US20050173029A1

US20050173029A1 - Magnesium-based alloy composition

Info

Publication number: US20050173029A1
Application number: US11/075,101
Authority: US
Inventors: Tetyukhin Valentinovich; Agalakov Vladimirovich; Kornaukhova Fedorovna; Pusohkarev Yuryevich
Original assignee: AVISMA Titanium-Magnesium Works JSC
Current assignee: AVISMA Titanium-Magnesium Works JSC; VSMPO Avisma Corp PSC
Priority date: 2001-12-26
Filing date: 2005-03-08
Publication date: 2005-08-11
Also published as: EP1460142B1; EP1460142A1; CA2458363A1; EP1460142A4; BR0213891A; US20050000605A1; US7135079B2; DE60239081D1; WO2003056050A1; AU2002308806A1; RU2218438C2

Abstract

Magnesium-based alloy compositions that are used in the automotive industry. The invention makes it possible to reduce the production costs of the alloy and to improve the performance characteristics thereof in order to extend the use of said alloy for the automobile industry. The magnesium-based alloy comprises aluminium, zinc, manganese and silicon wherein the constituents specified are in the following components, wt. %: Aluminium—2.5-3.4; Zinc—0.11-0.25; Manganese—0.24-0.34; Silicon—0.8-1.1; and Magnesium—remainder.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 10/496,024, filed May 19, 2004, which, in turn, claims the benefit of PCT/RU02/00189, filed Apr. 22, 2002.

BACKGROUND OF THE INVENTION

1. Field of the Invention
This invention relates generally to magnesium-based alloys and more specifically to magnesium alloy compositions that are for use in the automotive industry.
2. Background Art
There are various alloys developed for special applications including, for example, die casting of automotive components. Among these alloys magnesium-aluminium alloys can be designated as cost-effective and widely used for manufacture of automotive parts, e.g. AM50A alloy (where AM means aluminium and manganese are in the composition of the alloy) containing approx. 5 to 6 wt. % aluminium and manganese traces, and magnesium-aluminium-zinc alloys, e.g. AZ9D (where AZ means aluminium and zinc are in the composition of the alloy) containing approx. 9 wt. % aluminium and 1 wt. % zinc.
The disadvantage of these alloys is their low strength and poor creep resistance at elevated operating temperatures. As a result, the above mentioned magnesium alloys are less suitable for motor engines where some components such as transmission cases are exposed to temperatures up to 150° C. Poor creep resistance of these components can lead to a decrease in fastener clamp load in bolted joints and, hence, to oil leakage.
Known in the present state of art is a magnesium-based alloy (Inventors' certificate No. 442225 issued in Invention Bulletin 33, 1974) containing aluminium, zinc, manganese, and silicon as alloying components in the following amounts:

- Aluminium—6-15 wt. %
- Zinc—0.3-3.0 wt. %
- Manganese—0.1-0.5 wt. %
- Silicon—0.6-2.5 wt. %
- Magnesium—balance.

The disadvantages of this alloy are its low ductility, high hot shortness, and insufficient strength of the alloy which keeps this alloy from automotive applications.
Known presently is another magnesium die cast alloy (“Magnesium alloys” in Collected works of Baikov Institute for Metallurgy edited by Nauka Publishing House, 1978, p. 140-144) which comprises aluminium, zinc, manganese, and silicon as alloying components in the following amounts:

- Aluminium—3.5-5.0 wt. %
- Zinc—under 0.12 wt. %
- Manganese—0.20-0.50 wt. %
- Silicon—0.5-1.5 wt.%
- Copper—under 0.06
- Nickel—0.03 wt. %

The drawback of this alloy is that the quantitative composition of the alloy selected provides poor mechanical properties, in particular, the alloy having a small solidification range is characterized with advanced susceptibility to cracking in case of hindered contraction and bad castability.
A well-known German standard EN 1753-1997 is taken as the closest prior art by its qualitative and quantitative composition and discloses the methods of manufacture of EN MB MgAl2Si and EN MB MgAl4Si alloys. The qualitative analysis of the alloys is the following, in wt. %:

- EN MB MgAl2Si:
- Al—1.9-2.5
- Mn—min 0.2
- Zn—0.15-0.25
- Si—0.7-1.2
- EN MB MgAl4Si (AS41):
- Al—3.7-4.8
- Mn—0.35-0.6
- Zn—max 0.10
- Si—0.6-1.4

The alloys of the above quantitative and qualitative compositions demonstrate better mechanical properties. However, at 150-250° C. these alloys have high creep that keeps these alloys from machine-building applications. Presently known is the method (PCT Patent No. 94/09168) for making magnesium-based alloy that provides for alloying components in a molten state being introduced into molten magnesium. Primary magnesium and alloying components are therefor heated and melted in separate crucibles.
A disadvantage of this method is the need to pre-melt manganese and other alloying elements (at the melting temperature of 1250° C.) that complicates alloy production and process instrumentation.
There are some other methods known (B. I. Bondarev “Melting and Casting of Wrought Magnesium Alloys” edited by Metallurgy Publishing House, Moscow, Russia 1973, pp 119-122) to introduce alloying components using a master alloy, e.g. a magnesium-manganese master alloy (at the alloying temperature of 740-760° C.).
This method is disadvantageous because the alloying temperature should be kept high. This leads to extremely high electric power consumption for metal heating and significant melting loss.
Also known is another method of producing a magnesium-aluminium zinc-manganese alloy (I. P. Vyatkin, V. A. Kechin, S. V. Mushkov in “Primary magnesium refining and melting” edited by Metallurgy Publishing House, Moscow, Russia 1974, pp.54-56, pp.82-93) which is taken as an analogue prototype. This method stipulates various ways for feeding molten magnesium and alloying components such as aluminium, zinc, and manganese. One of these approaches includes simultaneous charging of solid aluminium and zinc into a crucible, then heating above 100° C., pouring in molten primary magnesium and again heating up to 700-710° C. and introducing titanium containing fusion cake together and manganese metal under continuous agitation.
The main shortcoming of the method is in considerable loss of alloying components, resulting in lower recovery of alloying components in magnesium and preventing from producing alloys with specified mechanical properties. Furthermore, this increases the cost of the alloy.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to improve mechanical properties of the alloy and, in particular, to decrease its creep and loss of alloying constituents in manufacturing the alloy.
The invention makes it possible to reduce the production costs of the alloy and to improve the performance characteristics thereof in order to extend the use of said alloy for the automobile industry.
These objects are accomplished due to the fact that the claimed magnesium-based alloy comprises aluminium, zinc, manganese and silicon, wherein the constituents specified are in the following amounts, wt. %:

- Aluminium—2.5-3.4
- Zinc—0.11-0.25
- Manganese—0.24-0.34
- Silicon—0.8-1.1
- Magnesium—balance.

To manufacture the alloy there is a method which consists of loading of alloying components, pouring of molten magnesium, introducing a titanium-containing fusion cake together with a flux agent and continuously agitating. The alloy is soaked and cast. The alloying components of aluminium, zinc, manganese, and silicon are added in the form of a ready-made solid master alloy of aluminium-zinc-manganese-silicon. After being poured in, the magnesium is heated, subjected to ageing and then stirred.
Further, the proportion of the master alloy to magnesium is 1:(18-20).
Further, magnesium is heated up to 720-740° C.
Further, the ageing process lasts for 1-1.5 hrs.
The quantitative composition of the magnesium-based alloy produces better mechanical properties of the alloy.
Aluminium added into magnesium contributes to its tensile strength at ambient temperature and alloy castability. However, it is well-known that aluminium is detrimental to creep resistance and strength of magnesium alloys at elevated temperatures. This results from the case that aluminium, when in higher quantities, tends to combine with magnesium to form great amounts of intermetallic Mg₁₇Al₁₂having a low melting temperature (437° C.) which impairs high-temperature properties of aluminium-based alloys. The aluminium content of 2.5-3.4 wt. % that was chosen for the proposed magnesium-based alloy provides better properties of magnesium-based alloys, such as creep resistance.
The properties of the alloy, especially its castability, are further influenced by zinc content; however, added in large amounts, zinc can lead to cracking. Therefore, proposed zinc content is within 0.11-0.25 wt. % to be optimum for the magnesium-based alloy.
In order to enhance service performance and functionality and expand the scope of application at higher temperatures (up to 150-200° C.) silicon added into the alloy as an active alloying additive to form a metallurgically stable phase of Mg₂Si that is precipitated slightly at grain boundaries and, hence, to increase creep resistance of the alloy at high temperatures. Silicon content of 0.8-1.1 wt. % claimed in accordance with the present invention promotes a decreasing creep level of the magnesium-based alloy.
The alloy is loaded with manganese in the amount of 0.24-0.34 wt. % in order to ensure corrosion resistance.
The alloying components are introduced in the form of the pre-prepared aluminium-zinc-manganese-silicon master alloy, which is added in a certain proportion to magnesium, i.e. 1:(18-20), and this, therefore, enhances recovery of the additives in magnesium, thus lowering losses of expensive chemicals.
It is another difficulty in making alloys with a silicon content that silicon and manganese as alloying components react to form heavy intermetallic phases Mn₃Si and MnSi₂, which deposit at the bottom of crucibles at the end of production process, and this hinders high level of recovery of these components. Thus, a better recovery of the alloying additives can be produced using the pre-prepared aluminium-based master alloy.
With process temperature maintained at 720-740° C. the level of recovery of alloying elements in the magnesium-based alloy can be 98.8-100% in case of aluminium, 68.2-71.1% in case of manganese, 89.3-97.4 in case of silicon, 85.9-94.4% in case of zinc.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preparation of AI—Mn—Si—Zn Master Alloy
Composition: aluminium-matrix, manganese—6.0-9.0 wt. %, silicon—24.0-28.0 vet. %, zinc—2.0-3.0 wt. %, inclusions, in wt. %: iron—0.4, nickel—0.005, copper—0.1, titanium—0.1. The master alloy is produced in ingots.
The master alloy is manufactured in an ‘AIAX’-type induction furnace. A97 grade aluminium (acc. to GOST 11069) is charged in the furnace and heated to 910-950° C.; the master alloy is melted under cryolite flux in the amount of 1-1.5% of the pre-weighted quantity required for the process. Kpl (Krl), grade crystalline silicon is fed in portions in the form of crushed pieces, or wrapped in aluminium foil or wetted with zinc chloride solution to prevent them from oxidation. Silicon is dissolved in small portions and thoroughly stirred. The composition obtained is thereafter added with manganese metal of MH95 grade (Mn95 acc. to GOST 6008) in the form of 100 mm pieces, stirred again and heated up to the temperature within 800-850° C.; finally added with LIl-grade zinc (Z1 acc., to GOST 3640). 16 kg ingots are cast in molds.

EXAMPLE 1

The solid master alloy of Al—Mn—Si—Zn in the form of ingots in the proportion of master alloy to magnesium 1:(18-20) are charged into a preheated crucible of furnace SMT-2. In the same crucible raw magnesium MT90 (MG-90 acc. to GOST 804-93) is poured in the amount of 1.8 tons from a vacuum ladle and is afterwards heated. On reaching 730-740° C. of the metal temperature a heated agitator is placed in the crucible. The alloy is left undisturbed in the crucible for 1-1.5 hrs prior to mixing and then mixed for max. 40-50 min; a titanium-containing fusion cake (TU 39-008) being in the compound with barium flux in the proportion of 1:1 is added, and mixed again; the temperature of the alloy is then reduced to 710-720° C. The alloy produced was left in the crucible for 60 min and thereafter the alloy was sampled for chemical analysis to define Al, Mn, Zn, Si content and impurities. The alloy composition was in wt. %: Al—2.5-3.4, Mn—min 0.23, Si—0.8-1.3, Be—0.0008-0.0012, Zn—min 0.18, Fe—min 0.003.

INDUSTRIAL APPLICABILITY

TABLE 1


Mechanical properties of the magnesium-based alloy at 150° C.

		Mechanical
	Creep test	properties at

Type of alloy	σ, MPa	Creep ratio σ, %	150° C., σ_BMPa

AZ91	45.0	0.82	136
EN MB MgAl₂Si	45.0	0.490	128
(AS 21)
EN MB MgAl₄Si	45.0	0.540	139
AS 31 alloy claimed	45.0	0.143	128

TABLE 2


Level of recovery of alloying elements in magnesium

Constituents	Recovery level, %

Aluminium	100
Manganese	73.5-96.3; at 720-740° C. and time of agitation 40-50 min
	recovery level of manganese is 80-96%
Silicon	80.8-92.5
Zinc	84.8

Tables 1 and 2 illustrate the level of recovery of alloying elements in the magnesium-based alloy depending on the temperature and time of agitation.

Thus, the magnesium-based alloy of said qualitative composition and the method to prepare it improve the mechanical properties of the alloy, particularly, to decrease creep ratio by 3-4 times and reduce production costs due to a better recovery of alloying components in magnesium.
While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.

Claims

1. A magnesium-based alloy containing aluminium, zinc, manganese and silicon, wherein the constituents specified are in the following amounts, wt. %:

Aluminium—2.5-3.4

Zinc—0.11-0.25

Manganese—0.24-0.34

Silicon—0.8-1.1

Magnesium—remainder.

2. The alloy of claim 1, comprising:

a. a master alloy including

i. Al

ii. Zn

iii. Si

iv. Mn;

b. molten Mg that is heated, aged, and stirred; and

c. a Ti-containing fusion cake with a fluxing agent that is continously agitated to form an intermediate composition before cooling, soaking and casting.

3. The alloy of claim 2, wherein the proportion of the master alloy content to magnesium is 1:(18-20).

4. The alloy of claim 2, wherein magnesium is heated up to 720-740° C.

5. The alloy of claim 2, wherein the ageing is carried out within 1-1.5 hrs.

6. The alloy of claim 2 wherein the master alloy is in the form of a ready-made solid master alloy.

7. The alloy of claim 2 wherein the Al in the master alloy is in the amount of 2.5-3.4 wt. %.

8. The alloy of claim 2 wherein the master alloy comprises Si in the amount of 0.8-1.1 wt. %, the Si forming a metallurgically stable phase of Mg₂Si that is precipitated at grain boundaries, thereby improving the mechanical properties of the alloy.

9. The alloy of claim 2 wherein the master alloy comprises Zn in the amount of 0.11-0.25 wt. % for fluidity.

10. The alloy of claim 2 wherein the master alloy comprises Mn in the amount of 0.24-0.34 wt. % for corrosion resistance.

11. The alloy of claim 2 wherein the master alloy comprises a ready-made solid master alloy in a proportion to Mg of 1:(18-20) for the recovery of additives and reducing the loss of chemicals.

12. The alloy of claim 2 wherein respective constituents following heating to 720-740° C., are recovered at these levels: Al (98.8-100%); Mn (68.2-71.1%); Si (89.3-97.4%); and Zn (85.9-94.4%).

13. The alloy of claim 2 wherein the master alloy comprises the following components, wt. %:

Mn—6.0-9.0

Si—24.0-28.0

Zn—2.0-3.0

an inclusion selected from a group consisting of Fe 0.4; Ni 0.005; Cu 0.1;

Ti 0.1 and combinations thereof; and

Al—remainder.

14. A magnesium-based alloy comprising, in wt. %:

aluminum—2.5-3.4

zinc≧0.18

manganese ≧ to 0.23

silicon—0.8-1.3

beryllium—0.0008-0.0012

iron—≧0.003

magnesium—remainder

15. A master alloy comprising in wt. %:

Manganese—6.0 -9.0

Silicon—24.0-28.0

Zinc—2.0-3.0

an inclusion comprising:

Iron—0.4

Nickel—0.005

Copper—0.1 &

Titanium—0.1.

16. The master alloy composition of claim 15 wherein the wt. % ratio of master alloy to magnesium is about 1:(18-20).