Al-Ce Alloy Based Composites

Abstract

MMC’s comprising an Al—RE alloy-based matrix and ceramic, metal and/or intermetallic reinforcement particulates dispersed in the alloy matrix provide improved strength and ductility wherein the reinforcement particulates have a higher melting temperature than the matrix alloy.

Claims

1. A metal matrix composite comprising an Al—RE alloy matrix containing reinforcement particulates having a higher melting temperature than the matrix alloy wherein the metal matrix composite exhibits improved mechanical properties over a temperature range.

2. The composite of claim 1 wherein the alloy matrix comprises about 1 to about 30 weight % RE material where RE material is selected from Ce, La, mischmetal, or any combination thereof, and balance aluminum (Al).

3. The composite claim 2 wherein the alloy matrix comprises about 1 to about 20 weight % RE material.

4. The composite of claim 3 wherein the alloy matrix comprises about 1 to about 18 weight % RE material.

5. The composite of claim 2 wherein the alloy matrix includes one or more additional alloying elements X that include at least one of Mg, Cu, Mn, Ca, Fe, Ni, Zr, Zn, Si, and Ti in an amount of about 1 to about 14 weight %.

6. The composite of claim 1 wherein Al content of the alloy matrix is controlled and represented by: Al content = Al-(18 - α wt %) LRE - α wt% X; where α = total weight (wt)) % of additional alloying elements X between 1 to12 weight % and where LRE is Ce or La or both Ce and La.

6. The composite of claim 1 wherein the reinforcement particulates are present in the alloy matrix in an amount of about 1 to about 40 volume %.

7. The composite of claim 1 wherein the reinforcement particulates comprise at least one of ceramic particulates, metal particulates, and intermetallic particulates having a higher melting temperature than the matrix alloy.

8. The composite of claim 7 wherein the reinforcement particulates comprise at least one of Al.sub.2O.sub.3, Ni.sub.3Al, ZrO.sub.2, SiC, B.sub.4C, CeO.sub.2, La.sub.2O.sub.3, and YSZ having a melting temperature higher than the matrix alloy.

9. The composite of claim 7 wherein the reinforcement particulates have a minimum average dimension that is in the range of 0.01 microns to 250 microns.

10. The composite of claim 1 having improved tensile strength as compared to the matrix alloy devoid of the reinforcement particles.

11. The composite of claim 1 which is at least one of a cast, extruded, thermal sprayed, cold sprayed, additive manufactured, and electrodeposited composite.

12. A method of making the metal matrix composite of claim 1 wherein the reinforcement particulates are added ex-situ in the alloy matrix or are formed in-situ in the alloy matrix.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. 1A shows a sealed copper can containing mixed powder for extrusion by the hot extrusion process (schematically shown FIG. 1B) and as described in Example 1.

[0010] FIG. 2 is a bar graph showing the results of Vicker’s hardness testing the MMC’s prepared in Example 1 with two different reinforcing particles.

[0011] FIG. 3A are backscattered electron (BSE) images and FIG. 3B are SEM images of Al-8%Ce-10%Mg/Al.sub.2O.sub.3 MMC prepared in Example 1 after Vicker’s hardness testing. The Al.sub.2O.sub.3 particles show cracking and fracturing from both extrusion process and hardness indentation, but no cracks are present at the particle/matrix interface, indicating good bonding there. The dashed boxes in the left views in FIGS. 3A and 3B delineate the boundaries of the measurement indentation.

[0012] FIG. 4 is a graph of uniaxial tensile properties of the Al-8%Ce-10%Mg/Al.sub.2O.sub.3 MMC prepared in Example 1 at a strain rate of 5E-4s.sup.-.sup.1 where strong work hardening behavior is observed together with ultimate tensile stress of 375 MPa and elastic modulus of 74 GPa.

[0013] FIG. 5A is an SEM image (scanning electron microscopy) of the Al-8%Ce-10%Mg/Ni.sub.3Al MMC prepared in Example 1 showing an reaction layer between the particles and the alloy matrix after extrusion attributed to the Al-rich alloy matrix reacting with the Ni of the Ni.sub.3Al particles. FIG. 5B is an enlarged SEM of a reinforcement particle of the MMC of Example 1.

[0014] FIG. 6A are BSE images and FIG. 6B are SEM images of the extruded microstructure of the Al-8%Ce-10%Mg/SiC MMC prepared in Example 2 after extrusion.

[0015] FIG. 7 is an SEM image of 3D printed Al—Ce—Mg + YSZ composite with the YSZ reinforcement particles (white phase) distributed in the alloy matrix.

DETAILED DESCRIPTION OF THE INVENTION

[0016] A metal matrix composite (MMC) is provided comprising an Al—RE alloy matrix and reinforcement particulates dispersed in the alloy matrix wherein the reinforcement particulates have a higher melting temperature than the matrix alloy. Such MMC’s exhibit excellent mechanical properties over a wide temperature range such as room temperature up to and above 230° C.

[0017] An illustrative MMC includes an aluminum-rare earth (Al—RE) alloy matrix that generally comprises about 1 to about 30 weight percent (hereafter: wt. %), preferably about 1 to about 20 wt. %, even more preferably about 1 to about 18 wt. %; and even further preferably about 1 to about 17 wt. % RE material where RE is selected from Ce, La, mischmetal, or any combination thereof, and balance aluminum (Al). The Al—RE alloy matrix can optionally include one or more additional alloying elements X that include at least one of Mg, Cu, Mn, Ca, Fe, Ni, Zr, Zn, Si and Ti in an amount of about 1 to about 14 wt. %. U.S. Pat. 9,963,770 describes such Al—RE alloys for use as the alloy matrix as well as natural mischmetal material as an optional source of RE for practice of certain aspects of the present invention, the entire disclosure of which patent is incorporated herein by reference to that end.

[0018] The Al—RE alloy matrix is formulated to include a relatively high weight percentage of a strengthening intermetallic Al.sub.11RE.sub.3 phase (or other intermetallic phases depending on alloy composition) in amounts from about 5 to about 30 wt. % of individual particles where RE is defined above. The alloy matrix is characterized as typically having a microstructure including the strengthening intermetallic Al.sub.11RE.sub.3 phase distributed in an aluminum-rich alloy matrix. The strengthening intermetallic Al.sub.11RE.sub.3 phase is characterized by being present in a relatively high phase fraction and by having closely spaced, fine lath microstructural features and/or rod microstructural features as well as fine lath spacing and is thermally stable as described in aforementioned U.S. Pat. 9,963,770.

[0019] A particular aspect of the present invention embodies a preferred composition wherein the Al content of the alloy matrix is controlled as represented by:

[0020] Al content = Al-(18 - α wt %) LRE - α wt% X where α = total weight (wt)) % of additional alloying elements X between 1 to 12 weight % and where LRE =Ce, La, or Ce+La (i.e. LRE is Ce or La or both Ce and La).

[0021] Illustrative of such alloy matrix compositions include but are not limited to: [0022] Al-16%Ce-2%Mg [0023] Al-9%Ce-6%Cu-3% Mn [0024] Al-8%Ce-10%Mg, where %’s are wt. %’s.

[0025] Certain aspects of the present invention include relatively hard reinforcement particulates in an amount of about 1 to about 40 volume % (or about 1 to about 50 weight %) of the MMC and can comprise ceramic, metal, and/or intermetallic reinforcement particulates of suitable shapes. As mentioned above, the reinforcement particulates have a higher melting temperature than the matrix alloy. Illustrative reinforcement particulates that can be used in practice of aspects of the present invention include, but are not limited to, Al.sub.2O.sub.3, Ni.sub.3Al, ZrO.sub.2, SiC, B.sub.4C, REO such as CeO.sub.2 and La.sub.2O.sub.3, YSZ, and others having a melting temperature higher than the matrix alloy.

[0026] In certain aspects of the present invention the reinforcement particulates have a minimum average dimension (such as minimum average diameter, length, sieve size, etc.) that is in the range of 0.01 microns to 250 microns. Although the Examples set forth below describe adding the reinforcement particulates ex situ (i.e. as an initial separate powder constituent together with a matrix alloy powder), the reinforcement particulates can be formed ex situ by adding the reinforcement particles to an alloy matrix melt or in situ in the alloy matrix by metallurgical reaction during composite processing methods described next.

[0027] Composites pursuant to certain aspects of the present invention can be made by methods that include, but are not limited to, melt processing, powder metallurgy, thermal-mechanical deformation (e.g. extrusion), thermal spray, cold spray, additive manufacturing such as 3D printing, and electrodeposition.

[0028] The following Examples are offered to further illustrate aspects of the present invention but not to limit the scope thereof.

Example 1

[0029] In Example 1, Al-8%Ce-10%Mg (all in wt%) powder that was commercially gas atomized was used to synthesize a series of MMC’s via uniaxial extrusion. Two composites were prepared comprised of Al-8%Ce-10%Mg/Al.sub.2O.sub.3 and the Al-8%Ce-10%Mg/Ni.sub.3Al. The Al.sub.2O.sub.3 and the Ni.sub.3Al reinforcement powders were obtained from commercial vendors.

[0030] The Al-8%Ce-10%Mg powder (< 53 microns particle size after sieving) was mixed with 15 wt% of Ni.sub.3Al (< 45 microns particle size after sieving) and 20 wt% Al.sub.2O.sub.3 (<45 microns particle size after sieving), respectively. Each of the two mixtures of powders 10 was sealed under vacuum in respective Cu cans 12 with an outside diameter of 1.1 inches. Each can 12 placed in a support body 15 was uniaxially extruded through a 0.375 inch die opening 14 (extrusion ratio = 9) at a temperature of 450° C. in extrusion furnace 16, FIG. 1B, to rod shape. After extrusion, the Vickers hardness of the different composites were tested as shown in FIG. 2. The microstructure of the Al.sub.2O.sub.3 reinforced composite after Vickers Hardness testing is shown in FIGS. 3A, 3B. While the ceramic reinforcement particles show clear cracking and fracturing from the indenter tip and possibly the extrusion process itself, no obvious cracking is seen at the interface. Moreover, the microstructure reveals that the Al.sub.11Ce.sub.3 particles in the surrounding alloy matrix have retained a small size despite the high (450° C.) extrusion temperature. These results highlight that the MMC’s pursuant to practice of aspects of the present invention composites are advantageous for use in various aerospace, automotive, and other service applications.

[0031] The uniaxial tensile properties for the Al-8%Ce-10%Mg alloys reinforced with 20 wt% of Al.sub.2O.sub.3 particles is shown in FIG. 4. The composite shows strong work hardening behavior along with a small amount of plastic strain prior to failure. Since the Al.sub.2O.sub.3 particles used in this composite had a large size distribution range up to 45 .Math.m and were irregular in morphology, it is expected that better mechanical performance can be achieved by tailoring the size and morphology of the second-phase particles along with the volume fraction.

[0032] The microstructure of the second phase reinforcement particles for the Al-8%Ce-10%Mg with 15 vol % Ni.sub.3Al is shown in FIGS. 5A, 5B. The reaction between the Ni in the particles in the Al in the matrix phase can be clearly seen at the interface, where a distinct interaction layer is formed. This creates a strong interface between the particles and the matrix, which helps partition the load between the two phases. As with the aforementioned extrusion containing the Al.sub.2O.sub.3 reinforcement particles, the mechanical properties of these composites can also be controlled by tailoring the size, volume fraction and morphology of the particles. Furthermore, the interface can be tailored by optimizing the processing conditions.

Example 2

[0033] In Example 2, Al-8%Ce-10%Mg powder that was commercially gas atomized as used to synthesize a MMC containing about 15 volume % SiC reinforcement particles via uniaxial extrusion using similar extrusion parameters as set forth in Example 1 other than use of a lower extrusion temperature of 350° C. The SiC reinforcement particles (10 micron size after sieving) were purchased from US Research Nanomaterials, Inc.

[0034] FIGS. 6A, 6B show BSE-SEM images (top row) and SE-SEM images (bottom row) of the extruded microstructure at various magnifications. The microstructure comprises the SiC particles (dark particles) dispersed in the alloy matrix. The relatively brighter bands of the extruded microstructure comprise regions of the Al—Ce—Mg powder that was larger in diameter than other particles, and thus, had coarser Al.sub.11Ce.sub.3 phase present. The extruded microstructure of these coarser powders is not as fine (smaller length-scale) as the rest of the matrix. The Vickers Hardness of the extruded samples was measured via 10 different measurements with an average value of 240.5.

Example 3

[0035] In Example 3, Al-8%Ce-10%Mg powder that was commercially gas atomized was used to synthesize a MMC containing about20 weight % of Al.sub.2O.sub.3 particles using similar extrusion parameters as set forth in Example 1.

[0036] The measured Vicker’s hardness of the MMC so produced was 159.4 as compared to the hardness values shown in FIG. 2 of the MMC’s samples prepared in Example 1. The extruded samples were machined into sub-size dogbones for uniaxial tensile testing at a strain rate of 5 x 10.sup.-4 s.sup.-1. The measured ultimate tensile strength of the composite was about 375 MPa.

Example 4

[0037] In this Example, Al—Ce—Mg powders (45-125 microns size distribution) were blended with yttria-stabilized zirconia (YSZ) particles (45-125 microns) and the powder mixture printed using directed energy deposition (DED) additive manufacturing (AM) to provide printed Al—Ce—Mg + YSZ (yttria stabilized zirconia) composites. Referring to FIG. 7, the YZS reinforcement particles (white phase) are seen to be distributed in the Al—Ce—Mg alloy matrix of the composite. In this Example, the ceramic YSZ particles do not alloy with the matrix alloy, but rather provide distinct second-phase particles.

[0038] Moreover, the Al—Ce—Mg + YSZ composites can be made using both powder bed methods (e-beam or laser) as well as DED methods. The reinforcing phase can be a ceramic (YZS, SiC, Al.sub.2O.sub.3 and others) that has much higher melting temperature than Al—Ce matrix alloy.

[0039] Although aspects of the present invention have been described and shown with respect to certain illustrative embodiments, those skilled in the art will appreciate that the invention is not limited to these aspects and that changes and modifications can be made therein within the scope of the invention as set forth in the appended claims.