KR20010038235A - The composite of magnesium-intermetallic compound intermixed with magnesium chloride, and process for preparing it - Google Patents

Abstract

PURPOSE: Provided is a mixture of a magnesium intermetallic compound and a magnesium chloride, which can be used as an energy source generating heat and hydrogen by reacting the mixture and an electrolyte water solution. CONSTITUTION: The mixture of the magnesium intermetallic compound and the magnesium chloride is produced by melt-reacting magnesium particles, metal chloride such as iron chloride, nickel chloride, copper chloride, or a mixture thereof, the metal powder of the metal chloride, and a pore forming agent/reductant such as a polymer of carbon and hydrocarbon, or PVA at 600-800 deg.C for 10-40 minutes under helium or argon, wherein the magnesium particles and the metal chloride are mixed in the weight ratio of 1:0.3-1:1.

Description

A mixture of a magnesium-based intermetallic compound and magnesium chloride, and a method for producing the same, and a method for preparing the same.

The present invention relates to a magnesium-based intermetallic compound and a magnesium chloride mixture. More specifically, magnesium-based intermetallic compounds such as magnesium-nickel, magnesium-iron, and magnesium-copper obtained by melt reaction of magnesium at a high temperature with nickel chloride, iron chloride or copper chloride, etc. ("magnesium-metal alloy" or " Magnesium-metal alloy) and a method for producing the same.

The present invention utilizes the properties of magnesium, and when contacted with water in the ambient air atmosphere, it rapidly reacts with corrosion, and as shown in the following thermodynamic equation, a magnesium-based intermetallic having a characteristic of generating a large amount of heat and hydrogen within a certain time The purpose of the preparation of the compound is to use it as an energy source.

Mg → Mg ⁺² + 2e ^- E ⁰ = -2.37

^{_{2H 2 O → 2OH - + 2H}} +

_{^{2H + + 2e - → H 2}} E 0 = 0

Mg + 2H ₂ O → Mg (OH) ₂ + H ₂

ΔH = nFE = 2 × 96,500 × (-2.37) = -457,410 J = -109,778 cal

These magnesium-based intermetallic compounds can be used to protect the body temperature of deep-sea divers, to heat emergency foods in combat, to fuel fueled thermal power engines, or as a source of thermal energy in the winter. The hydrogen-generating or rapid corrosion characteristics of the magnesium-based intermetallic compound can be applied.

In general, pure magnesium is a very active metal and is known as a violent oxidation reaction in the atmosphere. However, when magnesium is in contact with moisture in the air, a stable protective film of magnesium hydroxide is formed on the contact surface between magnesium and moisture, so that it is generally known that no further reaction proceeds at room temperature. Pure magnesium is also highly corrosion resistant because of its very low galvanic activity.

However, when magnesium is contaminated with metals such as iron, nickel, copper, or other impurities such as chloride, nitride, or oxide, it is found that the contact with the aqueous chloride solution rapidly increases the dielectric activity and accelerates corrosion.

Conventionally, by using the corrosion properties of the magnesium to quickly corrode magnesium within a certain time to use the corrosion properties themselves, or look at the prior art for using the corrosion reaction heat and hydrogen can be roughly divided into two.

One of them is to make magnesium in the form of a plate to make a positive electrode, and heavy metals such as copper, iron, or nickel to form a plate of negative electrode, and act by adding an electrolyte. It is a prior art in the form of a battery (gavanic cell) that looks like a battery that reacts electrochemically in aqueous chloride solution. However, this technique has problems in the expansion of the surface area of the plate-shaped bipolars, the control or fixation of the bipolar gaps, the treatment of magnesium hydroxide and hydrogen, reaction products that act as reaction inhibitors, and the formation of two metals to produce an efficient electrochemical reaction. Since the plate-like shape must be manufactured, it is difficult to change the shape of the plate into various shapes for various uses.

Another technique is to homogeneously mix a certain proportion of magnesium and a certain proportion of heavy metal (especially iron) powders, thereby making the two powders adhere to, adhere, bond, or bond between the powders by various means, and then By electrochemically reacting in an aqueous solution, each of the powder-to-powder binders takes the form of a very small dielectric paper. Such techniques are disclosed in detail in US Pat. Nos. 3942511, 4017414, 4264362 and the like.

According to these patents, a homogeneous mixture of the two powders and a special ball mill with a specially heavy ball mill are used to make the two powders homogeneously mixed in the process of mixing and compressing and grinding the ball mill. At the same time, the powders are bonded or homogeneously mixed, and the two powders are press-bonded, bonded by a binder, or subjected to a post-treatment process such as high temperature sintering to ensure reliable powder-to-powder bonding. However, in order for each magnesium particle-particle to be the most efficient ultra-small dielectric paper, magnesium particles and iron or nickel powders must be homogeneously mixed in a specific ratio to bond between the powders. Although it can be said that homogeneous mixing is performed on an arithmetic average as a whole due to the mixing characteristics of the inner compound, in terms of individual particles of magnesium, the two powders are ideally mixed at a specific binding ratio, so that the inter-powder bonding can be simulated. May be composed of a ratio different from the desired ratio, that is, more than the ratio, less than or not bound at all. Therefore, only particles in which magnesium and iron powder form a powder-to-powder binder at a specific ratio are very inefficient because they act as dielectric papers with the highest efficiency.

In addition, even if the powder particles of magnesium and heavy metal each form an ideal powder-to-particle bond, it is merely a contact bonding between the particles and the particles. Since the electrochemical reaction occurs only at the surface of the particles, the reaction does not reach the inside of the particles. The disadvantage is that many remain unreacted.

The present inventors earnestly studied to solve the above problems, unlike the prior art, it is possible to obtain a magnesium-based intermetallic compound by reacting magnesium and metal chloride (hereinafter, also referred to as a pair compound of magnesium) at high temperature The present invention was completed.

That is, an object of the present invention is to provide a magnesium-based intermetallic compound prepared by mixing a metal chloride such as magnesium and iron, followed by high temperature melting reaction, and a method for producing the same.

Another object of the present invention is to provide a magnesium-based intermetallic compound prepared by mixing a small amount of metal chloride and a small amount of metal in magnesium, and then hot-melting the same.

Another object of the present invention is to provide a mixture of magnesium-based intermetallic alloy and magnesium chloride and a method for producing the same by hot-melting magnesium and metal chloride, or magnesium, metal chloride and metal at high temperature.

It is still another object of the present invention to provide a porous magnesium-based intermetallic compound and a method for producing the same by hot-melt-reacting magnesium, a metal chloride, and a metal compound together with a reducing agent / pore forming agent.

The production method of the present invention is to provide a production method characterized in that carried out in an inert gas atmosphere.

Hereinafter, the present invention will be described in detail.

FIG. 1 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to the mixing ratio of magnesium and ferric chloride in Example 1 over time.

FIG. 2 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium over time according to the amount of ferric chloride added when 0.3 g of iron powder is added in Example 2. FIG.

FIG. 3 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to iron content when 0.3 g of ferric chloride is added in Example 3. FIG.

FIG. 4 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to the blending ratio of PVA as a pore-forming agent in Example 4.

FIG. 5 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to the melting reaction temperature over time in Example 5. FIG.

FIG. 6 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to melting reaction time at 680 ° C. in Example 6. FIG.

FIG. 7 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium with melting reaction time at 700 ° C. in Example 7. FIG.

FIG. 8 is a graph showing the amount of hydrogen generating corrosion tendency of magnesium according to the HDPE content of the binder in Example 8 over time.

FIG. 9 is a graph showing the amount of hydrogen generating a corrosion tendency of magnesium according to a change in the sintering temperature of HDPE as a binder in Example 9. FIG.

Magnesium-based intermetallic compound prepared by the method of the present invention was prepared by melting, substitution, bonding reaction at a high temperature (640 ~ 800 ℃) due to the nature of the manufacturing method, it is prepared by physically bonding particles and particles in the prior art Magnesium-metal binders are completely different in their composition, bonding strength, and bond density.

As magnesium used in this reaction, 30-120 mesh powder was used. It is also possible to use large powders of 30 mesh or more, but this is not preferred because of poor reactivity. In addition, the use of fine powders of 120 mesh or less is preferable in terms of reactivity, but there is a concern that the stable protective surface already generated during storage and transportation may be problematic because of the relatively large size, and additional cost may be required due to additional milling. There is a disadvantage that increases. Commercially available anhydrous ferric chloride, ferric chloride, nickel chloride, copper chloride, and the like are preferred as metal chlorides which react with magnesium powder. Although nickel chloride and copper chloride are used, magnesium-based intermetallic compounds having an effect equivalent to that of iron chloride can be obtained, but iron chloride is most preferred in consideration of cost and the like.

As a result of the reaction between magnesium particles and the metal chloride, the reactivity of the magnesium-based intermetallic compound in the form of alloy obtained by the reaction in the weight ratio in the range of 1: 0.67 to 1: 1.35 was fast. Was fast. However, it is advantageous to generate as little as possible because a large amount of chlorine gas is generated in the reaction for producing a product in this alloy form. For this purpose, if the amount of metal chloride is reduced to about 1/10, and the metal powder is added to the metal chloride in an amount of about 0.2 to 2 times (weight ratio) to the amount and reacted in an inert gas atmosphere, The emission of the gas is considerably lowered, and the activity of the magnesium-based intermetallic compound is greatly improved.

First, the reaction conditions of this invention are demonstrated.

In the present invention, the entire process is performed in an inert gas, such as argon or helium, from the initial compounding process to the melting reaction and the crushing of the reaction product, the compounding with the binder, and the sintering and packaging.

In the present invention, the melting reaction temperature of the magnesium particles and the metal chloride is 640 ° C. or more and less than 800 ° C., preferably 680-720 ° C. If the reaction temperature exceeds 800 ℃, an uncontrolled reaction occurs, the effect of the desired product can not be obtained. Uneconomical

In the present invention, the melting reaction of the magnesium particles and the metal and metal chloride is carried out in an inert gas atmosphere. At this time, argon is particularly preferable as the inert gas. When reacted in air, the magnesium reacts with moisture and oxygen in the air to form magnesium hydroxide and magnesium oxide before reacting with the metal chloride, thereby reducing the efficiency of manufacturing the desired magnesium-based intermetallic compound.

Magnesium particles are often exposed to air or moisture during production, packaging, transportation, and sale to react with oxygen, moisture, and moisture in the air to form magnesium oxide or magnesium hydroxide film on the surface of magnesium particles. Magnesium oxide or magnesium having a magnesium hydroxide film is very stable and does not react with metal chlorides in the reaction temperature range. In the above-mentioned US patent, it is necessary to pay attention to the fact that the magnesium particles formed with such a protective film cannot be used as they are, so that they are ground with a special ball mill and physically combined with magnesium and iron powder in the original particles where the film is not formed. However, in the present invention, the magnesium particles having such a coating are used as they are, and a reducing agent (sometimes referred to herein as a "pore forming agent") having a reducing action and a pore-forming action is added thereto to provide high temperature in a metal chloride and argon atmosphere. When the melt reaction is carried out, the magnesium particles in which the coating is formed are reduced to bind and react with the metal chloride to obtain an magnesium-based intermetallic compound in the form of an alloy. Although it does not restrict | limit especially as a reducing agent which can be used in this reaction, A polymer like carbon, PVA, etc. are especially preferable. These reducing agents act as reducing agents during the reaction and are also removed with carbon dioxide at high temperatures. By this action, many pores are formed in the magnesium-based intermetallic compound, thereby easily reacting with magnesium in the electrolyte solution in the final product to generate hydrogen and at the same time, effectively exothermic reaction at high temperature. Such reducing agent / pore-forming agent is preferably used in an amount of 15 to 50% by weight based on the amount of magnesium.

In the present invention, by using the pure heavy metal chloride powder together to act as a binding medium between the magnesium acting as a positive electrode (+) and the heavy metal acting as a negative electrode (-).

The magnesium chloride produced together with the produced intermetallic compound acts as an aqueous solution of the electrolyte by interacting with water, and at the same time, causes a hydration reaction to instantly increase the initial reaction temperature so that the intermetallic compound works most efficiently with the electrolyte. That is, the magnesium-based intermetallic compound generally reacts faster as the temperature of the electrolyte solution in contact is higher. Therefore, if the compound contains an electrolyte such as magnesium chloride, the magnesium chloride will hydrate upon contact with water to form a hexahydrate thereof. At this time, heat of hydration is generated to accelerate the initial reaction between the magnesium-based intermetallic compound and the electrolyte solution. Exothermic reaction.

In the magnesium-based intermetallic compound obtained by the method of the present invention, the bonding between magnesium and metal is somewhat uniform, but it cannot be concluded that a perfect homogeneous bonding is theoretically achieved. That is, in the present invention, the reaction of magnesium and metal chloride powders in the molten state does not occur stoichiometrically, such as a liquid phase reaction or a gas phase reaction, and the reaction starts at the melt surface of the powders and gradually proceeds to the inside of the melt. . Furthermore, in the reaction of the present invention, when a reducing agent such as carbon or PVA is used, it reacts with magnesium oxide or magnesium coated with magnesium hydroxide to remove oxygen or hydroxyl groups to form metal magnesium, and the metal magnesium It is easily welded and combined with heavy metals.

In addition, in the case of using a metal chloride corresponding to the metal chloride, it is preferable that the size of the corresponding metal is about 80 to 150 mesh. In addition, in the case of using such a metal, the amount of metal chloride and metal can be blended in a small amount relative to the amount of magnesium, and at this time, the chlorine gas generated from the metal chloride can be suppressed to the maximum, and the chlorine gas generated is It acts as a reducing agent and reacts with magnesium and heavy metals to produce metal chlorides. As shown in Example 2, it is confirmed that almost all magnesium in the magnesium-based intermetallic compound reacts efficiently because the degree of corrosion of the magnesium-based intermetallic compound with water increases to 90% or more with the addition of the metal powder. Can be.

The reaction according to the present invention is represented by the following scheme.

FeCl ₃ + Mg → (Fe-Mg) + MgCl ₂ + Cl ₂

FeCl ₂ + Mg → (Fe-Mg) + MgCl ₂ + Cl ₂

CuCl ₂ + Mg → (Cu-Mg) + MgCl ₂ + Cl ₂

NiCl ₂ + Mg → (Ni-Mg) + MgCl ₂ + Cl ₂

FeCl ₃ + Mg + Fe → (Fe-Mg) -Fe + MgCl ₂ + Cl ₂

FeCl ₂ + Mg + Fe → (Fe-Mg) -Fe + MgCl ₂ + Cl ₂

CuCl ₂ + Mg + Cu → (Cu-Mg) -Cu + MgCl ₂ + Cl ₂

NiCl ₂ + Mg + Ni → (Ni-Mg) -Ni + MgCl ₂ + Cl ₂

(Reaction coefficient cannot be determined because the reaction is heterogeneous reaction)

The magnesium-metal alloy obtained as described above is pulverized in an argon or helium atmosphere, and then mixed and stirred with additional electrolyte salts and binders such as high density polyethylene (HDPE), low density polyethylene, and various polymers, followed by sintering, for example , A molded article obtained by sintering at 145 to 180 ° C. may be put in a moisture proof pack, for example, an aluminum pack, a moisture proof coating sheet pack, or the like, and sealed to produce a molded article of an alloy of magnesium and metal.

In addition, since the molded product contains magnesium chloride during the reaction, the molded product functions as an electrolyte when reacted with water. However, the molded product may be prepared by further mixing an electrolyte salt such as magnesium chloride, calcium chloride or sodium chloride, if necessary. At this time, the amount of the electrolyte salt to be used is preferably blended so as to have a weight ratio of 2% to 40% with respect to the water added in use to make the aqueous electrolyte solution to prepare a molded article.

EXAMPLE

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited by these examples.

Example 1

3 g of magnesium and 1 g, 2 g, 3 g, and 4 g of well-dried ferric chloride particles (50 to 100 mesh) were combined in an argon atmosphere, and placed in a reactor, and placed in a reactor, at 30 to 720 ° C. under an argon air stream atmosphere. The reaction was carried out for a minute to obtain a mixture of an alloy of magnesium-iron and magnesium chloride. The produced magnesium-iron alloy was placed in a sealed container, and 20 ml of a 3% aqueous sodium chloride solution was added thereto to collect hydrogen generated, and the reaction of magnesium was measured as the amount of hydrogen generated. Since 22.4 liters of hydrogen is generated per 1 mol of magnesium, the theoretical value of the amount of hydrogen generated is about 3 liters at room temperature when water is reacted with a magnesium-iron alloy obtained using 3 g of magnesium.

In Table 1 below, the corrosion rate (reaction rate) of magnesium in the resulting alloy obtained according to the compounding ratio of magnesium and trivalent iron chloride was used over time using the amount of hydrogen (ml). In addition, this result is shown graphically in FIG.

Measurement time (minutes) Compounding ratio * (g) (3: 1) (3: 2) (3: 3) (3: 4) 0 0 0 0 0 2 190 280 260 330 4 400 540 740 590 6 620 800 1260 800 8 890 1070 1640 950 10 1070 1330 1720 1040 Corrosion degree (%) 36 45 58 35

*: The compounding ratio is a compounding ratio of magnesium and ferric chloride.

As shown in Table 1, when reacting with magnesium and ferric chloride, the compounding ratio (weight ratio) of magnesium and ferric chloride shows the fastest rate in the case of 3: 2 to 3: 3.

Example 2

In Example 1, 3 g of magnesium, 0.3 g of iron powder (particle size: 100 mesh), 1 g of PVA as a pore-forming agent were used, and the reaction was performed at 700 ° C. for 20 minutes. The reaction was carried out in the same manner as in Example 1 except that the amount was changed as shown in Table 2 below. The reaction rate of the obtained magnesium-iron alloy and water was measured in the same manner as in Example 1. The results are shown in Table 2 together.

In Table 2 below, the corrosion rate (reaction rate) of magnesium in the resulting alloy obtained according to the blending ratio of magnesium and trivalent iron chloride was used over time using the amount of hydrogen (ml). In addition, this result is shown in FIG. 2 graphically.

Measurement time (minutes) Ferric Chloride Content (g) 0.1 0.2 0.3 0.4 0.5 0 0 0 0 0 0 2 1420 1390 1300 1160 1060 4 2070 2240 1910 1790 1450 6 2370 2690 2310 2120 1800 8 2570 2880 2620 2290 2080 10 2710 2950 2710 2480 2160 Corrosion degree (%) 92 99 92 84 73

As shown in Table 2, when iron powder is added in an amount of 1/10 to magnesium, a pore-forming agent is added thereto, and ferric chloride is mixed and melted to react, ferric chloride is added to magnesium. When reacted with 1/5 to 1/30, the reaction of magnesium in the magnesium-iron alloy with water is significantly faster than when magnesium and ferric chloride are reacted.

Example 3

In Example 1, 3 g of magnesium, 0.3 g of ferric chloride, 1 g of PVA as a pore-forming agent, and a melting reaction of 700 to 725 ° C. were reacted for 30 minutes. The reaction was carried out in the same manner as in Example 1 except that the amount was changed as shown in Table 3, and the reaction rate of magnesium in the magnesium-iron alloy was measured according to the iron content.

The results are shown in Table 3 together. In addition, it is shown in FIG.

Measurement time (minutes) Iron content (g) 0.2 0.3 0.4 0.5 0 0 0 0 0 2 1080 1100 1150 1100 4 1650 1660 1680 1670 6 1950 2020 1950 2020 8 2100 2150 2100 2150 10 2200 2200 2200 2200 Corrosion degree (%) 74 74 73 74

As shown in Table 3, when the ferric chloride is added in an amount of 1/10 to magnesium, the iron content is almost the same as the amount of ferric chloride, or even if a slight excess or a small amount is not changed. As in Example 2, the reaction of magnesium in the magnesium-iron alloy with water is significantly faster when the iron powder is blended than when magnesium and ferric chloride are reacted.

Example 4

In Example 1, 3g of magnesium, 0.3g of iron powder (particle size: 100 mesh), 0.3g of ferric chloride, and melting reaction at 720 to 725 ° C. were allowed to react for 30 minutes. It was reacted in the same manner as in Example 1 except for changing as shown in Table 4. The rate of reaction with water of the obtained magnesium-iron alloy was measured in the same manner as in Example 1. The results are shown in Table 4 together. In addition, it is shown in FIG.

Measurement time (minutes) Amount of PVA (g) 0.5 0.7 One 1.2 1.5 0 0 0 0 0 0 2 770 1030 1140 1570 1420 4 1300 1640 1880 2340 2070 6 1680 1970 2360 2770 2370 8 1900 2160 2650 2820 2550 10 1970 2310 2730 2830 2600 Corrosion degree (%) 67 78 92 96 88

As shown in Table 4, when the pore-forming agent is added in an amount of 1/3 to 1/2 with respect to the amount of magnesium, it can be seen that the reaction rate is faster. However, it depends on the type of pore-forming agent, and the above is limited to the case of using PVA.

Example 5

In Example 2, 3 g of magnesium, 0.3 g of iron powder (particle size: 100 mesh), 0.3 g of ferric chloride, and 1 g of PVA as a pore-forming agent were used to confirm the reactivity of the target product according to the melting reaction temperature of the present reaction. The reaction was carried out while the melt reaction temperature was changed from 600 ° C. to 720 ° C. under the condition of reacting for 20 minutes. The rate of reaction with water of the obtained magnesium-iron alloy was measured in the same manner as in Example 1. The results are shown in Table 5 together. In addition, it is shown in FIG.

Measurement time (minutes) Melt Reaction Temperature (℃) 600 630 650 680 700 720 0 0 0 0 0 0 0 2 570 950 1060 1160 1300 1530 4 910 1490 1530 2020 2180 2360 6 1130 1850 1890 2590 2600 2710 8 1340 2200 2250 2820 2780 2800 10 1530 2420 2420 2830 2830 2830 Corrosion degree (%) 52 82 82 96 96 96

As shown in Table 5, the melting reaction of the magnesium-metal alloy of the present invention can be confirmed that the fastest occurs 680 ~ 720 ℃.

Example 6

In Example 2, 3g of magnesium, 0.3g of iron powder (particle size: 100 mesh), 0.3g of ferric chloride, 1g of PVA as pore-forming agent, melted to confirm the reactivity of the target product according to the melting reaction time of the reaction. The reaction was carried out at a temperature of reaction temperature of 680 DEG C while varying the reaction time for 10 to 30 minutes. The rate of reaction with water of the obtained magnesium-iron alloy was measured in the same manner as in Example 1. The results are shown in Table 6 together. In addition, it is shown in FIG.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 1140 1160 1180 4 1820 2020 2000 6 2260 2590 2470 8 2500 2860 2650 10 2650 2880 2660 Corrosion degree (%) 92 97 90

As shown in Table 6, the melting reaction time of the magnesium-metal alloy of the present invention is not significantly different from 10 to 30 minutes, it can be confirmed that the reaction for 20 to 30 minutes.

Example 7

Except having made melting reaction temperature 700 degreeC in Example 6, it was the same. The results are shown in Table 7 together. In addition, it is shown in FIG.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 1340 1360 1300 4 2140 2150 2120 6 2590 2550 2510 8 2800 2730 2640 10 2830 2830 2710 Corrosion degree (%) 96 96 92

As shown in Table 7, the melting reaction time of the magnesium-metal alloy of the present invention can be seen that there is almost no difference at only 10-30 minutes when the reaction temperature is 700 ℃. Therefore, it can be confirmed that it is optimal to set the melting reaction temperature to 700 ° C.

Example 8

4.7 g of the alloy compound of the present reaction prepared in Example 2 and 1.2 g of sodium chloride were used under high pressure polyethylene (HDPE) in an argon atmosphere, and the mixture was sintered at 165 ° C. for 20 minutes to be molded. At this time, the reaction of water of the present invention according to the change of the HDPE content to the alloy compound as shown in Table 8 was measured. The results are shown in Table 8 together. In addition, it is shown in FIG.

Measurement time (minutes) Content ratio of HEPE (%) 10 20 30 40 50 0 0 0 0 0 0 2 1180 1060 1060 1060 1060 4 2830 2480 2480 2360 2480 6 3540 3420 3360 3300 3250 8 3750 3660 3660 3600 3600 10 3840 3780 3780 3720 3720 Corrosion degree (%) 97 96 96 94 94

As shown in Table 8, it was confirmed that the melting reaction of the magnesium-metal alloy of the present invention does not depend greatly on the amount of HDPE as a binder.

Example 9

The molding was carried out in the same manner as in Example 9 except that the sintering temperature was changed from 145 ° C to 175 ° C in Example 9. The results are shown in Table 9 together. In addition, it is shown in FIG.

Measurement time (minutes) Sintering Temperature (℃) 145 155 165 175 0 0 0 0 0 2 1300 1360 1060 890 4 2890 2830 2480 2240 6 3670 3540 3360 3190 8 3890 3780 3660 3540 10 3950 3840 3780 3660 Corrosion degree (%) 99 97 96 93

As shown in Table 9, it was confirmed that the sintering temperature during the molding of the magnesium-metal compound of the present invention does not significantly affect the performance of the product within the range of 145 ℃ to 165 ℃.

Example 10

Except for using nickel chloride instead of ferric chloride was carried out in the same manner as in Example 1 to obtain the results of Table 10.

Measurement time (minutes) Compounding ratio (g) (3: 1) (3: 2) (3: 3) (3: 4) 0 0 0 0 0 2 150 550 550 550 4 350 750 1000 950 6 580 1050 1450 1200 8 850 1350 1800 1380 10 1150 1800 2200 1550 Corrosion degree (%) 38 60 73 52

Example 11

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder, and the same procedure as in Example 2 was carried out to obtain the results of Table 11 below.

Measurement time (minutes) Nickel Chloride Content (g) 0.1 0.2 0.3 0.4 0.5 0 0 0 0 0 0 2 1250 1300 1550 1550 1800 4 2300 2500 2500 2450 2400 6 2750 2950 2900 2750 2600 8 2800 3000 2950 2900 2650 10 2800 3000 2950 2900 2650 Corrosion degree (%) 93 100 98 97 88

Example 12

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Nickel content (g) 0.2 0.3 0.4 0.5 0.7 One 0 0 0 0 0 0 0 2 850 950 1000 1300 1550 1800 4 2000 2500 2500 2600 2650 2750 6 2650 2750 2700 2750 2900 3000 8 2800 2800 2750 2800 2950 3000 10 2800 2800 2750 2800 2950 3000 Corrosion degree (%) 93 93 92 93 98 100

Example 13

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Amount of PVA (g) 0.5 0.7 One 1.2 1.5 0 0 0 0 0 0 2 1150 1200 1300 1300 1150 4 2150 2300 2350 2500 2350 6 2270 2650 2950 2950 2750 8 2300 2700 2970 3000 2800 10 2300 2700 2970 3000 2800 Corrosion degree (%) 77 90 99 100 93

Example 14

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Melt Reaction Temperature (℃) 600 630 650 680 700 720 0 0 0 0 0 0 0 2 550 950 700 950 95 950 4 1000 1750 1750 2350 2500 1700 6 1450 2170 2350 2800 2900 2400 8 1700 2500 2650 2850 2950 2850 10 1750 2600 2700 2900 2950 2900 Corrosion degree (%) 58 87 90 97 98 97

Example 15

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 950 950 700 4 2200 2350 2200 6 2650 2800 2750 8 2850 2950 2900 10 2900 2950 2900 Corrosion degree (%) 97 98 97

Example 16

Nickel chloride was used instead of ferric chloride, and nickel powder (100 mesh) was used instead of iron powder, and the same procedure as in Example 7 was carried out to obtain the results of Table 16 below.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 900 950 700 4 2300 2500 2300 6 2750 2870 2750 8 2900 2950 2900 10 2950 2970 2900 Corrosion degree (%) 98 99 97

Example 17

Except for using copper chloride instead of ferric chloride was carried out in the same manner as in Example 1 to obtain the results of Table 17.

Measurement time (minutes) Compounding ratio (g) (3: 1) (3: 2) (3: 3) (3: 4) 0 0 0 0 0 2 150 550 550 550 4 370 900 1050 950 6 640 1180 1600 1300 8 850 1540 2000 1650 10 1000 2100 2350 2100 Corrosion degree (%) 34 71 79 71

Example 18

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder, and the same operation as in Example 2 was carried out to obtain the results of Table 18.

Measurement time (minutes) Copper Chloride Content (g) 0.1 0.2 0.3 0.4 0.5 0 0 0 0 0 0 2 950 1100 1650 1700 2400 4 2250 2450 2750 2750 2750 6 2500 2630 2800 2750 2750 8 2550 2650 2800 2750 2750 10 2550 2650 2800 2750 2750 Corrosion degree (%) 86 89 94 93 93

Example 19

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Copper content (g) 0.2 0.3 0.4 0.5 0.7 One 0 0 0 0 0 0 0 2 500 950 950 1050 2000 2350 4 1800 2600 2700 2700 2850 2970 6 2650 2700 2750 2850 2900 2970 8 2650 2700 2750 2850 2900 2970 10 2650 2700 2750 2850 2900 2970 Corrosion degree (%) 89 91 93 96 98 99

Example 20

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder.

Measurement time (minutes) Amount of PVA (g) 0.5 0.7 One 1.2 1.5 0 0 0 0 0 0 2 1150 1200 1200 950 750 4 2650 2700 2650 2500 2300 6 2750 2750 2800 2700 2700 8 2750 2750 2800 2700 2700 10 2750 2750 2800 2700 2700 Corrosion degree (%) 93 93 94 91 91

Example 21

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder, and the same operation as in Example 5 was carried out to obtain the results of Table 21 below.

Measurement time (minutes) Melt Reaction Temperature (℃) 600 630 650 680 700 720 0 0 0 0 0 0 0 2 400 750 350 600 600 300 4 850 1800 1700 2350 2550 850 6 1250 2250 2450 2600 2700 1800 8 1600 2350 2550 2650 2750 2550 10 1900 2450 2600 2650 2750 2600 Corrosion degree (%) 64 82 88 89 93 88

Example 22

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder, and the same operation as in Example 6 was carried out to obtain the results of Table 22.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 650 650 450 4 2350 2350 1950 6 2570 2650 2650 8 2600 2650 2700 10 2600 2650 2700 Corrosion degree (%) 88 89 91

Example 23

Copper chloride was used instead of ferric chloride, and copper powder (100 mesh) was used instead of iron powder, and the same operation as in Example 7 was carried out to obtain the results of Table 23.

Measurement time (minutes) Response time (minutes) 10 20 30 0 0 0 0 2 450 600 650 4 2100 2550 2250 6 2550 2750 2630 8 2650 2750 2650 10 2650 2750 2650 Corrosion degree (%) 89 93 89

Example 24

In Example 1, 3 g of magnesium, 0.3 g of iron powder (particle size: 100 mesh), 0.2 g of ferric chloride, and 1 g of PVA as a pore-forming agent were used, and the melting reaction temperature was 700 ° C. for 20 minutes. 4.0 g of the alloy compound of the present reaction was taken, mixed with magnesium chloride, and the temperature rise was measured while reacting with 20 ml of water, respectively. The results are shown in Table 24 together.

Measurement time (minutes) Electrolyte salt (MgCl ₂ ) addition amount (g) 0.5 1.0 2.0 3.0 4.0 5.0 6.0 0 0 ℃ 0 ℃ 0 ℃ 0 ℃ 0 ℃ 0 ℃ 0 ℃ 2 97 ℃ 99 ℃ 103 ℃ 115 ℃ 118 ℃ 117 ℃ 114 ℃ 4 91 ℃ 93 ℃ 106 ℃ 108 ℃ 110 ℃ 109 ℃ 106 ℃ 6 87 ℃ 99 ℃ 101 ℃ 102 ℃ 103 ℃ 99 ℃ 100 ℃ 8 80 ℃ 92 ℃ 93 ℃ 97 ℃ 98 ℃ 97 ℃ 96 ℃ 10 79 ℃ 84 ℃ 87 ℃ 89 ℃ 91 ℃ 90 ℃ 88 ℃

As shown in Table 24, the addition of magnesium chloride as the electrolyte salt in a weight ratio of 50% to 150% relative to the amount of the alloying compound had an effect on the temperature rise.

Among the above embodiments, a high density polyethylene was used as the binder, but low density polyethylene, various polymers, and the like may be appropriately selected. In addition, although only PVA was mentioned as an Example as a pore forming agent, since the same result is obtained even if it uses various polymer, carbon powder, etc., it abbreviate | omitted this in the Example.

In addition, magnesium chloride was used as the electrolyte salt, but calcium chloride may also be selected. Even if calcium chloride is used, the effect of temperature increase according to the addition of the electrolyte salt can be obtained the same effect is omitted in the embodiment.

From the above results, a magnesium-based intermetallic compound produced by using ferric chloride, nickel chloride, copper chloride, or the like in addition to ferric chloride as a pair compound of magnesium in the magnesium-based intermetallic compound is an object of the present invention. You can see that it can be used according to. However, ferric chloride and ferric chloride are preferred in view of various factors such as price and availability of waste fish compounds.

As described above, the magnesium-based intermetallic compound obtained by the present invention exhibits an exothermic reaction that generates a large amount of heat and hydrogen in a short time when reacted with water or an aqueous electrolyte solution. It can be usefully used for heating of emergency food, fuel of thermal power engine, etc.

Claims (21)

A mixture of a magnesium-based intermetallic compound and magnesium chloride obtained by melting a magnesium metal particle with a metal chloride. The mixture of magnesium-based intermetallic compound and magnesium chloride according to claim 1, obtained by melting and reacting magnesium metal particles and metal chlorides with a pore-forming agent / reducing agent. 3. The mixture of magnesium-based intermetallic compound and magnesium chloride according to claim 2, wherein the pore forming agent / reducing agent is a polymer of carbon and hydrocarbon. 3. The mixture of magnesium-based intermetallic compound and magnesium chloride according to claim 2, wherein the pore forming agent is PVA. The mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 1 or 2, wherein the metal chloride is iron chloride, nickel chloride, copper chloride or a mixture of these metal chlorides. The magnesium-based intermetallic compound and magnesium chloride according to claim 1, 2, 3 or 4, which are obtained by mixing and melting iron, nickel, copper particles or a mixture of these metal particles. mixture. Magnesium-based intermetallic compound and magnesium chloride, characterized in that the magnesium metal particles and metal chlorides are mixed in an argon or helium atmosphere and melted in an argon or helium atmosphere at a temperature of 600 to 800 ° C. for 10 to 40 minutes. Method for preparing a mixture of 8. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 7, wherein the metal chloride is iron chloride, nickel chloride, copper chloride or a mixture of these metal chlorides. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 7 or 8, wherein the mixing ratio of the magnesium particles and the metal chloride is 1: 0.3 to 1: 1 by weight. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 7, wherein the metal powder corresponding to the metal chloride is added and blended in an argon atmosphere to melt. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 10, wherein the metal powder is iron, copper, nickel or a mixture of these metal powders. 12. The method according to claim 10 or 11, wherein the mixing ratio of magnesium and metal chloride is 1: 0.03 to 1: 0.2 by weight, and the mixing ratio of magnesium and metal powder is 1: 0.03 to 1: 0.2 by weight to mix and melt. A method for producing a mixture of a magnesium-based intermetallic compound and magnesium chloride. The method for producing a mixture of a magnesium-based intermetallic compound and magnesium chloride obtained by blending a pore-forming agent / reducing agent with a melt reaction. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 13, wherein the pore forming agent / reducing agent is a polymer of carbon and hydrocarbon. The method for producing a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 13, wherein the pore forming agent / reducing agent is PVA. A magnesium-based metal, characterized in that the mixture of the magnesium-based intermetallic compound and magnesium chloride according to claim 7 is pulverized under an argon atmosphere, and then mixed and mixed with an electrolyte salt, and then the obtained powder is placed in a pack and sealed. Molded body of a mixture of liver compounds and magnesium chloride. 17. The formed body of a mixture of magnesium-based intermetallic compounds and magnesium chloride according to claim 16, wherein the electrolyte salt is sodium chloride, calcium chloride, magnesium chloride or a mixture of these electrolyte salts. 18. The molded article according to claim 16 or 17, wherein the electrolyte salt is blended so as to have a weight ratio of 2% to 40% with respect to water added during use to make the electrolyte solution. The magnesium-based intermetallic compound according to claim 7 and magnesium chloride are ground in an argon atmosphere, and then mixed with an electrolyte salt and a binder, and then the molded article obtained by sintering is put into a pack and sealed. A molded product of a mixture of an intermetallic compound and magnesium chloride. 20. The molded body of the mixture of magnesium-based intermetallic compound and magnesium chloride according to claim 19, wherein the binder is high density polyethylene (HDPE). 20. The molded article of the mixture of magnesium-based intermetallic compound and magnesium chloride according to claim 19, wherein the sintering temperature for making the molded article is 145 to 180 deg.