Molybdenum-based alloy (variants)

FIELD: metallurgy, in particular molybdenum alloys of formula Mo-Si-B of improved oxidation resistance doped by iron, nickel, cobalt, copper or mixture thereof.

SUBSTANCE: invention relates to molybdenum-based alloy and its variants. Molybdenum alloy containing silicium and boron in disclosed, wherein said alloy comprises molybdenum with space-centered cubic lattice and intermetallic phases, as well as one from element compositions selected on the base of points on the next structural diagrams: metal alloy-Si 1.0 mass%-B 0.5 mass %; metal alloy-Si 1.0 mass %-B 4.0 mass %; metal alloy-Si 4.5 mass%-B 0.5 mass %; and metal alloy-Si 4.5 mass %-B 4.0 mass %. Said metal alloy contains molybdenum as the main component and additionally at least one element from group Fe, Ni, Co, Cu in amount of (mass %): Fe 0.01-2.0; Ni 0.01-2.0; Co 0.01-2.0; Cu 0.01-2.0. In another embodiment alloy composition is determined according to the next structural diagrams: Mo-Si 1.0 mass %-B 0.5 mass %; Mo-Si 1.0 mass %-B 4.0 mass %; Mo-Si 4.5 mass %-B 0.5 mass %; and Mo-Si 4.5 mass %-B 4.0 mass %. In additionally alloy contains 0.01-2.0 of at least one element from Fe, Ni, Co, Cu or mixture thereof. Claimed alloys have oxidation resistance at 12000C or above.

EFFECT: molybdenum-based alloys with high oxidation resistance.

3 cl, 3 dwg, 1 tbl, 1 ex

 

The technical field to which the invention relates.

The present invention relates to alloys of Mo-Si-B and first of all to alloys of Mo-Si-B with high resistance to oxidation due to the additives of transition metals selected from the group comprising Fe, Ni, Co, cu, and mixtures thereof.

The level of technology

Molybdenum is characterized by extremely high resistance, and therefore it attracts attention when use of designs intended for operation at high temperatures. However, in most cases, the use of molybdenum and base alloys of molybdenum is limited due to their low resistance to oxidation at high temperatures. The main product in the oxidation of molybdenum in an oxidizing environment is molybdenum trioxide. The molybdenum trioxide is characterized by a high saturated vapor pressure and at temperatures above 1100°F (593,3° (C) is its sublimation at high speed, which leads to rapid loss of metal from the alloy. Thus, the use of molybdenum and base alloys of molybdenum at high temperatures largely limited to use in a non-oxidizing environment with the exception of some forms of use are printed on the surface of the metal coating for protection against oxidation.

In U.S. patent No 5693156 selected as Blige is our analogue this paper describes a new class of alloys of molybdenum, which is resistant to oxidation at high temperature alloys Mo-Si-B with the addition of elements selected from the group comprising C, Hf, Ti, Zr, W, Re, Al, Cr, V, Nb and TA, and in U.S. patent No 5595616 disclosed methods for such alloys.

In such alloys, silicon and boron, which remain in the alloy after evaporation of the original surface layer of molybdenum trioxide, oxidized with the formation of a protective film on the basis of borosilicate. After appropriate processing such alloys exhibit mechanical properties comparable with other similar alloys of molybdenum and characterized by a rather high resistance to oxidation at high temperatures (1500°F-2500°F[815,6°C-1371,1°]). This combination of mechanical properties and resistance to oxidation allows the use of these materials in structures intended for operation at high temperatures.

The oxidation resistance of these alloys Mo-Si-B largely depends on the content of silicon and boron in the alloy. With the increasing content of silicon in the presence of boron increased resistance of the alloy to oxidation, but it also increases the volumetric content of the silicide. High volumetric content of the silicide is not only complicates the processing of the alloy, but also does not allow to obtain an alloy with equivalent the mi mechanical properties compared with other alloys of molybdenum. In patent ‘595 shown that when added to the alloy as the fourth Supplement of a number of elements, namely, Hf, Ti, Zr, W, Re, Al, Cr, V, Nb and TA, are improving the resistance to oxidation of the alloy Mo-Si-B without increasing the volume content of silicide. Alloys containing these additives as the fourth component of the alloy, have a high resistance to oxidation at 2200°F (1204,4°C) and 2500°F (1371,1° (C) in comparison with the ternary alloy of Mo-Si-B containing an equivalent amount of silicide.

Naturally, there is a need to further increase resistance to oxylene alloys Mo-Si-B in a wide temperature range.

In this regard, the main task of the present invention is the development of improved alloys Mo-Si-B, which are characterized by extremely high resistance to oxidation at high temperatures, i.e. above 2200°F (1204,4°C).

The invention

This task is achieved using the method according to the present invention, in which the resistance to oxidation of ternary alloys of Mo-Si-B at high temperatures increases with the inclusion of minor amounts of certain transition metals such as Fe, Ni, Co, si. While the inclusion of the additives described in the prior art, leads to the formation of an oxide coating, which provides protection during the decade, the Cove hours at 2500° F (1371,1° (C), the additive of the present invention result in the formation of the oxide film which provides protection for hundreds of hours (700 hours or more) at 2500°F (1371,1°). A minor amount of additives of these metals in the alloy increases its high-temperature oxidation resistance, with no significant effect on the oxidation resistance of the alloys at low and medium temperatures.

List of drawings and other materials

Figure 1 presents a graph of illustrating the effect of small amounts of transition metals according to the present invention as additives in the alloy resistance to oxidation at 1500°F (815,6°).

Figure 2 presents a graph of illustrating the effect of small amounts of transition metals according to the present invention as additives in the alloy, the oxidation resistance at 2000°F (1093,3°).

Figure 3 presents a graph of illustrating the effect of small amounts of transition metals according to the present invention as additives in the alloy, the oxidation resistance at 2500°F (1371,1°).

Information confirming the possibility of carrying out the invention

Alloys of Mo-Si-B of the present invention obtained when the mixing elements in the following ratio defined by points on f the OIC diagram for systems of ternary alloys: metal - 1.0 wt.% Si - 0.5 wt.% In the metal to 1.0 wt.% Si - 4.0 wt.% In the metal - 4.5 wt.% Si - 0.5 wt.% In metal - 4.5 wt.% Si - 4.0 wt.% In where the metal mainly composed of molybdenum as a main component (more than 50 wt.% molybdenum), and in the alloy additionally contains the following amounts of at least one element from the group of Fe, Ni, Co, si or mixtures thereof. Alloys of molybdenum consist of molybdenum with volume-centered cubic lattice structure and intermetallic phases, and the composition of the alloys is determined by the points on the phase diagram for systems of ternary alloys: alloy metal to 1.0 wt.% Si - 0.5 wt.% In the alloy of the metals to 1.0 wt.% Si - 4.0 wt.% In the alloy of the metals to 4.5 wt.% Si - 0.5 wt.% And alloy metals to 4.5 wt.% Si - 4.0 wt.% In where the metal comprises molybdenum, and the alloy metals" means an alloy of molybdenum with the above transition metals. Small amounts of silicon and boron do not provide satisfactory resistance to oxidation and a higher content leads to the formation of too brittle alloys, which cannot be used in designs. Alloys and obtaining them are described in detail in U.S. patent No 5595616 and 5693156, which are included in this description as a reference.

According to the present invention in the above-mentioned compositions of the alloys in the composition of the metal molybdenum includes one or more of the following transition metal is low as additives, thus, the amount of the additive replaces an equivalent amount of molybdenum.

The content of the element in the final alloy, wt.%
A WIDE RANGEPREPOST. RANGE
Fefrom 0.01 to 2.0from 0.05 to 1.0
Nifrom 0.01 to 2.0from 0.10 to 1.0
Cofrom 0.01 to 2.0from 0.05 to 1.0
Cfrom 0.01 to 2.0from 0.01 to 1.0

According to the present invention, the oxidation resistance of ternary alloys of Mo-Si-B increases in a wide range of temperatures as a result of inclusion in the alloy as additives minor amounts of transition metals. While the inclusion of the additives described in the prior art, leads to the formation of the oxide film which provides protection for tens of hours at 2500°F (1371,1° (C), the additive of the present invention result in the formation of the oxide film which provides protection for hundreds of hours (700 hours or more) at 2500°F (1371,1°). Minor amounts of additives these elements increase high-temperature strength of the alloys to oxidation, for this class is as alloys not observed negative effect on the oxidation resistance at low and medium temperatures. Positive impact minor amounts of additives described is observed not only in the case of alloys, in which the additive of the above elements are included as the fourth component of the alloy, but also in the case of combinations of such additives and alloys that include these additives in combination with the additives of higher order (i.e. systems containing 5 and 6 components).

The increased oxidation resistance of the alloys of the present invention is demonstrated in the following example.

EXAMPLE

Samples for research is obtained by melting 75-100 g components using technologies arc-melting and formation in the horn of hardened copper. The samples are crushed to a powder and utverjdayut by hot isostatic pressing (CIP). Then the pressed material from an alloy of Mo-Si-B cut into pieces and incubated in an air oven at the specified temperature, in the process keeping periodically measure the mass of the samples to determine trends in weight loss. In addition, measure the thickness of the samples before incubation and after final curing in an oven to determine the reduction in thickness. The positive impact of inclusion as an additive a minor amount of transition elements is not limited to alloys, polucen the mi according to the described technology. It is shown that the improved resistance to oxidation is observed for the materials obtained with the use of other technologies.

The trend of mass loss for these types of alloys are presented in figures 1, 2 and 3. As seen in the drawings, for alloys of the present invention there is a considerably increased resistance to oxidation as compared with the alloys of the prior art, particularly at high temperatures above 2000°F (1093,3°C) for extended periods of time.

The present invention may have other embodiments or may be implemented in other ways without deviating from the idea or essence of the invention. Therefore, this embodiment of the invention can be considered in all respects as illustration and not as limitation, and the volume of claims is determined by the attached claims and assumes that it covers all possible changes, the prisoners within the equivalence of concepts.

1. Molybdenum alloy containing silicon and boron, characterized in that it consists of molybdenum with volume-centered cubic lattice and intermetallic phases, and the alloy contains one of the songs of the items selected in the following ratios defined by points on the plots of phase diagrams: alloy metal to 1.0 wt.% Si - 0.5 wt.% In the alloy of the metals to 1.0 wt.% Si - 4,0 the AC.% In, alloy metals to 4.5 wt.% Si - 0.5 wt.% And alloy metals to 4.5 wt.% Si - 4.0 wt.% In where the above-mentioned alloy metal consists mainly of molybdenum as a main component and optionally contains at least one element from the group of Fe, Ni, Co, si in the following amount, wt.%:

Fe from 0.01 to 2.0

Ni of 0.01 to 2.0

With from 0.01 to 2.0

C from 0.01 to 2.0.

2. Molybdenum alloy according to claim 1, characterized in that it contains at least one element from the group of Fe, Ni, Co, si in the following amount, wt.%:

Fe from 0.05 to 1.0

Ni from 0.10 to 1.0

With from 0.05 to 1.0

C) from 0.01 to 1.0.

3. Molybdenum alloy containing silicon and boron, characterized in that it consists of molybdenum with volume-centered cubic lattice and intermetallic phases, and the alloy contains one of the songs of the items selected in the following ratios defined by points on the plots of phase diagrams: molybdenum - 1.0 wt.% Si - 0.5 wt.% In, molybdenum - 1.0 wt.% Si - 4.0 wt.% In, molybdenum - 4.5 wt.% Si - 0.5 wt.% In and molybdenum - 4.5 wt.% Si - 4.0 wt.% In and additionally contains at least one element selected from the group of Fe, Ni, Co, cu, any of which may be contained in an amount of from 0.01 to 2.0 wt.%, or mixtures thereof.



 

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3 cl, 1 tbl, 10 ex

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3 cl, 1 tbl, 10 ex

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3 cl, 3 dwg, 1 tbl, 1 ex

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1 dwg

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