Classifications

• • 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

Definitions

• the present invention relates -to a heat resistant magnesium die casting alloy and a d ⁇ e cast product of that alloy.
• BACKGROUND ART In recent years, to deal with -the demand for reduction of the weight of vehicles , greater application of alloys of magnesium, the lightest of the practical metals, has been desired.
• conventional die casting magnesium alloys greatly deform at high temperatures. Not much progress has been made for parts having bolted portions exposed to high temperature environments (120°C or more).
• various heat resistant magnesium die casting alloys have been developed, but it has not been possible to simultaneously improve the heat resistance (high temperature strength and creep resistance) and castability (hot-cracking resistance and die-sticking resistance during die casting) and therefore the range of application has been limited.
• JP-A-2001-316752 has proposed a die casting magnesium alloy comprised of 2 to 6 wt% Al, 0.3 to 2 wt% Ca, 0.01 to 1 wt% Sr, 0.1 to 1 wt% Mn, and the balance of Mg and unavoidable impurities. Due to this, it becomes possible to simultaneously improve the heat resistance and castability and expand the range of application. Even with the magnesium alloy of the above proposal, however, it has not been possible to sufficiently cover the range of applications required, so development of a heat resistant magnesium die casting alloy with further improved combination of heat resistance and castability has been desired.
• the present invention has as its object to provide a heat resistant magnesium die casting alloy simultaneously improved in heat resistance and castability and expanded in range of applications and a die cast product of the same alloy.
• a heat resistant magnesium die casting alloy comprising, by wt%, the following composition: Al: over 6% to not more than 10%, Ca: 1.8 to 5%, Sr: 0.05 to 1.0%, Mn: 0.1 to 0.6%, and Bal: Mg and unavoidable impurities, the ratio Ca/Al of the Ca content to the Al content being 0.3 to 0.5.
• the present invention is characterized by limiting the ratio Ca/Al of the contents of Al and Ca to within a predetermined range so as to improve the combination of the heat resistance and castability over the conventional limits without causing deterioration of characteristics even if adding Al and Ca to high contents considered unsuitable in the past.
• JP-A-2001-316752 sets the upper limit of -the Al content to 6 wt% and the upper limit of the Ca content to 2 wt%.
• the reason for the limitations is explained as being that if the Al content is over 6 wt%, the creep resistance rapidly deteriorates, while if the Ca content exceeds 2 wt%, casting cracks easily occur (see paragraph 0010 to 0012 of the publication).
• FIG. 1 is a graph comparing the retained bolt loads of various types of Mg alloys.
• FIG. 2 is a graph of the relationship between the high temperature retained bolt load and.
• FIG. 3 is a graph of the relationship between the casting crack length and Ca/Al ratio.
• FIGS. 4A and 4B are graphs of the (A) change in corrosion weight loss and (B) change in corrosion rate with respect to the test duration of a salt water spray test for Mg alloys with various RE contents.
• FIG. 5 is a graph of the change in the corrosion rate with respect to the RE content for specific test durations (numbers of days).
• FIGs. 6A and 6B are graphs of the (A) 0.2% proof stress and tensile strength and the (B) elongation in the temperature range of room temperature to 250 °C.
• composition of the heat resistant magnesium die casting alloy of the present invention is limited due to the following reasons. Note that in this description, unless otherwise specified, the "%" in the indications of the content of the components mean "wt%”. [Al: over 6% to not more than 10%] Al raises the strength at room temperature and high temperature by dispersion strengthening (in particular grain boundary strengthening) by forming Al-Ca-based, Al- Sr-based, and Mg-Al-based intermetallic compounds.
• the Ca content 1.8% to 5% under a predetermined range of the Ca/Al ratio, ⁇ t is possible to improve the proof strength and creep resistance over the conventional limits in the copresence with Al.
• the upper limit of the Ca content is made 5%.
• the Ca content is preferably over 2% and not more than 5%, more preferably 2.5 to 3.5%.
• Sr 0.05 to 1.0%
• Sr is added to further improve the effect of prevention of casting cracks and securing creep resistance. To obtain this effect, it is necessary to add Sr to at least 0.05%. The effect becomes greater with increasing the amount of addition. However, even if added over 1.0%, the effect does not increase not much at all.
• Mn 0.1 to 0.6%
• Mn is added to secure a good corrosion resistance. To obtain this effect, it is necessary to make the Mn content at least 0.1%. However, if Mn is present in excess, free Mn precipitates and embrittlement occurs, so the upper limit of the Mn content is made 0.6%.
• the magnesium alloy of the present invention is remarkably improved in corrosion resistance by further adding a rare earth metal (RE) to the above composition in the range of 0.1 to 3%. To realize this effect, it is necessary to make the RE content at least 0.1%. However, if the RE content exceeds 3%, the castability rapidly deteriorates, casting cracks and misruns end up occurring, and a sound casting is not obtained, so the upper limit of the RE content is made 3%.
• the heat resistant magnesium alloy of the present invention is particularly limited to one for die casting. By die casting, a fine network comprised of Al-Ca-based or Al-Sr-based intermetallic compounds is formed and a good heat resistance can be secured.
• the basic process for obtaining a product by applying the alloy of the present invention to die casting is as follows: Alloy metal ⁇ charging into crucible (*1) ⁇ melting ⁇ temperature adjustment ⁇ die casting (*2) ⁇ removal of product *1)
• the crucible used is made of iron. *2)
• the die casting is by a cold chamber, hot chamber, etc.
• the die casting heat resistance magnesium alloy of the present invention is particularly advantageous when applied to parts requiring heat resistance such as parts of automobile engines, in particular, oil pans, headlight covers, etc. and also transmission cases.
• EXAMPLES [Example 1] The following experiment was performed to confirm the effect of improvement of the castability and heat resistance by alloy compositions of the present invention.
• Mg alloys of the compositions of Table 1 were die cast under the following conditions using a 135 ton cold chamber die casting machine.
• the obtained alloy samples were subjected to tensile tests (test temperature: room temperature (RT), 150°C) and measured for crack length at casting and bolt load retention. As the bolt load retention, the retained bolt load was measured under the following conditions. The measurement results are shown all together in Table 2 and Table 3.
• FIG. 1 is a graph showing the high temperature retained bolt loads of different alloy samples
• FIG. 2 the relationship between the high temperature retained bolt load and Ca/Al ratio
• FIG. 3 the relationship between the casting crack length and Ca/Al ratio.
• the retained bolt load increases with increasing the Ca/Al ratio and that to secure the practically required retained bolt load of at least 70%, it is necessary that Ca/Al ratio ⁇ 0.3. From the results of FIG.
• Example 2 The following experiment was performed to confirm the effect of improvement of the corrosion resistance by RE addition in the alloy composition of the present invention.
• the Mg alloys of the compositions of Table 4 were die cast in the same way as in Example 1.
• the alloy compositions of No. 101 to 105 shown in Table 4 were basically comprised (target values) of 7%Al-3%Ca-0.5%Sr- 0.3%Mn with amounts of RE added (target values) of successively 0% (no addition), 0.1%, 0.5%, 2.0%, and 3.0% (analysis values of added RE elements of 0.08%, 0.44%, 1.77%, and 2.68%).
• a Ce-rich (50%) misch metal was used for the RE addition.
• the obtained alloy samples were subjected to salt water spray tests under the following conditions to evaluate the corrosion resistance.
• ⁇ Salt Spray Test Method> 1. Cut out test piece (width 70 mm x length 50 mm x thickness 3 mm) from the die cast product in the as- cast state. 2. Immerse the test piece in acetone and ultrasonically clean it for 15 minutes, then measure its weight (initial weight). 3. Mask the parts of the surface of the test piece finished being measured for weight other than the as-cast surface (test surface). 4. Perform the salt spray test by a 5% NaCl aqueous solution under conditions defined in JIS Z2371. 5.
• FIG. 4A and FIG. 4B show changes in the corrosion weight loss and corrosion rate for different test durations (numbers of days). Compared with the no-RE material 101, the RE-added materials 102 to 105 all had small corrosion weight losses and small corrosion rates. At FIG. 4A showing the change along with time of the corrosion weight loss, the curves are convex upward. In FIG.
• FIG. 5 is a graph of the effects of the RE content on the progression of corrosion.
• the corrosion rate was plotted against the RE content for a test duration of one day and 10 days. At both test durations, the corrosion rate clearly decreases by the addition of 0.08% of RE as compared with no RE (0%). With increasing the amount of addition of 0.44% and 1.77%, the corrosion rate further decreases. However, if increasing the amount of addition to 2.68%, the corrosion rate conversely starts to increase, but even so the corrosion rate is far smaller than with no addition.
• FIGS. 6A and 6B show the (A) 0.2% proof strength and tensile strength and (B) elongation at the test temperature from room temperature to 250°C. At all test temperatures, it was learned that the 0.44% RE material ( ⁇ plot) was provided with similar strength characteristics to the non-addition material (0 plot) .
• FIG. 7 compares the high temperature retained bolt loads of a 0.44% RE material (103), a non-addition material (101), and an AZ91D (typical known heat resistant Mg die casting alloy). The test procedure was the same as that in Example 1.
• the alloy of the present invention is far larger in retained bolt load compared with the conventional use alloy AZ91D regardless of the addition of RE. Further, in the alloys of the present invention, the 0.44% RE material (103) fell in retained bolt load by about 10% compared with the non-addition material (101), but sufficiently secured the practically required at least 70%, so was provided with both the practically sufficient heat resistance and corrosion resistance. Simultaneously, an excellent castability was also provided and it was possible to die cast without any problem. Table 4
• a heat resistant magnesium die casting alloy simultaneously improved in heat resistance and castability and able to be used for a wider range of applications than the past is provided. Further, due to the RE addition, in addition to the heat resistance and castability, the corrosion resistance may also be simultaneously improved.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Molds, Cores, And Manufacturing Methods Thereof (AREA)
• Forging (AREA)
• Continuous Casting (AREA)
• Prevention Of Electric Corrosion (AREA)

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• 2004
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