TWI460280B - Magnesium alloy for normal temperature and manufacturing method thereof - Google Patents
Magnesium alloy for normal temperature and manufacturing method thereof Download PDFInfo
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- TWI460280B TWI460280B TW100110089A TW100110089A TWI460280B TW I460280 B TWI460280 B TW I460280B TW 100110089 A TW100110089 A TW 100110089A TW 100110089 A TW100110089 A TW 100110089A TW I460280 B TWI460280 B TW I460280B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
Description
本發明涉及常溫用高強度/高延伸率鎂合金及其製造方法。The present invention relates to a high strength/high elongation magnesium alloy for normal temperature and a method for producing the same.
目前，工業上廣泛使用Mg-Al類合金。若在Mg合金中添加Al，則因Al所引起的高溶強化及因β-Mg17 Al12 相的形成所引起的粒界強化，Mg合金的強度變大，熔點變低，流動性變大，從而變得更適合壓鑄。但因為脆性大的β相的增加，將降低其柔軟性。若要將鎂合金用於汽車部件等，則不能在受到衝擊時立即斷裂，而需吸收衝擊能量保持原狀，從而在常溫下需要高的柔軟性。而且，隨柔軟性的增加，也可確保加工性及產品成型性能。Currently, Mg-Al alloys are widely used in the industry. When Al is added to the Mg alloy, the high-solubility strengthening due to Al and the grain boundary strengthening due to the formation of the β-Mg 17 Al 12 phase increase the strength of the Mg alloy, lower the melting point, and increase the fluidity. , thus becoming more suitable for die casting. However, because of the increase in the fragile β phase, the softness is lowered. In order to use a magnesium alloy for an automobile part or the like, it is not possible to immediately break when subjected to an impact, and it is necessary to absorb the impact energy to maintain the original state, thereby requiring high flexibility at normal temperature. Moreover, as the flexibility increases, workability and product molding properties are also ensured.
因此，為了確保強度和鑄造性，需要開發一種Mg-Al類合金，其在維持高水準的Al添加比率的同時，具備高水準的柔軟性。柔軟性的提高，一般會犧牲強度。若柔軟性的提高導致強度的降低，則將會限制合金的應用範圍，因此，難以達到合金商用化的目的。Therefore, in order to secure strength and castability, it is required to develop a Mg-Al-based alloy which has a high level of flexibility while maintaining a high level of Al addition ratio. The increase in softness generally results in a sacrifice of strength. If the increase in flexibility leads to a decrease in strength, the application range of the alloy will be limited, and therefore, it is difficult to achieve the purpose of commercialization of the alloy.
因此，需同時考慮柔軟性和強度。若要提高Mg-Al合金的柔軟性，則需添加與Mg或Al的反應性強的元素，從而形成新的相，以抑制脆性大的β相。Therefore, it is necessary to consider both softness and strength. In order to improve the flexibility of the Mg-Al alloy, it is necessary to add an element having high reactivity with Mg or Al to form a new phase to suppress the β phase having a large brittleness.
本發明的目的在於提供一種常溫用鎂合金及其製造方法，其向鎂或鎂合金的金屬溶液添加鹼土金屬氧化物(尤其是氧化鈣)，以製造鎂合金。An object of the present invention is to provide a magnesium alloy for normal temperature and a method for producing the same, which comprises adding an alkaline earth metal oxide (particularly calcium oxide) to a metal solution of magnesium or a magnesium alloy to produce a magnesium alloy.
另外，本發明的另一目的在於提供一種常溫用鎂合金及其製造方法，其向鎂合金添加鹼土金屬氧化物，即CaO，以減少氧化物、夾雜物、氣孔等，提高鑄件的內部完整性，從而同時提高其柔軟性及強度。In addition, another object of the present invention is to provide a magnesium alloy for normal temperature and a method for producing the same, which comprises adding an alkaline earth metal oxide, that is, CaO, to a magnesium alloy to reduce oxides, inclusions, pores, etc., and improve the internal integrity of the casting. , thereby improving its softness and strength.
本發明的目的不受如上所述目的的限制，而對於本領域的普通技術人員而言，未提及的其他技術目的從下麵的說明中變得顯而易見。The object of the present invention is not limited by the above-described objects, and other technical objects not mentioned will become apparent to those skilled in the art from the following description.
為達到上述目的，本發明常溫用鎂合金製造方法，包括如下步驟：熔化鎂或鎂合金；向熔化有上述鎂或鎂合金的金屬溶液表面添加0.05~1.2wt%的CaO；藉由表面攪拌消耗CaO，以藉由上述金屬溶液和所添加的上述CaO的充分反應，使CaO基本上不殘留於反應物中；及使上述去除氧成分的Ca充分反應，從而使其基本上不殘留於上述鎂或鎂合金中。In order to achieve the above object, the method for producing a magnesium alloy for normal temperature according to the present invention comprises the steps of: melting a magnesium or a magnesium alloy; adding 0.05 to 1.2 wt% of CaO to the surface of the metal solution in which the magnesium or magnesium alloy is melted; and consuming by surface agitation CaO is such that CaO does not substantially remain in the reactant by the sufficient reaction of the above metal solution and the added CaO; and Ca of the oxygen-removing component is sufficiently reacted so as not to remain substantially in the magnesium Or in magnesium alloys.
具體而言，上述所添加的CaO量為0.2wt%至0.9 wt%，而較佳地，上述所添加的CaO量為0.3wt%至0.7wt%。Specifically, the amount of CaO added is 0.2% by weight to 0.9% by weight, and preferably, the amount of CaO added is 0.3% by weight to 0.7% by weight.
因添加上述CaO所生成的化合物有Mg2 Ca或Al2 Ca或(Mg、Al)2 Ca中的至少一種。The compound formed by adding the above CaO is at least one of Mg 2 Ca or Al 2 Ca or (Mg, Al) 2 Ca.
為達到上述目的，本發明常溫用鎂合金，其特徵在於：向鎂或鎂合金的金屬溶液添加0.05~1.2 wt%的CaO之後，藉由上述金屬溶液和所添加的上述CaO的還原反應，消耗上述CaO的一部分或全部，以使Ca和上述鎂類合金中的Mg元素或構成合金的其他元素結合生成化合物，從而使合金的常溫機械物性大於添加CaO之前的鎂或鎂合金的常溫機械物性。In order to achieve the above object, the magnesium alloy for normal temperature according to the present invention is characterized in that after adding 0.05 to 1.2 wt% of CaO to a metal solution of magnesium or a magnesium alloy, consumption is performed by a reduction reaction of the above metal solution and the added CaO. Some or all of the CaO described above is such that Ca and the Mg element in the magnesium alloy or other elements constituting the alloy are combined to form a compound, so that the normal temperature mechanical properties of the alloy are greater than the room temperature mechanical properties of the magnesium or magnesium alloy before the addition of CaO.
具體而言，上述常溫機械物性是指常溫屈服強度、常溫拉伸強度或常溫延伸率中的一種。Specifically, the above-mentioned room temperature mechanical property refers to one of normal temperature yield strength, normal temperature tensile strength, or normal temperature elongation.
隨上述CaO的添加量的增加，合金的常溫機械物性增加；隨上述CaO的添加量的增加，合金的常溫屈服強度或常溫拉伸強度和常溫延伸率同時增加。As the amount of CaO added increases, the mechanical properties of the alloy increase at room temperature; as the amount of CaO added increases, the room temperature yield strength or the normal temperature tensile strength and the room temperature elongation increase simultaneously.
上述所添加的CaO量為0.2wt%至0.9 wt%，而較佳地，上述所添加的CaO量為0.3wt%至0.7wt%；而因添加上述CaO所生成的化合物有Mg2 Ca或.Al2 Ca或(Mg、Al)2 Ca中的至少一種。The amount of CaO added is 0.2% by weight to 0.9% by weight, and preferably, the amount of CaO added is 0.3% by weight to 0.7% by weight; and the compound formed by adding the above CaO is Mg 2 Ca or. At least one of Al 2 Ca or (Mg, Al) 2 Ca.
如上所述，本發明向商用鎂合金中添加CaO，從而使鎂合金的組織變細並形成Al2 Ca相等。另外，抑制脆性大的β-Mg17 Al12 相的形成，大幅減少鑄造缺陷。結果，藉由添加CaO，同時提高鎂合金的強度和柔軟性。As described above, the present invention adds CaO to a commercial magnesium alloy to make the microstructure of the magnesium alloy thin and form Al 2 Ca equal. In addition, the formation of a β-Mg 17 Al 12 phase having a large brittleness is suppressed, and casting defects are greatly reduced. As a result, the strength and flexibility of the magnesium alloy are simultaneously improved by adding CaO.
下面，結合附圖對本發明較佳實施例進行詳細說明。在附圖中，在任何地方對相同的結構儘量使用相同的標記。另外，省略對有可能給本發明的技術思想帶來混淆的已公開功能及結構的說明。Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used as much as possible for the same structure anywhere. In addition, the description of the disclosed functions and structures that may cause confusion to the technical idea of the present invention is omitted.
本發明涉及將氧化鈣添加於鎂金屬溶液而製造新合金的方法及利用上述方法製造而成的合金，而所要解決的技術課題是將上述鈣添加於鎂時的問題並克服物性的限制。The present invention relates to a method of producing a new alloy by adding calcium oxide to a magnesium metal solution and an alloy produced by the above method, and the technical problem to be solved is to solve the problem of adding calcium to magnesium and to overcome the limitation of physical properties.
圖1為本發明鎂類合金製造方法順序圖。Fig. 1 is a sequence diagram showing a method for producing a magnesium-based alloy of the present invention.
如圖1所示，本發明鎂合金製造方法，包括如下步驟：形成鎂類金屬溶液S1；添加鹼土金屬氧化物(在本發明中為氧化鈣CaO)S2；攪拌S3；消耗鹼土金屬氧化物S4；進行鹼土金屬反應(在本發明中為鈣Ca)S5；鑄造S6；及固化S7。上述消耗鹼土金屬氧化物的步驟S4和上述進行鹼土金屬反應的步驟S5，雖然為了說明的便利而分為單獨的步驟，但兩個工序S4、S5幾乎同時發生。即，若在S4步驟中開始供應鹼土金屬，則開始S5步驟。As shown in FIG. 1, the method for producing a magnesium alloy of the present invention comprises the steps of: forming a magnesium-based metal solution S1; adding an alkaline earth metal oxide (in the present invention, calcium oxide CaO) S2; stirring S3; and consuming an alkaline earth metal oxide S4. Conducting an alkaline earth metal reaction (in the present invention, calcium Ca) S5; casting S6; and curing S7. The step S4 of consuming the alkaline earth metal oxide and the step S5 of performing the alkaline earth metal reaction described above are divided into separate steps for convenience of explanation, but the two steps S4 and S5 occur almost simultaneously. That is, if the supply of the alkaline earth metal is started in the step S4, the step S5 is started.
在上述形成鎂類金屬溶液的步驟S1，在將鎂或鎂合金投入熔爐之後，在保護氣體氣氛下提供400至800℃的溫度。則上述熔爐內的鎂合金經熔化成為鎂類金屬溶液。In the above step S1 of forming a magnesium-based metal solution, after the magnesium or magnesium alloy is introduced into the furnace, a temperature of 400 to 800 ° C is supplied under a protective gas atmosphere. Then, the magnesium alloy in the above furnace is melted into a magnesium-based metal solution.
鎂或鎂合金的熔化溫度Melting temperature of magnesium or magnesium alloy
在本發明中，鎂或鎂合金的熔化解溫度是指純鎂金屬熔化的溫度和鎂合金熔化的溫度。根據合金種類的不同，熔化溫度有可能存在差異。為進行充分的反應，在鎂或鎂合金完全被熔化的狀態下投入氧化鈣。鎂或鎂合金的熔化溫度，只要是能使固態充分熔化成完全的液態的溫度即可。但在本發明中，考慮到氧化鈣的投入會降低金屬溶液的溫度，需在有充分餘量的溫度範圍內維持金屬溶液的作業。In the present invention, the melting temperature of the magnesium or magnesium alloy means the temperature at which the pure magnesium metal is melted and the temperature at which the magnesium alloy is melted. Depending on the type of alloy, there may be differences in the melting temperature. In order to carry out a sufficient reaction, calcium oxide is put in a state in which the magnesium or magnesium alloy is completely melted. The melting temperature of the magnesium or magnesium alloy may be any temperature which can sufficiently melt the solid state into a completely liquid state. However, in the present invention, in consideration of the fact that the input of calcium oxide lowers the temperature of the metal solution, it is necessary to maintain the operation of the metal solution in a temperature range having a sufficient margin.
在此，若溫度低於400℃，則難以形成鎂合金金屬溶液，而若溫度高於800雙聲道，則存在可使鎂類金屬溶液燃燒的危險。另外，雖然在上述鎂的情況下，大致在600℃以上的溫度形成金屬溶液，但在鎂合金的情況下，也可在400~600℃之間的溫度形成金屬溶液。一般而言，在金屬學上，大多情況下隨著形成合金其熔點將降低。Here, if the temperature is lower than 400 ° C, it is difficult to form a magnesium alloy metal solution, and if the temperature is higher than 800 double channels, there is a risk that the magnesium metal solution can be burned. Further, in the case of the above magnesium, the metal solution is formed at a temperature of approximately 600 ° C or higher, but in the case of the magnesium alloy, the metal solution may be formed at a temperature between 400 and 600 ° C. In general, in metallurgy, in most cases, the melting point will decrease as the alloy is formed.
若熔化溫度過高，則將發生液體金屬的氣化，而且，根據鎂的特點容易燃燒，因此，可導致金屬溶液量的損失，且也給最終物性帶來不利的影響。If the melting temperature is too high, vaporization of the liquid metal occurs, and it is easy to burn according to the characteristics of magnesium. Therefore, the amount of the metal solution can be lost, and the final physical property is adversely affected.
用於上述鎂類金屬溶液形成步驟的鎂，可為從純鎂、鎂合金及其等價物中選擇的任何一種。另外，上述鎂合金可為從AZ91D、AM20、AM30、AM50、AM60、AZ31、AS41、AS31、AS21X、AE42、AE44、AX51、AX52、AJ50X、AJ52X、AJ62X、MRI153、MRI230、AM-HP2、Mg-Al、Mg-Al-Re、Mg-Al-Sn、Mg-Zn-Sn、Mg-Si、Mg-Zn-Y及其等價物中選擇的任何一種，但本發明不受這些鎂合金的限制。可選用通常用於工業的任何鎂合金。The magnesium used in the above magnesium metal solution forming step may be any one selected from pure magnesium, magnesium alloy and equivalents thereof. In addition, the above magnesium alloy may be from AZ91D, AM20, AM30, AM50, AM60, AZ31, AS41, AS31, AS21X, AE42, AE44, AX51, AX52, AJ50X, AJ52X, AJ62X, MRI153, MRI230, AM-HP2, Mg- Any one selected from the group consisting of Al, Mg-Al-Re, Mg-Al-Sn, Mg-Zn-Sn, Mg-Si, Mg-Zn-Y, and the equivalent thereof, but the present invention is not limited by these magnesium alloys. Any magnesium alloy commonly used in industry can be selected.
在上述添加鹼土金屬氧化物的步驟S2，向上述鎂金屬溶液添加粉末狀的氧化鈣。在此，為促進與鎂合金的反應，氧化鈣以粉末狀為宜。In the step S2 of adding the alkaline earth metal oxide described above, powdered calcium oxide is added to the magnesium metal solution. Here, in order to promote the reaction with the magnesium alloy, calcium oxide is preferably in the form of a powder.
氧化鈣的粉末狀態Powder state of calcium oxide
為進行反應而投入的氧化鈣，可以任何形式投入。但為了有效的反應，取可增加反應表面積的粉末狀為宜。但是，若小於0.1 μm，則因氣化的鎂或熱風飛散，從而不易投入到爐中。另外，相互凝聚，不易與液態的熔融金屬混合並結塊。但若過大，則因不利於增加表面積而不可取。理想的粉末粒度為小於500 μm以下為宜。而更加為200 μm以下。The calcium oxide which is supplied for the reaction can be supplied in any form. However, in order to carry out an effective reaction, it is preferred to take a powder which increases the surface area of the reaction. However, if it is less than 0.1 μm, vaporized magnesium or hot air scatters, and it is difficult to put it into the furnace. In addition, they agglomerate each other and are not easily mixed with a liquid molten metal and agglomerated. However, if it is too large, it is not desirable because it is not conducive to increasing the surface area. An ideal powder particle size of less than 500 μm is preferred. It is more than 200 μm.
而為了防止粉末相的飛散，也可投入凝聚粉末的丸狀氧化鈣。In order to prevent scattering of the powder phase, it is also possible to introduce a pelletized calcium oxide of the powder.
所投入的鹼土金屬氧化物(氧化鈣)Alkaline earth metal oxide (calcium oxide)
作為向金屬溶液添加的鹼土金屬氧化物，本發明使用氧化鈣(CaO)。此外，也可為從SrO、BeO或MgO及其等價物中選擇的至少一種。As the alkaline earth metal oxide added to the metal solution, the present invention uses calcium oxide (CaO). Further, it may be at least one selected from the group consisting of SrO, BeO or MgO and equivalents thereof.
用於上述添加鹼土金屬氧化物的步驟的鹼土金屬氧化物，一般可添加0.001至30 wt%。The alkaline earth metal oxide used in the above step of adding an alkaline earth metal oxide can be generally added in an amount of 0.001 to 30% by weight.
鹼土金屬氧化物的投入量取決於最終目標合金的成分。即，根據鎂合金中所要包含的Ca的量，藉由逆計算決定CaO的量。若鎂合金中從CaO間接包括Ca的量超過21.4wt%(CaO為30wt%)，則鎂合金的物性將超出原來的物性，因此，上述投入量需在低於30.0wt%的範圍內調節。The amount of alkaline earth metal oxide input depends on the composition of the final target alloy. That is, the amount of CaO is determined by inverse calculation based on the amount of Ca to be contained in the magnesium alloy. If the amount of Ca indirectly included in the magnesium alloy from CaO exceeds 21.4% by weight (CaO is 30% by weight), the physical properties of the magnesium alloy will exceed the original physical properties, and therefore, the above-mentioned input amount needs to be adjusted within a range of less than 30.0% by weight.
在本發明中，用作鹼土金屬氧化物的氧化鈣的投入量為0.05wt%至1.2wt%。在氧化鈣的投入量低於1.2wt%時，可獲得優秀的常溫高強度(拉伸強度/屈服強度)和優秀的常溫高延伸率的物性值。但若氧化鈣的投入量低於0.05wt%，則上述物性值的改善效果相對較小。較佳地，上述氧化鈣的投入量為0.2wt%至0.9wt%。而更加為0.3wt%至0.7wt%。在氧化鈣的投入量為0.3wt%至0.7wt%範圍內時，可獲得優秀的常溫高強度/高延伸率的物性值。與此同時，在0.3wt%至0.7wt%的範圍內，常溫機械物性值(拉伸強度、屈服強度、延伸率)，隨氧化鈣的量的增加而增加。In the present invention, the amount of calcium oxide used as the alkaline earth metal oxide is from 0.05% by weight to 1.2% by weight. When the amount of calcium oxide is less than 1.2% by weight, excellent physical strength at room temperature, high strength (tensile strength/yield strength), and excellent room temperature and high elongation can be obtained. However, if the amount of calcium oxide added is less than 0.05% by weight, the effect of improving the physical property value described above is relatively small. Preferably, the above calcium oxide is supplied in an amount of 0.2% by weight to 0.9% by weight. More preferably, it is 0.3 wt% to 0.7 wt%. When the input amount of calcium oxide is in the range of 0.3% by weight to 0.7% by weight, an excellent physical property value at room temperature, high strength, and high elongation can be obtained. At the same time, in the range of 0.3 wt% to 0.7 wt%, the mechanical properties (normal tensile strength, yield strength, elongation) at room temperature increase as the amount of calcium oxide increases.
在上述攪拌步驟S3，以1秒~60分鐘/所添加的氧化鈣0.1wt%的標準，攪拌上述鎂金屬溶液。In the stirring step S3, the magnesium metal solution is stirred for 1 second to 60 minutes/0.1% by weight of the added calcium oxide.
在此，若攪拌時間少於1秒/0.1wt%，則不能氧化鈣充分混合至鎂金屬溶液，而若攪拌時間多餘60分鐘/0.1wt%，則造成鎂金屬溶液的攪拌時間的浪費。一般而言，攪拌時間取決於金屬溶液的量和所投入的氧化鈣的量。Here, if the stirring time is less than 1 second / 0.1 wt%, calcium oxide cannot be sufficiently mixed to the magnesium metal solution, and if the stirring time is excessive 60 minutes / 0.1 wt%, the stirring time of the magnesium metal solution is wasted. In general, the stirring time depends on the amount of the metal solution and the amount of calcium oxide charged.
在投入氧化物粉末時，可採用一次性投入的方法，也可為促進反應，降低粉末的凝聚可能性，採用第一次投入之後經過一定時間之後再次投入的方法，或採用分為適當兩依次投入的方法。When the oxide powder is introduced, a one-time input method may be employed, or the reaction may be promoted to reduce the possibility of agglomeration of the powder, and the method may be re-input after a certain period of time after the first input, or may be divided into appropriate two. The method of input.
攪拌方法及條件Stirring method and conditions
為本發明鎂或鎂合金和氧化鈣的有效反應，進行攪拌為宜。一般的攪拌方法是在盛有金屬溶液的爐周圍具備可施加電磁場的裝置，以藉由產生電磁場引起金屬溶液的對流。另外，也可從外部人為地對金屬溶液進行攪拌(機械攪拌)。若進行機械攪拌，可進行適當攪拌以防止所投入的氧化鈣粉末凝聚。在本發明中，攪拌的最終目的是幫助金屬溶液和所投入的粉末的還原反應。In order to effectively react the magnesium or magnesium alloy of the present invention with calcium oxide, stirring is preferred. A general agitation method is to provide a device for applying an electromagnetic field around a furnace containing a metal solution to cause convection of the metal solution by generating an electromagnetic field. Alternatively, the metal solution may be artificially stirred (mechanically stirred) from the outside. If mechanical agitation is performed, appropriate agitation may be performed to prevent aggregation of the input calcium oxide powder. In the present invention, the ultimate purpose of the agitation is to assist in the reduction reaction of the metal solution and the powder to be charged.
根據金屬溶液的溫度和所投入的粉末的狀態(預熱狀態)等，攪拌時間可存在差異。較佳地，原則上攪拌至在金屬溶液表面看不見粉末為止。其原因是，因粉末的比重比金屬溶液小，因此，在正常狀態下粉末將漂浮於金屬表面之上，而若在金屬溶液表面看不見粉末，則可間接判斷已充分反應。在此，充分反應是指氧化鈣基本上都與金屬溶液反應而被消耗的狀態。The stirring time may vary depending on the temperature of the metal solution and the state of the powder to be charged (preheating state) and the like. Preferably, it is stirred in principle until no powder is visible on the surface of the metal solution. The reason is that since the specific gravity of the powder is smaller than that of the metal solution, the powder will float on the metal surface under normal conditions, and if the powder is not visible on the surface of the metal solution, it can be indirectly judged to have sufficiently reacted. Here, the sufficient reaction means a state in which calcium oxide is substantially consumed by reacting with a metal solution.
即使在金屬溶液表面看不見粉末，但也不能排出其存在於金屬溶液之中的可能性，因此，在經過攪拌時間之後，有可能在維持一定時間的同時，確認是否存在未來得及浮上的粉末，以完全消耗還未反應的粉末。Even if the powder is not visible on the surface of the metal solution, the possibility of being present in the metal solution cannot be discharged. Therefore, after the stirring time, it is possible to confirm whether or not there is a powder that can be floated in the future while maintaining a certain period of time. To completely consume the unreacted powder.
攪拌時機Mixing time
攪拌的時機以在投入氧化物粉末的同時進行為宜。另外，也可在氧化物從金屬溶液獲得熱量以達到一定溫度以上之後，開始攪拌以促進反應。直至看不見投入至金屬溶液表面的氧化物粉末為止進行攪拌。氧化鈣藉由反應完全消耗之後結束攪拌。The timing of the stirring is preferably carried out while the oxide powder is being charged. Alternatively, after the oxide is obtained from the metal solution to reach a certain temperature or higher, stirring may be started to promote the reaction. Stirring was carried out until the oxide powder charged on the surface of the metal solution was not visible. The calcium oxide is stirred after the reaction is completely consumed.
表面反應Surface reaction
一般而言，若向金屬溶液直接添加鹼土金屬中的Ca和Sr，則因比重的差異，從而向重較小的鎂的金屬溶液下沉的同時完成反應。因此，只藉由攪拌金屬溶液，即可幫助Ca的熔化，生成合金。In general, when Ca and Sr in an alkaline earth metal are directly added to a metal solution, the reaction is completed while sinking to a metal solution having a small weight due to a difference in specific gravity. Therefore, the melting of Ca can be assisted only by stirring the metal solution to form an alloy.
與此相反，若向金屬溶液投入氧化鈣，則同樣因比重的差異，不向金屬溶液下沈而在金屬溶液表面漂浮。On the other hand, when calcium oxide is added to the metal solution, it also floats on the surface of the metal solution without sinking to the metal solution due to the difference in specific gravity.
通常，在生成合金時，藉由在金屬溶液和金屬之間形成對流(convection)或對其進行攪拌(stirring)，促進積極的反應，幫助金屬溶液內部的反應。但是，在本發明中，若促進反應，則因投入金屬溶液的氧化物來不及反應而殘留於最終的材料之中，從而成為降低物性值或導致缺陷的原因。即，若促進非金屬溶液表面的金屬溶液內部的反應，則不能促進金屬溶液表面的反應，從而最終使氧化鈣殘留於金屬溶液之中相對較多。Generally, in the formation of an alloy, a positive reaction is promoted by forming a convection or stirring between the metal solution and the metal to assist the reaction inside the metal solution. However, in the present invention, when the reaction is promoted, the oxide of the metal solution is not added to the final material due to the reaction, and the physical property value or the cause of the defect is lowered. That is, when the reaction inside the metal solution on the surface of the non-metal solution is promoted, the reaction on the surface of the metal solution cannot be promoted, and finally, the calcium oxide remains relatively much in the metal solution.
因此，在本發明中，需創造一種反應條件，以使氧化物在非金屬溶液內部的金屬溶液表面進行反應。為此，需不將漂浮於金屬溶液表面的氧化物，強制攪拌進金屬溶液內部。較佳地，在暴露於空氣的金屬溶液的表面，將鹼土金屬氧化物均勻鋪開。更加地，在供應氧化物時，用氧化物塗布金屬溶液的全部表面。Therefore, in the present invention, it is necessary to create a reaction condition for reacting an oxide on the surface of a metal solution inside a non-metal solution. For this reason, it is necessary to forcibly stir the oxide floating on the surface of the metal solution into the inside of the metal solution. Preferably, the alkaline earth metal oxide is evenly spread over the surface of the metal solution exposed to the air. More specifically, when the oxide is supplied, the entire surface of the metal solution is coated with an oxide.
較之不進行攪拌，進行攪拌更能促進反應，而較之在金屬溶液的內部進行攪拌，在外部表面(上層部表面)進行攪拌更能促進反應。即，金屬溶液在外部表面(上層部表面)更好地與露出至空氣中的氧化物粉末進行反應。真空或氣氛氣體環境下的結果不是很好。為了充分的反應，需藉由上層部攪拌促進表面反應。在此，充分的反應是指所投入的鹼土金屬氧化物全部與金屬溶液反應，從而基本上不殘留於金屬溶液中的反應。在本發明中，該促進表面的攪拌稱之為表面攪拌。即，藉由添加至Mg金屬溶液的表面的CaO的還原反應(表面還原反應)生成的Ca，將作為Mg或Mg合金的元素。The stirring is more effective than the stirring, and the stirring is performed on the outer surface (the upper surface) to promote the reaction as compared with stirring in the inside of the metal solution. That is, the metal solution is better reacted on the outer surface (upper layer surface) with the oxide powder exposed to the air. The results in vacuum or atmospheric gas environments are not very good. In order to fully react, it is necessary to promote the surface reaction by stirring the upper layer. Here, the sufficient reaction means a reaction in which all of the alkaline earth metal oxides charged are reacted with the metal solution so as not to substantially remain in the metal solution. In the present invention, the agitation of the promoting surface is referred to as surface agitation. That is, Ca produced by a reduction reaction (surface reduction reaction) of CaO added to the surface of the Mg metal solution is an element of Mg or Mg alloy.
下表1為在向AM60B鎂合金金屬溶液各添加5、10、15wt%的70 μm粒子大小的氧化鈣之後，按不同的攪拌方法測得的鎂合金內的氧化鈣殘餘量。攪拌方法分金屬溶液的上部層攪拌、金屬溶液的內部攪拌及其餘的未攪拌。此時，對上部層的攪拌在從上述金屬溶液表面位元於全部金屬溶液深度的10%左右的上部層進行。根據不同的攪拌條件，只對上部層進行攪拌的情況，較之未攪拌情況和進行內部攪拌的情況，在各添加5、10、15wt%的氧化鈣的情況下，氧化鈣的殘餘量分別為0.001、0.002、0.005wt%，其殘留量最少。即，為了使CaO在Mg金屬溶液表面進行表面而對金屬溶液上部層進行攪拌的情況下，所添加的絕大部分CaO分離為Ca。即，向商用AM60B的合金添加CaO，以藉由還原反應向合金添加Ca。Table 1 below shows the residual amount of calcium oxide in the magnesium alloy measured by different stirring methods after adding 5, 10, 15 wt% of calcium oxide having a particle size of 70 μm to each of the AM60B magnesium alloy metal solution. The stirring method is divided into the upper layer of the metal solution, the internal stirring of the metal solution, and the rest without stirring. At this time, the stirring of the upper layer was performed on the upper layer from the surface of the metal solution to about 10% of the depth of the entire metal solution. According to different stirring conditions, only the upper layer is stirred, compared with the case of no stirring and internal stirring, in the case of adding 5, 10, 15 wt% of calcium oxide, the residual amount of calcium oxide is 0.001, 0.002, 0.005 wt%, the residue is the least. That is, in order to stir CaO on the surface of the Mg metal solution and stir the upper layer of the metal solution, most of the added CaO is separated into Ca. That is, CaO is added to the alloy of commercial AM60B to add Ca to the alloy by a reduction reaction.
氧化鈣的氧成分藉由上述對金屬溶液上部層的攪拌，基本上從金屬溶液表面去除。上述攪拌在從上述金屬溶液表面位元於全部金屬溶液深度的20%左右的上部層進行為宜。在20%以上的深度，不能產生作為本發明較佳實施例的表面反應。而較佳地，上述攪拌在從上述金屬溶液表面位元於全部金屬溶液深度的10%左右的上部層進行為宜。這是藉由控制使漂浮的氧化鈣基本上位於金屬溶液深度10%的上部層，以最大限度地減少金屬溶液的擾亂。The oxygen component of the calcium oxide is substantially removed from the surface of the metal solution by agitation of the upper layer of the metal solution as described above. The agitation is preferably carried out in an upper layer from the surface of the metal solution to about 20% of the depth of the entire metal solution. At a depth of 20% or more, the surface reaction which is a preferred embodiment of the present invention cannot be produced. Preferably, the agitation is preferably carried out in an upper layer from the surface of the metal solution to about 10% of the depth of the entire metal solution. This is achieved by controlling the floating calcium oxide to be substantially at the upper layer of the metal solution at a depth of 10% to minimize the disturbance of the metal solution.
在上述消耗鹼土金屬氧化物的步驟S4，藉由上述金屬溶液和上述所添加的氧化鈣的反應，使氧化鈣至少一部分或基本上(substantially)不殘留於鎂合金中。在本發明中，所投入的氧化鈣藉由充分的反應全部消耗為宜。但是，即使存在一部分未反應而殘留於合金內的氧化鈣，需不能對物性產生很大的影響。In the step S4 of consuming the alkaline earth metal oxide, the calcium oxide is at least partially or substantially not retained in the magnesium alloy by the reaction of the metal solution and the added calcium oxide. In the present invention, it is preferred that the calcium oxide to be charged is completely consumed by a sufficient reaction. However, even if there is a part of calcium oxide which remains unreacted and remains in the alloy, it is not required to have a large influence on physical properties.
在此，消耗氧化鈣是指從鹼土金屬氧化物中去除氧成分。上述氧成分可以氧(O2 )氣體的形式去除，或藉由與金屬溶液中的鎂或其合金成分的結合，以浮渣(dross)或沉澱物形式去除。在此，氧化鈣所提供的Ca，較之合金內的Mg，更傾向於與其他的成分元素化合。另外，上述氧成分藉由對金屬溶液上部層的攪拌，基本上從金屬溶液表面去除。Here, consumption of calcium oxide means removal of an oxygen component from an alkaline earth metal oxide. The above oxygen component may be removed in the form of oxygen (O 2 ) gas or in the form of dross or precipitate by combination with magnesium or an alloy component thereof in the metal solution. Here, Ca provided by calcium oxide is more likely to combine with other constituent elements than Mg in the alloy. Further, the oxygen component is substantially removed from the surface of the metal solution by stirring the upper layer of the metal solution.
圖3為在本發明中，藉由對鎂金屬溶液上部層的攪拌使氧化鈣(CaO)解離的模式圖。Fig. 3 is a schematic view showing the dissociation of calcium oxide (CaO) by stirring the upper layer of the magnesium metal solution in the present invention.
在上述進行鹼土金屬反應的步驟S5，使藉由上述消耗氧化鈣而生成的鈣進行反應，以使鈣至少一部分或基本上不殘留於鎂合金中。在此，藉由消耗而生成的鈣，與上述鎂合金中的鎂、鋁或上述金屬溶液中的其餘合金元素(成分)中的至少一種化合，以基本上不殘留於鎂合金中。在此，化合物是指藉由金屬和金屬的結合而生成的金屬間化合物。In the step S5 of performing the alkaline earth metal reaction described above, the calcium produced by the above-described consumption of calcium oxide is reacted so that at least a part of the calcium or substantially does not remain in the magnesium alloy. Here, the calcium generated by the consumption is combined with at least one of magnesium, aluminum, or the remaining alloying elements (components) in the above-described metal alloy so as not to substantially remain in the magnesium alloy. Here, the compound means an intermetallic compound formed by a combination of a metal and a metal.
在本發明中，消耗全部所投入的氧化鈣時，其效果達到最佳。可藉由金屬溶液和氧化鈣的充分反應，使氧化鈣不殘留於鎂合金中。金屬溶液中不殘留上述氧化鈣時，其機械物性值達到最高。若因某些原因氧化鈣未藉由反應全部消耗，而只消耗其中的一部分，則較之全部消耗的情況，其物性值較低。但即使是消耗一部分的情況，其物性值優於相同成分的未投入氧化鈣的鎂合金的物性。In the present invention, when all of the added calcium oxide is consumed, the effect is optimized. The calcium oxide does not remain in the magnesium alloy by sufficient reaction of the metal solution and the calcium oxide. When the above calcium oxide is not left in the metal solution, the mechanical property value thereof is the highest. If, for some reason, calcium oxide is not consumed by the reaction and only a part of it is consumed, the physical property value is lower than in the case of total consumption. However, even in the case where a part is consumed, the physical property value is superior to the physical properties of the magnesium alloy which is not charged with calcium oxide of the same composition.
結果，所添加的氧化鈣，藉由與作為金屬溶液的鎂合金的反應，至少一部分或基本上去除氧成分，而去除氧成分的鈣，與上述鎂合金中的鎂、鋁或上述金屬溶液中的其餘合金元素中的至少一種化合，以至少一部分或基本上不殘留於鎂合金中。As a result, the added calcium oxide removes the oxygen component by at least partially or substantially removing the oxygen component by reaction with the magnesium alloy as the metal solution, and is in the magnesium, aluminum or the above metal solution in the above magnesium alloy. At least one of the remaining alloying elements is combined to remain at least partially or substantially not in the magnesium alloy.
在上述消耗鹼土金屬的步驟S5，在進行鹼土金屬氧化物的還原反應時，在金屬溶液表面產生閃光。而這種閃光可稱為判斷是否結束還原反應的標誌。若在產生閃光的過程中出鐵而結束反應，則所添加的鹼土金屬氧化物有可能沒有完全消耗。即，在作為還原反應的間接判斷標誌的閃光結束之後再出鐵。In the above-described step S5 of consuming the alkaline earth metal, when the reduction reaction of the alkaline earth metal oxide is carried out, a flash is generated on the surface of the metal solution. This kind of flash can be called a sign to judge whether or not to end the reduction reaction. If the reaction is terminated by iron extraction during the generation of the flash, the added alkaline earth metal oxide may not be completely consumed. That is, iron is discharged after the end of the flash as an indirect judgment flag of the reduction reaction.
至今為止說明的過程，如圖1和圖2所示。圖2為在本發明中，添加於鎂金屬溶液中的氧化鈣(CaO)的解離順序圖。The process described so far is shown in Figures 1 and 2. Fig. 2 is a dissociation sequence diagram of calcium oxide (CaO) added to a magnesium metal solution in the present invention.
另外，在鑄造步驟S6，將上述鎂金屬溶液倒入常溫或預熱狀態的模具中進行鑄造。在此，上述模具為從金屬模具、陶瓷模具、石墨模具及其等價物中選擇的至少一種。另外，鑄造方式可採用重力鑄造、連續鑄造及其等價方式。Further, in the casting step S6, the magnesium metal solution is poured into a mold at a normal temperature or a preheated state for casting. Here, the mold is at least one selected from the group consisting of a metal mold, a ceramic mold, a graphite mold, and the like. In addition, the casting method may employ gravity casting, continuous casting, and the equivalent thereof.
在上述固化步驟S7，將上述模具冷卻至常溫之後，從模具中取出鎂合金(例如鎂合金鑄錠)。In the above curing step S7, after the mold is cooled to normal temperature, a magnesium alloy (for example, a magnesium alloy ingot) is taken out from the mold.
藉由上述製造方法製造而成的鎂類合金的硬度(HRF)可為40至80。但上述硬度值根據加工方法及熱處理等的不同存在各種變化，因此，本發明鎂類合金不受上述硬度值的限制。The magnesium alloy produced by the above production method may have a hardness (HRF) of 40 to 80. However, the above hardness values vary depending on the processing method, heat treatment, etc., and therefore, the magnesium alloy of the present invention is not limited by the above hardness value.
若為純鎂金屬溶液，則金屬溶液中的鎂成分與鹼土金屬進行反應而生成鎂(鹼土金屬)化合物。在本發明中，因鹼土金屬氧化物為CaO，因此，生成Mg2 Ca。另外，原來構成CaO的氧，或變成O2 排出至金屬溶液外，或與Mg結合生成MgO，從而以浮渣形式排出(請參考下面的反應式1)。In the case of a pure magnesium metal solution, the magnesium component in the metal solution reacts with the alkaline earth metal to form a magnesium (alkaline earth metal) compound. In the present invention, since the alkaline earth metal oxide is CaO, Mg 2 Ca is formed. Further, the oxygen which originally constitutes CaO is either O 2 discharged to the outside of the metal solution, or is combined with Mg to form MgO, and is discharged as scum (refer to Reaction Formula 1 below).
反應式1Reaction formula 1
Pure Mg+CaO->Mg(Matrix)+Mg2 Ca...[生成O2 +生成MgO浮渣]Pure Mg+CaO->Mg(Matrix)+Mg 2 Ca...[Generate O 2 + to form MgO scum]
若為鎂金屬溶液，則金屬溶液中的鎂成分與鹼土金屬進行反應而生成鎂(鹼土金屬)化合物或鋁(鹼土金屬)化合物。另外，鎂的合金元素與鎂或鋁一起與鹼土金屬生成化合物。在本發明中，若鹼土金屬氧化物為CaO，則生成Mg2 Ca、Al2 Ca或(Mg、Al、其他合金元素)2 Ca。另外，原來構成CaO的氧，與純鎂的情況一樣，或變成O2 排出至金屬溶液外，或與Mg結合生成MgO，從而以浮渣形式排出(請參考下面的反應式2)。In the case of a magnesium metal solution, the magnesium component in the metal solution reacts with the alkaline earth metal to form a magnesium (alkaline earth metal) compound or an aluminum (alkaline earth metal) compound. Further, an alloying element of magnesium forms a compound with an alkaline earth metal together with magnesium or aluminum. In the present invention, when the alkaline earth metal oxide is CaO, Mg 2 Ca, Al 2 Ca or (Mg, Al, other alloying elements) 2 Ca is formed. Further, the oxygen constituting CaO originally is discharged in the form of scum as in the case of pure magnesium, or O 2 is discharged to the outside of the metal solution, or is combined with Mg to form scum (refer to Reaction Scheme 2 below).
反應式2Reaction formula 2
Mg Alloy+CaO->Mg Alloy(Matrix)+(Mg2 Ca+Al2 Ca+(Mg、Al、其他很近元素)2 Ca}...[生成O2 +生成MgO浮渣]Mg Alloy+CaO->Mg Alloy(Matrix)+(Mg 2 Ca+Al 2 Ca+(Mg, Al, other very close elements) 2 Ca}...[Generate O 2 + to form MgO scum]
如上所述，本發明提供比現有技術的鎂合金生產方法更經濟的鎂合金製造工藝。鹼土金屬(例如，Ca)相對於鹼土金屬氧化物(例如，CaO)高價的合金元素，成為使鎂合金價格上升的主要原因。另外，藉由利用鹼土金屬氧化物替代鹼土金屬添加至鎂或鎂合金中，從而較容易形成合金。與此相反，不直接添加鹼土金屬(例如，Ca)，而藉由添加化學穩定性好的鹼土金屬氧化物(例如，CaO)，從而獲得相同或更高的合金生成效果。即，藉由添加至Mg金屬溶液的CaO的還原反應生成的Ca，將作為Mg或Mg合金的元素。As described above, the present invention provides a magnesium alloy manufacturing process which is more economical than the prior art magnesium alloy production method. An alloying element of an alkaline earth metal (for example, Ca) with respect to an alkaline earth metal oxide (for example, CaO) is a major cause of an increase in the price of a magnesium alloy. Further, it is easier to form an alloy by using an alkaline earth metal oxide instead of an alkaline earth metal added to the magnesium or magnesium alloy. On the contrary, the alkaline earth metal (for example, Ca) is not directly added, and the same or higher alloy formation effect is obtained by adding an alkaline earth metal oxide (for example, CaO) having good chemical stability. That is, Ca produced by the reduction reaction of CaO added to the Mg metal solution will be an element of Mg or Mg alloy.
另外，若將鹼土金屬(Ca)直接投入鎂或鎂合金中，則在鎂合金中發生一定量的鹼土金屬的熔化，但若採用本發明的技術，則在添加鹼土金屬氧化物(CaO)時，較之直接添加鹼土金屬(Ca)的情況，不發生熔化或量很少。較之直接添加Ca，藉由CaO間接添加的方式，更容易形成包括Al2 Ca在內的金屬間化合物。因此，為提高鎂合金的物性，需添加一定百分比以上的鹼土金屬，但若添加鹼土金屬氧化物製造鎂合金，則因相當量的鹼土金屬直接形成鎂或Al的金屬間化合物(例如，Mg2 Ca或Al2 Ca)，從而較之直接添加Ca，其物性得到提高。包括Al2 Ca在內的其他金屬間化合物的形成，其約95%以上形成於結晶粒界，而其餘約5%形成於結晶粒內。Further, when the alkaline earth metal (Ca) is directly introduced into the magnesium or magnesium alloy, a certain amount of alkaline earth metal is melted in the magnesium alloy. However, when the alkaline earth metal oxide (CaO) is added by the technique of the present invention, In the case where the alkaline earth metal (Ca) is directly added, no melting or a small amount occurs. An intermetallic compound including Al 2 Ca is more easily formed by indirect addition of CaO than the direct addition of Ca. Therefore, in order to improve the physical properties of the magnesium alloy, it is necessary to add a certain percentage or more of alkaline earth metal. However, if an alkaline earth metal oxide is added to produce a magnesium alloy, an equivalent amount of an alkaline earth metal directly forms an intermetallic compound of magnesium or Al (for example, Mg 2 ). Ca or Al 2 Ca), whereby the physical properties are improved as compared with the direct addition of Ca. The formation of other intermetallic compounds including Al 2 Ca is formed at about 95% of the crystal grain boundaries, and the remaining about 5% is formed in the crystal grains.
圖4a為作為比較例利用AZ91D的壓鑄產品微細構造照片，而圖4b和4c為在本發明中，在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金的壓鑄產品微細構造照片。在本發明中，「添加CaO」是指在添加之後經過還原反應過程。在進行冷凍室(Cold Chamber)壓鑄之後拍攝細微構造照片。較之本發明比較例，合金的組織細緻而緻密。這樣的傾向隨添加於Mg合金的CaO的含量的增加而變得明顯。這是隨CaO的添加均勻分佈形成相的Al2 Ca或其他相形成物[(Mg2 Ca及(Mg、Al、其他合金元素)2 Ca)]所造成的。4a is a micro-structured photograph of a die-cast product using AZ91D as a comparative example, and FIGS. 4b and 4c are micro-structures of a die-cast product of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D in the present invention. photo. In the present invention, "addition of CaO" means a process of undergoing a reduction reaction after the addition. A fine structure photograph was taken after performing a cold chamber die casting. The microstructure of the alloy is finer and denser than the comparative example of the present invention. Such a tendency becomes apparent as the content of CaO added to the Mg alloy increases. This is caused by the uniform distribution of CaO to form Al 2 Ca or other phase formers [(Mg 2 Ca and (Mg, Al, other alloying elements) 2 Ca)].
圖5a至圖5d為本發明中向AM60B合金的金屬溶液添加0.45wt%的CaO製造而成的鎂合金的EDS成分分析圖片。如圖所示，形成Al2 Ca相並抑制β-Mg17 Al12 相的形成。5a to 5d are diagrams showing an EDS component analysis of a magnesium alloy produced by adding 0.45 wt% of CaO to a metal solution of an AM60B alloy in the present invention. As shown, the Al 2 Ca phase is formed and the formation of the β-Mg 17 Al 12 phase is suppressed.
Al和Ca的存在區域的分佈也類似。即，從添加於鎂金屬溶液的CaO分離的Ca與Al生成化合物。因此，現有Mg-Al類合金中存在的脆性大的β-Mg17 Al12 相的形成被抑制，並提高鎂合金的柔軟性，而與此同時，藉由Al2 Ca相的形成，增加合金的強度。The distribution of the presence regions of Al and Ca is also similar. That is, Ca separated from CaO added to the magnesium metal solution and Al to form a compound. Therefore, the formation of the brittle large β-Mg 17 Al 12 phase existing in the existing Mg-Al alloy is suppressed, and the flexibility of the magnesium alloy is improved, and at the same time, the alloy is increased by the formation of the Al 2 Ca phase. Strength of.
圖6a為商用AM60B合金，而圖6b至圖6d為向AM60B添加CaO製造而成的鎂合金的拉伸試片破損面SEM圖像照片。Fig. 6a is a commercial AM60B alloy, and Figs. 6b to 6d are SEM image photographs of a tensile test piece of a tensile test piece of a magnesium alloy produced by adding CaO to AM60B.
因合金內的氣孔等鑄造缺陷，常見酒窩(Dimple)結構(凹陷的部分)。與此相比，添加CaO製造而成的合金(在圖6b中向AM60B中添加0.25wt%的CaO，在圖6c中向AM60B中添加0.58wt%的CaO，而在圖6d中向AM60B中添加0.98wt%的CaO)的拉伸試片破損面的酒窩結構明顯減少。即，隨CaO的添加，合金的氣孔減少，且氧化物、夾雜物等減少，從而減少鑄造缺陷。Due to casting defects such as pores in the alloy, the Dimple structure (the recessed portion) is common. In contrast, an alloy made of CaO was added (0.25 wt% of CaO was added to AM60B in Fig. 6b, 0.58 wt% of CaO was added to AM60B in Fig. 6c, and to AM60B in Fig. 6d). The dimple structure of the damaged surface of the 0.98 wt% CaO) tensile test piece was significantly reduced. That is, with the addition of CaO, the pores of the alloy are reduced, and oxides, inclusions, and the like are reduced, thereby reducing casting defects.
圖7為向鎂合金中添加氧化鈣時的常溫屈服強度(TYS)圖表。而實線表示未添加CaO的AM60B合金的常溫屈服強度。Fig. 7 is a graph showing the room temperature yield strength (TYS) when calcium oxide is added to a magnesium alloy. The solid line indicates the room temperature yield strength of the AM60B alloy to which CaO is not added.
在實施例中，向AM60B鎂合金添加0.2wt%至1.0wt%範圍的氧化鈣進行了實驗。In the examples, experiments were carried out by adding calcium oxide in the range of 0.2 wt% to 1.0 wt% to the AM60B magnesium alloy.
如圖7所示，若向鎂合金中添加0.3wt%的氧化鈣，則常溫屈服強度約為130至137[MPa]；若向鎂合金中添加0.7wt%的氧化鈣，則常溫屈服強度約為151至168[MPa]；而若向鎂合金中添加0.9wt%的氧化鈣，則屈服強度約為156[MPa]。在所添加的CaO的量在0.3wt%至0.7wt%範圍內時，隨CaO的量的增加，常溫屈服強度也一同增加。As shown in FIG. 7, if 0.3% by weight of calcium oxide is added to the magnesium alloy, the room temperature yield strength is about 130 to 137 [MPa]; if 0.7% by weight of calcium oxide is added to the magnesium alloy, the room temperature yield strength is about It is 151 to 168 [MPa]; and if 0.9% by weight of calcium oxide is added to the magnesium alloy, the yield strength is about 156 [MPa]. When the amount of CaO added is in the range of 0.3 wt% to 0.7 wt%, the room temperature yield strength also increases as the amount of CaO increases.
上述隨氧化鈣wt%的屈服強度如下表2所示：The above yield strength with wt% of calcium oxide is shown in Table 2 below:
因此，如上表2所示，在向鎂合金添加0.7wt%的氧化鈣的附近，常溫屈服強度(TYS)最好。Therefore, as shown in Table 2 above, the room temperature yield strength (TYS) is the best in the vicinity of adding 0.7 wt% of calcium oxide to the magnesium alloy.
圖8為向鎂合金中添加氧化鈣時的常溫拉伸強度(UTS)圖表。而實線表示未添加CaO的AM60B合金的常溫拉伸強度。Fig. 8 is a graph showing the normal temperature tensile strength (UTS) when calcium oxide is added to a magnesium alloy. The solid line indicates the room temperature tensile strength of the AM60B alloy to which CaO was not added.
在實施例中，向AM60B鎂合金添加0.2wt%至1.0wt%範圍的氧化鈣進行了實驗。In the examples, experiments were carried out by adding calcium oxide in the range of 0.2 wt% to 1.0 wt% to the AM60B magnesium alloy.
如圖8所示，若向鎂合金中添加0.3wt%的氧化鈣，則常溫拉伸強度約為205至230[MPa]；若向鎂合金中添加0.7wt%的氧化鈣，則常溫拉伸強度約為240至261[MPa]；而若向鎂合金中添加0.9wt%的氧化鈣，則拉伸強度約為245至251[MPa]。在所添加的CaO的量在0.3wt%至0.7wt%範圍內時，隨CaO的量的增加，常溫拉伸強度也一同增加。As shown in Fig. 8, if 0.3% by weight of calcium oxide is added to the magnesium alloy, the tensile strength at room temperature is about 205 to 230 [MPa]; if 0.7% by weight of calcium oxide is added to the magnesium alloy, stretching at room temperature The strength is about 240 to 261 [MPa]; and if 0.9% by weight of calcium oxide is added to the magnesium alloy, the tensile strength is about 245 to 251 [MPa]. When the amount of CaO added is in the range of 0.3% by weight to 0.7% by weight, the tensile strength at room temperature increases as the amount of CaO increases.
上述隨氧化鈣wt%的常溫拉伸強度如下表3所示：The above-mentioned normal temperature tensile strength with the weight % of calcium oxide is as shown in Table 3 below:
因此，如上表3所示，在向鎂合金添加0.5至0.8wt%範圍的氧化鈣時，常溫拉伸強度最好。Therefore, as shown in the above Table 3, when calcium oxide is added in the range of 0.5 to 0.8% by weight to the magnesium alloy, the tensile strength at room temperature is the best.
圖9為向鎂合金中添加氧化鈣時的常溫延伸率(elongation)圖表。而實線表示未添加CaO的AM60B合金的常溫延伸率。Fig. 9 is a graph showing the room temperature elongation when calcium oxide is added to a magnesium alloy. The solid line indicates the room temperature elongation of the AM60B alloy to which CaO is not added.
在實施例中，向AM60B鎂合金添加0.2wt%至1.0wt%範圍的氧化鈣進行了實驗。In the examples, experiments were carried out by adding calcium oxide in the range of 0.2 wt% to 1.0 wt% to the AM60B magnesium alloy.
如圖9所示，若向鎂合金中添加0.3wt%的氧化鈣，則常溫延伸率約為6至10[%]；若向鎂合金中添加0.7wt%的氧化鈣，則常溫延伸率約為13至15[%]；而若向鎂合金中添加0.9wt%的氧化鈣，則延伸率約為13至14[%]。在所添加的CaO的量在0.3wt%至0.7wt%範圍內時，隨CaO的量的增加，常溫延伸率也一同增加。As shown in FIG. 9, when 0.3% by weight of calcium oxide is added to the magnesium alloy, the room temperature elongation is about 6 to 10 [%]; if 0.7% by weight of calcium oxide is added to the magnesium alloy, the room temperature elongation is about It is 13 to 15 [%]; and if 0.9% by weight of calcium oxide is added to the magnesium alloy, the elongation is about 13 to 14 [%]. When the amount of CaO added is in the range of 0.3% by weight to 0.7% by weight, as the amount of CaO increases, the room temperature elongation also increases.
上述隨氧化鈣wt%的常溫延伸率如下表4所示：The above-mentioned normal temperature elongation with wt% of calcium oxide is shown in Table 4 below:
因此，如上上表4所示，在向鎂合金添加0.5至0.8wt%範圍的氧化鈣時，延伸率最好。Therefore, as shown in the above Table 4, the elongation is the best when calcium oxide is added in the range of 0.5 to 0.8% by weight to the magnesium alloy.
下表5表示根據本發明製造而成的鎂合金的機械特性平均值。各資料藉由約200個實驗測量值取平均值。Table 5 below shows the average mechanical properties of the magnesium alloys produced in accordance with the present invention. Each data was averaged by approximately 200 experimental measurements.
如圖7、圖8及圖9所示，利用添加至Mg金屬溶液的CaO的還原反應製造而成的Mg合金，較之未添加CaO的Mg合金，其常溫屈服強度、常溫拉伸強度及常溫延伸率都得到提高。另外，這些常溫機械物性的提高，隨CaO的添加量的增加而增加。而且，這些傾向在CaO的添加量在0.3wt%至0.7wt%時變得最明顯。這些常溫機械物性的增加，是因為隨CaO的添加，形成Mg2 Ca或Al2 Ca或(Mg、Al)2 Ca化合物的相。As shown in FIG. 7 , FIG. 8 and FIG. 9 , the Mg alloy produced by the reduction reaction of CaO added to the Mg metal solution has a normal temperature yield strength, a normal temperature tensile strength and a normal temperature as compared with a Mg alloy not added with CaO. The elongation rate has been improved. In addition, the improvement of these mechanical properties at room temperature increases as the amount of CaO added increases. Moreover, these tendencies become most apparent when the amount of addition of CaO is from 0.3% by weight to 0.7% by weight. The increase in these mechanical properties at room temperature is due to the formation of a phase of Mg 2 Ca or Al 2 Ca or (Mg, Al) 2 Ca compound with the addition of CaO.
圖10為比較根據本發明製造而成的鎂類合金和現有合金的常溫屈服強度和和常溫延伸率的圖表。Fig. 10 is a graph comparing the room temperature yield strength and the room temperature elongation of a magnesium-based alloy and a conventional alloy manufactured according to the present invention.
如圖所示，現有的AM(添加鋁和錳的鎂合金)和AE(添加向鋁添加稀土類金屬的鎂合金)的常溫屈服強度和常溫延伸率成反比。As shown in the figure, the conventional AM (magnesium alloy to which aluminum and manganese are added) and AE (magnesium alloy to which rare earth metal is added to aluminum) are inversely proportional to the room temperature yield strength and the room temperature elongation.
添加CaO的鎂合金，雖然其常溫屈服強度增加，但其常溫延伸率也增加。一般而言，如圖表的圓點(Mg-Al-RE合金)或三角形點(Mg-Al-Mn合金)的傾向，若延伸率增加，則合金的屈服強度將減少。即，一般而言，延伸率的增加，將犧牲屈服強度。但如上述圖表的矩形點(添加CaO的鎂合金)所示，若添加CaO，則隨常溫延伸率的增加，常溫屈服強度也一同增加。The magnesium alloy to which CaO is added, although its room temperature yield strength increases, its room temperature elongation also increases. In general, as the dot of the graph (Mg-Al-RE alloy) or the triangular point (Mg-Al-Mn alloy) tends to increase, if the elongation increases, the yield strength of the alloy will decrease. That is, in general, the increase in elongation will sacrifice the yield strength. However, as shown by the rectangular point of the above graph (magnesium alloy to which CaO is added), when CaO is added, the room temperature yield strength also increases as the room temperature elongation increases.
圖11為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的硬度的圖表。利用各合金進行冷凍室(Cold Chamber)壓鑄之後，測量鉻氏硬度。添加CaO的Mg合金的硬度大於未添加CaO的合金的硬度。另外，隨CaO添加量的增加，其常溫硬度也增加。在本發明中，「添加CaO」是指在添加之後經過還原反應過程。Fig. 11 is a graph comparing the hardness of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not doped with CaO. The chromium hardness was measured after a cold chamber die casting using each alloy. The hardness of the Mg alloy to which CaO is added is greater than the hardness of the alloy to which CaO is not added. In addition, as the amount of CaO added increases, the room temperature hardness also increases. In the present invention, "addition of CaO" means a process of undergoing a reduction reaction after the addition.
圖12為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫屈服強度的圖表。利用熱室(Hot Chamber)壓鑄法製造試片之後，測量常溫屈服強度。添加CaO的Mg合金的常溫屈服強度大於未添加CaO的合金的常溫屈服強度。較之未添加CaO之前，添加0.7wt%的CaO之後，常溫屈服強度約增加15%左右。另外，隨CaO添加量的增加，其常溫屈服強度也增加。Fig. 12 is a graph comparing the room temperature yield strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not added with CaO. After the test piece was produced by a hot chamber (Hot Chamber) die-casting method, the room temperature yield strength was measured. The normal temperature yield strength of the Mg alloy to which CaO is added is greater than the room temperature yield strength of the alloy to which CaO is not added. The normal temperature yield strength increased by about 15% after adding 0.7 wt% of CaO before adding CaO. In addition, as the amount of CaO added increases, the room temperature yield strength also increases.
圖13為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫拉伸強度的圖表。利用熱室(Hot Chamber)壓鑄法製造試片之後，測量常溫拉伸強度。Fig. 13 is a graph comparing the normal temperature tensile strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not containing CaO. After the test piece was produced by a hot chamber die casting method, the room temperature tensile strength was measured.
添加CaO的Mg合金的常溫拉伸強度大於未添加CaO的合金的常溫拉伸強度。較之未添加CaO之前，添加0.7wt%的CaO之後，常溫拉伸強度約增加14%左右。另外，隨CaO添加量的增加，其常溫拉伸強度也增加。The normal temperature tensile strength of the Mg alloy to which CaO is added is greater than the normal temperature tensile strength of the alloy to which CaO is not added. The tensile strength at room temperature increased by about 14% after adding 0.7 wt% of CaO before CaO was added. In addition, as the amount of CaO added increases, the tensile strength at room temperature also increases.
圖14為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫延伸率的圖表。添加CaO的Mg合金的常溫延伸率大於未添加CaO的合金的常溫延伸率。較之未添加CaO之前，添加0.7wt%的CaO之後，常溫延伸率約增加三倍左右。另外，隨CaO添加量的增加，其常溫延伸率也增加。Fig. 14 is a graph comparing the room temperature elongation of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not containing CaO. The room temperature elongation of the Mg alloy to which CaO is added is larger than the room temperature elongation of the alloy to which CaO is not added. The normal temperature elongation was increased by about three times after the addition of 0.7 wt% of CaO before the addition of CaO. In addition, as the amount of CaO added increases, the room temperature elongation also increases.
圖15為表示在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫延伸率和常溫屈服強度關係的圖表。添加CaO的Mg合金的常溫延伸率大於未添加CaO的合金的常溫延伸率。另外，隨CaO添加量的增加，其常溫屈服強度和常溫延伸率同時增加。Fig. 15 is a graph showing the relationship between the room temperature elongation and the room temperature yield strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not containing CaO. The room temperature elongation of the Mg alloy to which CaO is added is larger than the room temperature elongation of the alloy to which CaO is not added. In addition, as the amount of CaO added increases, the room temperature yield strength and the room temperature elongation increase simultaneously.
如上所述，本發明向商用鎂合金中添加CaO，從而使鎂合金的組織變細並形成Al2 Ca及Mg2 Ca或(Mg、Al、其他合金元素)2 Ca相等。另外，抑制脆性大的β-Mg17 Al12 相的形成，大幅減少鑄造缺陷。結果，可藉由添加CaO利用還原反應間接使Ca形成合金，因此，可同時增加鎂合金的常溫強度和常溫柔軟性。As described above, the present invention adds CaO to a commercial magnesium alloy to make the structure of the magnesium alloy fine and form Al 2 Ca and Mg 2 Ca or (Mg, Al, other alloying elements) 2 Ca. In addition, the formation of a β-Mg 17 Al 12 phase having a large brittleness is suppressed, and casting defects are greatly reduced. As a result, Ca can be indirectly alloyed by the reduction reaction by adding CaO, and therefore, the room temperature strength and the room temperature flexibility of the magnesium alloy can be simultaneously increased.
上述實施例僅用以說明本發明而非限制，本領域的普通技術人員應當理解，可以對本發明進行修改、變形或者等同替換，而不脫離本發明的精神和範圍，其均應涵蓋在本發明的申請專利範圍範圍當中。The above-described embodiments are only intended to illustrate the invention and are not to be construed as limiting the scope of the invention. Within the scope of the patent application scope.
圖1為本發明鎂類合金製造方法順序圖；Figure 1 is a sequence diagram of a method for producing a magnesium alloy according to the present invention;
圖2為在本發明中，添加於鎂金屬溶液中的氧化鈣(CaO)的解離順序圖；2 is a dissociation sequence diagram of calcium oxide (CaO) added to a magnesium metal solution in the present invention;
圖3為在本發明中，藉由對鎂金屬溶液上部層的攪拌使氧化鈣(CaO)解離的模式圖；Figure 3 is a schematic view showing the dissociation of calcium oxide (CaO) by stirring the upper layer of the magnesium metal solution in the present invention;
圖4a為作為比較例利用AZ91D的壓鑄產品微細構造照片；圖4b和4c為在本發明中，在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金的壓鑄產品微細構造照片；4a is a photograph of a fine structure of a die-cast product using AZ91D as a comparative example; and FIGS. 4b and 4c are photographs of a micro-structure of a die-cast product of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D in the present invention. ;
圖5a至圖5d為根據本發明鎂類合金製造方法製造而成的鎂合金的EDS實驗結果照片；5a to 5d are photographs of EDS experimental results of a magnesium alloy produced by the method for producing a magnesium alloy according to the present invention;
圖6a至圖6d為根據本發明製造而成的鎂合金的拉伸試片破損面SEM圖像照片；6a to 6d are SEM image photographs of the fracture surface of the tensile test piece of the magnesium alloy manufactured according to the present invention;
圖7為在本發明中，為了與不使用CaO的鎂合金的常溫屈服強度進行比較，以不同CaO添加量製造而成的鎂合金的常溫屈服強度測量圖表；Figure 7 is a graph showing the measurement of the normal temperature yield strength of a magnesium alloy produced by different CaO addition amounts in comparison with the normal temperature yield strength of a magnesium alloy not using CaO in the present invention;
圖8為在本發明中，為了與不使用CaO的鎂合金的常溫拉伸強度進行比較，以不同CaO添加量製造而成的鎂合金的常溫拉伸強度測量圖表；8 is a graph showing a measurement of a normal temperature tensile strength of a magnesium alloy produced by different CaO addition amounts in comparison with a normal temperature tensile strength of a magnesium alloy not using CaO in the present invention;
圖9為在本發明中，為了與不使用CaO的鎂合金的常溫延伸率進行比較，以不同CaO添加量製造而成的鎂合金的常溫延伸率測量圖表；9 is a graph showing a normal temperature elongation measurement of a magnesium alloy produced by different CaO addition amounts in comparison with a room temperature elongation of a magnesium alloy not using CaO in the present invention;
圖10為在本發明中，比較以不同CaO添加量製造而成的鎂合金的常溫延伸率和常溫屈服強度和不使用CaO的鎂合金的常溫延伸率和常溫屈服強度的圖表；Figure 10 is a graph comparing the normal temperature elongation and the normal temperature yield strength of a magnesium alloy produced by different CaO addition amounts and the normal temperature elongation and the normal temperature yield strength of a magnesium alloy not using CaO in the present invention;
圖11為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫硬度的圖表；11 is a graph comparing normal temperature hardness of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not added with CaO;
圖12為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫屈服強度的圖表；12 is a graph comparing normal temperature yield strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not added with CaO;
圖13為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫拉伸強度的圖表；13 is a graph comparing normal temperature tensile strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not added with CaO;
圖14為比較在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫延伸率的圖表；14 is a graph comparing normal temperature elongation of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not added with CaO;
圖15為表示在AZ91D中添加0.3wt%和0.7wt%的CaO製造而成的Mg合金和未添加CaO的AZ91D Mg合金的常溫延伸率和常溫屈服強度關係的圖表。Fig. 15 is a graph showing the relationship between the room temperature elongation and the room temperature yield strength of a Mg alloy produced by adding 0.3 wt% and 0.7 wt% of CaO to AZ91D and an AZ91D Mg alloy not containing CaO.
Claims (11)
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| KR1020100028151A KR101147655B1 (en) | 2010-03-29 | 2010-03-29 | Magnesium alloy for normal temperature and manufacturing method thereof |
| KR1020110001557A KR101367894B1 (en) | 2011-01-06 | 2011-01-06 | Magnesium alloy for normal temperature |
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| TW201202435A TW201202435A (en) | 2012-01-16 |
| TWI460280B true TWI460280B (en) | 2014-11-11 |
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| US4705561A (en) * | 1986-01-27 | 1987-11-10 | The Dow Chemical Company | Magnesium calcium oxide composite |
| IL125681A (en) * | 1998-08-06 | 2001-06-14 | Dead Sea Magnesium Ltd | Magnesium alloy for high temperature applications |
| RU2215056C2 (en) * | 2001-12-26 | 2003-10-27 | Открытое акционерное общество "АВИСМА титано-магниевый комбинат" | Magnesium-based alloy and a method for preparation thereof |
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| AU2011233968A1 (en) | 2012-10-18 |
| EP2374906B1 (en) | 2017-03-15 |
| EP2374906A1 (en) | 2011-10-12 |
| AU2011233968B2 (en) | 2014-10-16 |
| CA2794897A1 (en) | 2011-10-06 |
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| PL2374906T3 (en) | 2017-08-31 |
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