comparative Example 2 were measured and shown in Table 11.

Yield strength / breaking strength Elongation (%) Example 14 84 ± 3/180 ± 10 11.8 ± 0.4 Example 15 2107 ± / 240 ± 5 13.9 ± 1.5 Example 16 97 ± 2/203 ± 10 9.5 ± 1 Example 17 103 ± 2/255 ± 14 12.2 ± 0.6 Example 18 109 ± 2/247 ± 11 14.6 ± 2 Comparative Example 2 87 ± 3/180 ± 10 10.5 ± 0.3

Test Example 6 Evaluation of Corrosion Rate When Ultrasonic Application to Biodegradable Magnesium Alloy

The biodegradable magnesium alloy specimens of Example 15 were cut into 9.65 cm in width, 19.66 cm in length, and 1.18 cm in thickness to prepare two specimens. After applying ultrasonic waves to the two specimens, it was immersed in the solution of Table 8 for 3 hours and the hydrogen generation amount was measured and shown in FIGS. 39 and 40.

39 and 40, it can be seen that the specimen to which ultrasonic waves are applied has a large amount of hydrogen generation and corrosion occurs more quickly.

Test Example 7: Characterization of surface when biodegradable magnesium alloy

Short peening was performed on the MgCa (Mg 95 wt%, Ca 5 wt%) alloy, and the results are shown in FIG. 41.

In FIG. 41, the MgCa alloy at the top is before the surface treatment, and the MgCa alloy at the bottom is after the surface treatment. Referring to FIG. 42, it can be seen that the MgCa alloy was glossy before the surface treatment, but disappeared after the surface treatment.

1 is a cross-sectional photograph of pure Mg (Fe 0.001-0.04%, Ni 0.0035-0.001%) casting material.

Figure 2 is a photograph of the appearance of the cast material produced in Example 2-5.

3 is a cross-sectional photograph of a cast material prepared in Example 2-1 (Mg _0.992 Ca _0.008 ).

Figure 4 is a cross-sectional photograph of the cast material prepared in Example 2-2 (Mg _0.95 Ca _0.05 ).

5 is a cross-sectional photograph of a cast material prepared in Example 2-3 (Mg _0.895 Ca _0.105 ).

6 is a cross-sectional photograph of a cast material prepared in Example 2-4 (Mg _0.77 Ca _0.23 ).

7 is a cross-sectional photograph of a cast material prepared in Example 2-5 (Mg _0.67 Ca _0.33 ).

Figure 8 is a cross-sectional photograph of the alloy prepared in Example 3 (Mg _0.67 Ca0 _.33).

9 is a cross-sectional photograph in the longitudinal and horizontal directions of Example 4-3 (extruded Mg _0.95 Ca _0.05 ).

FIG. 10 shows the biological material (Ti alloy) on which the coating film is formed by the method described above, and cuts the coating cross-section to reveal the coating cross section, and then observes the result by electron microscope.

FIG. 11 is a photograph of a magnesium alloy coating layer formed by Example 5 on a Ti 6 V 4 Al alloy with a diamond tip, and then observed with an electron microscope. FIG.

12 is a compressive strength test results of the Mg alloy cast material produced by varying the amount of Ca added.

13 is a compressive strength measured after extruding the Mg alloy cast material produced by varying the amount of Ca added.

14 is a measurement result of the corrosion current density change of the Mg material according to the impurity content, Ca addition amount, extrusion processing.

15 is a diagram showing the corrosion current density change and the yield strength of the Mg material according to the impurity content, Ca addition amount, extrusion or not.

16 is an external photograph of an alumina structure in which pores are impregnated with Mg.

17 is a cross-sectional photograph of an alumina structure filled with pores with Mg.

18 is an external photograph of a Ti porous structure prepared by sintering Ti powder.

19 is a cross-sectional photograph of a Ti porous structure filled with pores with Mg.

20 is a shape of an experimental scene and a tip used to investigate the surface strength of the porous structure and the porous structure filled with pores with Mg.

21 is a graph showing the change of the surface penetration depth of the alumina porous structure according to the added load.

22 is a graph showing the change of the surface penetration depth of the alumina structure filled with pores with Mg according to the added load.

FIG. 23 is a graph showing the results of measuring compressive strength of an alumina structure filled with a magnesium-based alloy. FIG.

24 is a graph showing the hydrogen generation amount according to the immersion time of Example 10, Example 11 and Comparative Example 1.

25 is a graph showing the results of mechanical strength evaluation of the biodegradable structures of Example 12, Example 13 and Comparative Example 3 before extrusion.

FIG. 26 is a graph showing the mechanical strength evaluation results of the biodegradable magnesium alloys of Example 12, Example 13, and Comparative Example 3 after extrusion.

27 is a graph showing the results of the hydrogen generation amount according to the needle time of Example 10, Example 11 and Comparative Example 3.

28 is a graph showing the results of hydrogen generation according to the bedtimes of Examples 11 to 13. FIG.

29 is a graph showing the results of the hydrogen generation amount according to the needle time of Examples 14 to 18, Comparative Example 3 and Comparative Example 5.

30 is a graph showing the results of hydrogen generation according to the zinc content.

31 is an electron micrograph showing the surface of the biodegradable magnesium alloy specimen of Example 14 left in the solution of Table 8 for 61 hours.

32 is a photograph of the surface of the biodegradable magnesium alloy specimen of Example 14 shown in FIG. 31 analyzed by EDS.

FIG. 33 is a photograph showing the removal of corrosive material from the biodegradable magnesium alloy specimen of Example 14 shown in FIGS. 31 and 32.

34 is a cross-sectional view of the biodegradable magnesium alloy specimen of Example 14 left in the solution of Table 8 for 61 hours.

35 is an enlarged photograph of the photo of FIG. 34.

36 is a photograph taken with the WDS (manufacturer: JEOL, product name: JXA-8500F) of the biodegradable magnesium alloy specimen of Example 14, which was left in the solution of Table 8 for 61 hours.

FIG. 37 is a cross-sectional view of the biodegradable magnesium alloy specimen of Example 15 left in the solution of Table 8 for 61 hours.

38 is a photograph taken with WDS (manufacturer: JEOL, product name: JXA-8500F) of Example 15 left in the solution of Table 8 for 61 hours.

FIG. 39 is a graph illustrating the generation of hydrogen over time by applying ultrasonic waves to one of two biodegradable magnesium alloy specimens of Example 15 and not applying the remaining ultrasonic waves, followed by immersion in the solution of Table 8.

FIG. 40 is a graph illustrating the generation of hydrogen over time by immersing the biodegradable magnesium alloy specimen of Example 15 in which ultrasonic waves were applied to the solution of Table 8.

Fig. 41 is a photograph showing MgCa alloys before and after surface treatment.

Claims (13)

Disposable article comprising a biodegradable magnesium alloy. The method according to claim 1, The biodegradable magnesium alloy is a disposable product, characterized in that represented by the following formula (1): <Formula 1> Mg _a Ca _b X _c In Chemical Formula 1, a, b, and c are molar ratios of the components, a + b + c = 1, 0.5 ≦ a <1, 0 ≦ b ≦ 0.4, 0 ≦ c ≦ 0.4, provided that at least one of b and c is 0 And c is 0, the content of Ca is included in an amount of 5 to 33 wt% based on the total weight of the biodegradable magnesium alloy, X is zirconium (Zr), molybdenum (Mo), niobium (Nb), tantalum (Ta), titanium (Ti), It is at least one selected from strontium (Sr), chromium (Cr), manganese (Mn), zinc (Zn), silicon (Si), phosphorus (P), nickel (Ni) and iron (Fe). The method according to claim 1, The biodegradable magnesium alloy is magnesium (Mg); Manganese (Mn) as an impurity; Including iron (Fe), nickel (Ni) and one selected from the group consisting of a mixture of iron (Fe) and nickel (Ni), the impurity content is greater than 0 to 1 part by weight based on 100 parts by weight of the magnesium It is below, {one type chosen from the group which consists of a mixture of iron (Fe), nickel (Ni), iron (Fe), and nickel (Ni)} / manganese (Mn) = 1 more than 5, The disposable product characterized by the above-mentioned. The method according to claim 1, The biodegradable magnesium alloy is represented by the following formula (2), relative to the total weight, Ca is greater than 0 to 23% by weight; Y is greater than 0 and less than or equal to 10 weight percent; And Mg is a disposable product, characterized in that it comprises a residual amount: <Formula 2> Mg-Ca-Y In Formula 2, Y is Mn or Zn. The method according to claim 1, The biodegradable magnesium alloy is a disposable product, characterized in that filled in the pores of the porous structure. The method according to claim 1, The disposable article is a disposable article, characterized in that it comprises a biodegradable resin. The method according to claim 1, The biodegradable resin is polylactic acid, polyglycolic acid, polycaprolactone, polybutylene succinate, polybutylene succinate o adipate copolymer, polyethylene succinate, polybutylene Adipate o terephthalate copolymer, polyethylene terephthalate o adipate copolymer, polyvinyl alcohol, polyurethane, polyester amide, polyaspartic acid, polyhydroxy butyrate, polyhydroxy butyrate oburate copolymer , Polyhydroxy valeric acid (polyhydroxy valeric acid), starch (starch), chitin, chitosan, cellulose acetate and acetyl cellulose disposable products, characterized in that one or two or more selected from the group consisting of. The method according to claim 1, The disposable product is a disposable product, characterized in that the disposable container or disposable cutlery. A packaging material comprising a biodegradable magnesium alloy. The method according to claim 9, The biodegradable magnesium alloy is a packaging material characterized in that represented by the following formula (1): <Formula 1> Mg _a Ca _b Xc In Chemical Formula 1, a, b, and c are molar ratios of the components, a + b + c = 1, 0.5 ≦ a <1, 0 ≦ b ≦ 0.4, 0 ≦ c ≦ 0.4, provided that at least one of b and c is 0 And c is 0, the content of Ca is included in an amount of 5 to 33 wt% based on the total weight of the biodegradable magnesium alloy, X is zirconium (Zr), molybdenum (Mo), niobium (Nb), tantalum (Ta), titanium (Ti), It is at least one selected from strontium (Sr), chromium (Cr), manganese (Mn), zinc (Zn), silicon (Si), phosphorus (P), nickel (Ni) and iron (Fe). The method according to claim 9, The biodegradable magnesium alloy is magnesium (Mg); Manganese (Mn) as an impurity; Including iron (Fe), nickel (Ni) and one selected from the group consisting of a mixture of iron (Fe) and nickel (Ni), the impurity content is greater than 0 to 1 part by weight based on 100 parts by weight of the magnesium The packaging material characterized by the following being {1 type chosen from the group which consists of a mixture of iron (Fe), nickel (Ni), iron (Fe), and nickel (Ni)} / manganese (Mn) = more than 5 or less. The method according to claim 9, The biodegradable magnesium alloy is represented by the following formula (2), with respect to the total weight, Ca is more than 0 to 23% by weight; Y is greater than 0 and less than or equal to 10 weight percent; And Mg comprises a residual amount: <Formula 2> Mg-Ca-Y In Formula 2, Y is Mn or Zn. The method according to claim 9, The biodegradable magnesium alloy is packed in the pores of the porous structure.

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