CN114406284A - Low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy - Google Patents
Low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy Download PDFInfo
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- CN114406284A CN114406284A CN202210232311.5A CN202210232311A CN114406284A CN 114406284 A CN114406284 A CN 114406284A CN 202210232311 A CN202210232311 A CN 202210232311A CN 114406284 A CN114406284 A CN 114406284A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
Abstract
The invention relates to the field of alloy materials, and provides a low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy, which consists of Mo, Si, B and Ti, wherein the content of Si is 10-12%, the content of B is 8-10%, the content of Ti is 10-15%, and the balance is Mo; the invention realizes the improvement of the strength and the high-temperature oxidation resistance of the existing Mo-Si-B alloy and the reduction of the density through the design of alloy components, and the provided alloy material consists of an alpha-Mo phase and Mo5SiB2Phase and Mo3Si phase composition, Ti solid-soluble in Mo5SiB2Phase and Mo3The Si phase forms solid solution strengthening, has high strength and thermal stability and excellent mechanical property, and has certain density reduction while retaining the advantages of high melting point and high strength of the existing Mo-Si-B series materialLow, and the high-temperature oxidation resistance is obviously improved, and the requirements of light weight and excellent high-temperature performance of materials in modern industry can be met.
Description
Technical Field
The invention belongs to the field of alloys, and particularly relates to a low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy.
Background
With the progress of science and technology and the development of industry, the high temperature phenomenon is more and more common in the industrial production life of people. In the process of exploring new high-temperature alloys, molybdenum-based alloys have entered the sight of people due to their excellent properties. The Mo-Si-B alloy has high melting point, good high-temperature strength and high-temperature creep resistance, so that the Mo-Si-B alloy has the potential of replacing nickel-based alloy and becoming a new-generation high-temperature structural material.
However, because of the high molybdenum content of the molybdenum alloy, the density value of the alloy is large, the alloy is easy to be oxidized in a high-temperature environment, and the Mo element in the alloy can generate volatile MoO during oxidation3. Light alloy elements with high oxygen affinity are usually added into a Mo-Si-B alloy system to realize modification, so that the density of the Mo-Si-B alloy is reduced and the high-temperature oxidation resistance of the Mo-Si-B alloy is improved on the premise of keeping the characteristics of high temperature resistance and high strength of the Mo-Si-B alloy, and the requirements of light weight and more excellent high-temperature performance of materials in modern industry are met.
Disclosure of Invention
The invention aims to exert the advantages of high temperature resistance and high strength of Mo-Si-B alloy, solve the problems of high density and poor high-temperature oxidation resistance of the Mo-Si-B alloy, and provide a low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy material by adding an alloy element Ti.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
A low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy consists of four elements, namely molybdenum (Mo), silicon (Si), boron (B) and titanium (Ti), wherein the atomic percentage of silicon is 10-12%, the atomic percentage of boron is 8-10%, the atomic percentage of titanium is 10-15%, and the balance is molybdenum; the alloy consists of alpha-Mo phase and Mo5SiB2Phase and Mo3And (4) Si phase composition.
Compared with the prior art, the invention has the following advantages:
(1) the invention discloses a low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy, which is mainly obtained by adding an alloy element Ti into a Mo-Si-B alloy, wherein the alloy is prepared from alpha-Mo and Mo5SiB2And Mo3Three-phase composition of Si, Ti is mainly solid-soluble in Mo5SiB2And Mo3In the Si phase, solid solution strengthening is formed, and the alloy is improvedMechanical properties of gold.
(2) The density value of the alloy is 8.63g/cm3～8.82g/cm3The density of the Mo-12Si-8B alloy is 9.43g/cm3In contrast, its density values are significantly reduced.
(2) The compressive strength of the alloy in the process of room temperature compression is more than 2800MPa, which is higher than 2678MPa of the prior Mo-12Si-8B alloy.
(3) The alloy shows good high-temperature oxidation resistance in the oxidation process at 1100 ℃, and compared with the existing Mo-12Si-8B alloy, the oxidation weight loss is 28.9-45.6% of that of the Mo-12Si-8B alloy after the oxidation at 1100 ℃ for 10h, and the oxidation resistance is obviously improved.
Drawings
FIG. 1 is a graph showing the results of X-ray diffraction analysis of Mo-12Si-8B-15Ti alloys in examples 1 and 2.
FIG. 2 is a scanning electron back-scattered photograph of the Mo-12Si-8B-15Ti alloy of example 1.
Detailed Description
In order that the present disclosure may be more readily understood, the following description illustrates the present disclosure by way of specific examples.
Example 1
The present example is a Mo-12Si-8B-15Ti alloy, which is composed of four elements, Mo, Si, B, and Ti, wherein the relative atomic percent content of Mo is 65%, the relative atomic percent content of Si is 12%, the relative atomic percent content of B is 8%, and the relative atomic percent content of Ti is 15%. The Mo-12Si-8B-15Ti alloy consists of alpha-Mo and Mo5SiB2And Mo3Three-phase composition of Si, Ti is mainly solid-soluble in Mo5SiB2And Mo3In the Si phase, as shown in FIGS. 1 and 2.
The purity of Mo, Si and Ti powder raw materials is higher than 99.9%.
The purity of the powder raw material of B is higher than 99.95%.
The Mo-12Si-8B-10Ti alloy is prepared by a laser additive manufacturing technology, and specifically comprises the following steps:
(1) according to the components of Mo-12Si-8B-15Ti (at%), Mo powder with the purity of 99.9% and the particle size of 5-10 μm, Si powder with the purity of 99.9% and the particle size of 10-15 μm, B powder with the purity of 99.5% and the particle size of 2-10 μm and Ti powder with the purity of 99.9% and the particle size of 10-15 μm are weighed and mixed.
(2) Putting the weighed materials into a ball mill, and performing ball milling and mixing for 6 hours to obtain uniformly mixed powder; the ball milling pot and the milling balls used for ball milling are made of agate materials; the ball-material ratio is 3:1, and the rotating speed of the ball mill is 300 r/min. And putting the mixed powder into a vacuum drying oven at 60 ℃ for drying for 4 hours.
(3) 304 stainless steel is used as a substrate, 1 wt% of PVA (polyvinyl alcohol) is added into the uniformly mixed powder to be used as a binder to be uniformly mixed, the uniformly mixed powder is laid on a metal substrate after rust removal and oil removal through a self-made mould, and a preset layer with the thickness of 1mm is formed after vacuum drying.
(4) Using a fiber laser processing system, setting laser process parameters: the laser power is 850W, the scanning speed is 5mm/s, the spot diameter is 2.65mm, and the lap joint rate is 30%. Sending inert protective gas with the gas flow rate of 15L/min. In the environment with oxygen content lower than 1000ppm (0.1%), laser irradiation scans through a preset layer, and the required product is synthesized through in-situ reaction to obtain the single-layer Mo-12Si-8B-15Ti alloy.
(5) And (4) repeating the step (3) and the step (4) by using the obtained single-layer alloy as a matrix, and performing multilayer cladding to obtain the bulk Mo-12Si-8B-15Ti alloy.
The obtained Mo-12Si-8B-15Ti alloy is subjected to X-ray diffraction analysis, the analysis result is shown in figure 1, and as can be seen from figure 1, the obtained product consists of an alpha-Mo phase and Mo5SiB2Phase and Mo3And (4) Si phase composition.
FIG. 2 is a scanning electron back-scattered photograph of a Mo-12Si-8B-15Ti alloy prepared in accordance with the foregoing examples, and the microstructure shown in FIG. 2 further illustrates that the resulting Mo-12Si-8B-15Ti alloy is composed of an α -Mo phase, Mo5SiB2Phase and Mo3Si phase, and Ti element is mainly solid-soluble in Mo5SiB2Phase and Mo3In the Si phase.
The density of the Mo-12Si-8B-15Ti alloy was measured and found to be 8.63g/cm3The density value of the alloy is 9.43g/cm compared with that of the existing Mo-12Si-8B alloy3Compare, decreaseThe reduction is 8.4%.
The high temperature oxidation resistance of the Mo-12Si-8B-15Ti alloy at 1100 ℃ is tested. The final oxidation weight loss of the alloy after 10h of high-temperature oxidation is 28.9 percent of that of the existing Mo-12Si-8B alloy, and the oxidation resistance of the alloy is obviously improved.
The room temperature compression mechanical property test of Mo-12Si-8B-15Ti shows that the compressive strength can reach 2984 MPa.
Example 2
The present example is a Mo-12Si-8B-10Ti alloy, which is composed of four elements, Mo, Si, B, and Ti, wherein the relative atomic percent content of Mo is 70%, the relative atomic percent content of Si is 12%, the relative atomic percent content of B is 8%, and the relative atomic percent content of Ti is 10%. The Mo-12Si-8B-10Ti alloy consists of alpha-Mo and Mo5SiB2And Mo3Three-phase composition of Si, Ti is mainly solid-soluble in Mo5SiB2And Mo3In the Si phase.
The purity of Mo, Si and Ti powder raw materials is higher than 99.9%.
The purity of the powder raw material of B is higher than 99.95%.
The Mo-12Si-8B-10Ti alloy is prepared by a laser additive manufacturing technology, and specifically comprises the following steps:
(1) according to the components of Mo-12Si-8B-10Ti (at%), Mo powder with the purity of 99.9% and the particle size of 5-10 μm, Si powder with the purity of 99.9% and the particle size of 10-15 μm, B powder with the purity of 99.5% and the particle size of 2-10 μm and Ti powder with the purity of 99.9% and the particle size of 10-15 μm are weighed and mixed.
(2) Putting the weighed materials into a ball mill, and performing ball milling and mixing for 6 hours to obtain uniformly mixed powder; the ball milling pot and the milling balls used for ball milling are made of agate materials; the ball-material ratio is 3:1, and the rotating speed of the ball mill is 300 r/min. And putting the mixed powder into a vacuum drying oven at 60 ℃ for drying for 4 hours.
(3) 304 stainless steel is used as a substrate, 1 wt% of PVA (polyvinyl alcohol) is added into the uniformly mixed powder to be used as a binder to be uniformly mixed, the uniformly mixed powder is laid on a metal substrate after rust removal and oil removal through a self-made mould, and a preset layer with the thickness of 1mm is formed after vacuum drying.
(4) Using a fiber laser processing system, setting laser process parameters: the laser power is 900W, the scanning speed is 5mm/s, the spot diameter is 2.65mm, and the lap joint rate is 30%. Sending inert protective gas with the gas flow rate of 15L/min. In the environment with oxygen content lower than 1000ppm (0.1%), laser irradiation scans through a preset layer, and the required product is synthesized through in-situ reaction to obtain the single-layer Mo-12Si-8B-10Ti alloy.
(5) And (4) repeating the step (3) and the step (4) by using the obtained single-layer alloy as a matrix, and performing multilayer cladding to obtain the bulk Mo-12Si-8B-10Ti alloy.
The density of the Mo-12Si-8B-15Ti alloy was measured and found to be 8.82g/cm3The density value of the alloy is 9.43g/cm compared with that of the existing Mo-12Si-8B alloy3Compared with the prior art, the reduction is 6.4%.
The high temperature oxidation resistance of the Mo-12Si-8B-15Ti alloy at 1100 ℃ is tested. The final oxidation weight loss of the alloy after 10h of high-temperature oxidation is 45.6 percent of that of the existing Mo-12Si-8B alloy, and the oxidation resistance of the alloy is obviously improved.
The room temperature compression mechanical property test of Mo-12Si-8B-10Ti shows that the compression strength can reach 2892 MPa.
The foregoing is a description of the preferred embodiments of the present invention. It should be noted that the present invention is not limited to the above embodiments, and any modifications, equivalent replacements, or improvements that can be made to the present invention are included in the protection scope of the present invention when the scope of the claims, the summary of the invention, and the accompanying drawings are satisfied.
Claims (7)
1. A low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy is characterized in that: the alloy consists of four elements of molybdenum, silicon, boron and titanium, wherein the atomic percentage of silicon is 10-12%, the atomic percentage of boron is 8-10%, the atomic percentage of titanium is 10-15%, and the balance is molybdenum.
2. The low density, high strength, high temperature oxidation resistant Mo-Si-B-Ti alloy of claim 1 wherein: when the high-strength high-temperature oxidation-resistant alloy is prepared, the purity of the selected Mo, Si, B and Ti raw materials is not less than 99%.
3. The low density, high strength, high temperature oxidation resistant Mo-Si-B-Ti alloy of claim 1 wherein: the grain size of the selected Mo powder is 5-10 mu m, the grain size of the selected Si powder is 10-30 mu m, the grain size of the selected B powder is 2-10 mu m, and the grain size of the selected Ti powder is 10-15 mu m.
4. A method for preparing a low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy according to any one of claims 1 to 3, which is prepared by the steps of:
(1) weighing Mo, Si, B and Ti powder in proportion, ball-milling and mixing at room temperature, and then heating to 60 ℃ in a vacuum drying oven for drying treatment for 6 hours.
(2) Then, the dried mixed powder is pre-placed on a 304 stainless steel substrate through a binder to form a pre-arranged bonding layer, processing is carried out through a laser processing system, and the high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy is obtained after multilayer cladding. The preparation environment is an argon protection box with oxygen content lower than 1000ppm (0.1%), and the laser process parameters are as follows: the laser power is 800-900W, the scanning speed is 4-6 mm/s, the diameter of a light spot is 2-3 mm, the lap joint rate is 25-40%, and argon is introduced for protection during preparation.
5. The method for preparing the low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy as claimed in claim 4, wherein the ball-to-material ratio is 3:1, the ball-milling rotation speed is 300r/min, and the ball-milling time is 6h during ball-milling and powder mixing.
6. The method of making a low density, high strength, high temperature oxidation resistant Mo-Si-B-Ti alloy of claim 4 wherein the production environment is an argon shield box with oxygen content less than 1000 ppm.
7. The method for preparing the low-density high-strength high-temperature oxidation resistant Mo-Si-B-Ti alloy as claimed in claim 4, wherein the laser process parameters are as follows: the laser power is 800-900W, the scanning speed is 4-6 mm/s, the diameter of a light spot is 2-3 mm, the lap joint rate is 25-40%, and argon is introduced for protection during preparation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094286A (en) * | 2022-06-15 | 2022-09-23 | 华中科技大学 | Rare earth microalloyed Mo-Ti-Si-B-Y ultrahigh temperature material and preparation method thereof |
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| US20060169369A1 (en) * | 2003-09-19 | 2006-08-03 | Plansee Se | Ods molybdenum-silicon-boron alloy |
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| CN111148852A (en) * | 2017-09-26 | 2020-05-12 | 西门子股份公司 | Powder consisting of an alloy comprising molybdenum, silicon and boron, use of the powder and additive manufacturing method for workpieces made from the powder |
| US10894290B1 (en) * | 2014-05-20 | 2021-01-19 | Trelleborg Applied Technologies | Oxidation resistance of molybdenum silicon boride composite |
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- 2022-03-09 CN CN202210232311.5A patent/CN114406284A/en active Pending
Patent Citations (5)
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| US20060169369A1 (en) * | 2003-09-19 | 2006-08-03 | Plansee Se | Ods molybdenum-silicon-boron alloy |
| CN103160701A (en) * | 2011-12-09 | 2013-06-19 | 北京有色金属研究总院 | Preparation method for high-temperature-resistant Mo-Si-B alloy |
| US10894290B1 (en) * | 2014-05-20 | 2021-01-19 | Trelleborg Applied Technologies | Oxidation resistance of molybdenum silicon boride composite |
| CN105506331A (en) * | 2016-01-19 | 2016-04-20 | 西安航天新宇机电设备厂 | Mo-Si-B-Ti-Zr-Al-Nb composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094286A (en) * | 2022-06-15 | 2022-09-23 | 华中科技大学 | Rare earth microalloyed Mo-Ti-Si-B-Y ultrahigh temperature material and preparation method thereof |
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