CN114433862A - Molybdenum-rhenium-lanthanum prealloyed powder and preparation method thereof - Google Patents
Molybdenum-rhenium-lanthanum prealloyed powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses molybdenum-rhenium-lanthanum prealloying powder and a preparation method thereof, which comprises the steps of weighing Re and La raw materials according to a general formula Mo-xRe-yLa to prepare an aqueous solution, and heating for full dissolution; adding ammonia water to adjust the pH value of the solution to form suspension containing lanthanum rhenate particles; adding MoO3Mixing the solid-liquid mixture with suspension liquid containing lanthanum rhenate particles, heating and stirring the mixture, and drying the mixture in vacuum to obtain composite oxide powder; and carrying out two-stage reduction on the dried composite oxide powder in a hydrogen atmosphere to prepare Mo-Re-La prealloy powder. The invention realizes the atomic-level mixing of the main additive element Re and the trace additive element La in the Mo powder while overcoming the defects of poor distribution of solid-solid mixed Mo and Re elements, inconsistent liquid-liquid mixed crystallization sequence, larger liquid evaporation capacity and the like. And the powder has fine particle size and high sintering activity.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and relates to molybdenum-rhenium-lanthanum prealloying powder and a preparation method thereof.
Background
The refractory metal molybdenum not only has excellent heat conduction, electric conduction and corrosion resistance, but also has low thermal expansion coefficient, higher hardness and good high-temperature strength, thereby having wide application in the fields of electronic industry, aerospace industry, energy industry and the like. However, the use of pure molybdenum is limited due to its disadvantages of room temperature brittleness, poor processability, poor weldability, etc. The Re element is considered to be the only material which can effectively improve the room temperature brittleness of the molybdenum at present. The rhenium element of 3-50 percent is added into the alloy, and the prepared molybdenum-rhenium alloy can generate a rhenium effect, not only can improve the room temperature brittleness of molybdenum and improve the welding performance, but also can reduce the anisotropy of the processed material, thereby being widely applied to the preparation of components in severe environments such as ultra-high temperature thermal fields, nuclear reactors and the like. However, the Re element in the earth crust is rare and extremely expensive, and trace rare earth La is added into the molybdenum-rhenium alloy2O3The dispersion strengthening effect can be achieved, the toughness of the alloy is improved, the recrystallization temperature of the Mo-Re alloy is greatly improved, and an effective way is provided for reducing the addition amount of Re in the alloy.
The powder metallurgy method is the main method for preparing molybdenum-rhenium-lanthanum alloy at present, and generally comprises the steps of mechanically mixing molybdenum powder, rhenium powder and lanthanum oxide, reducing the mixture by hydrogen, and then pressing and sintering the mixture to prepare the molybdenum-rhenium-lanthanum alloy bulk material. In the alloy, the elements Mo and Re are not distributed uniformly, so that the elements cannot be diffused fully in the sintering process of the alloy, and brittle chi-phase and sigma-phase are formed in the alloy, so that the material performance is deteriorated, and the rhenium effect is weakened. La2O3The particles are unevenly distributed, secondary phase particles are easily aggregated, and finally the dispersion strengthening effect cannot be achieved. In a molybdenum-rhenium-lanthanum alloy system, the proportion of Re is 3-40 wt%, the proportion of La is less than 1 wt%, and the density difference between the two elements and the main molybdenum element is large, so that how to realize high-uniformity mixing among the three elements with the densities and the component contents of Re, La and Mo which are greatly different is the key for fully playing the performance of the material.
At present, in order to solve the problem of homogenization of Mo-Re alloy, molybdenum oxide powder and ammonium rhenate powder are mechanically mixed, then are decomposed and are reduced by hydrogen in the industry to prepare prealloy powder, but in the method, solid powder is still mixed as raw materials, and then Mo and Re elements in the powder are promoted to be homogenized by utilizing thermal diffusion between the Mo and Re elements in the hydrogen reduction process. Compared with the common Mo powder and Re powder, the Mo and Re element distribution homogenization in the powder stage is improved, but the mutual diffusion degree of the Mo and Re elements is limited due to the lower reduction temperature, and the La and Re elements are mixed2O3The mutual diffusion behavior does not exist between the Mo element and the Re element, and the high-uniformity mixing of the Mo element, the Re element and the La element is difficult to realize.
Patent CN 111112641 discloses a preparation method of nano molybdenum-rhenium composite powder, which is to mix ammonium molybdate with an aqueous solution of ammonium rhenate, then dry the mixture by a combustion method to prepare precursor powder, and finally prepare the Mo-Re pre-alloy powder by hydrogen reduction. However, the problem of uniform distribution of La element in Mo and Re powder is still not considered, and the evaporation amount of liquid is large and the cost is high.
Therefore, the development of a high-efficiency, low-cost and high-homogeneity molybdenum-rhenium-lanthanum prealloy powder is a technical problem to be solved in the field at present, which is to fully exert the performance of the molybdenum-rhenium-lanthanum alloy and reduce the usage amount of rhenium in the molybdenum-rhenium-lanthanum alloy.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method of molybdenum-rhenium-lanthanum prealloying powder. The method overcomes the defects of poor distribution of solid-solid mixed Mo and Re elements, inconsistent liquid-liquid mixed crystallization sequence, large liquid evaporation capacity and the like, and realizes the atomic-level mixing of the main additive element Re and the trace additive element La in the molybdenum powder.
The invention is realized by the following technical scheme.
In one aspect of the invention, a preparation method of molybdenum-rhenium-lanthanum prealloying powder is provided, which comprises the following steps:
step 1, weighing raw materials Re and La according to a general formula Mo-xRe-yLa, wherein x is 3-40% and y is 0.1-1% to prepare an aqueous solution with the mass concentration of W, and heating for full dissolution; adding ammonia water to adjust the pH value of the solution to form suspension containing lanthanum rhenate particles;
step 2, according to the mass ratio (1-x-y) of Mo to Re and La, 59-96.9% of MoO3Mixing the solid-liquid mixture with 3.01-41% of suspension liquid containing lanthanum rhenate particles, heating, stirring, and drying in vacuum to obtain composite oxide powder;
and 3, carrying out two-stage reduction on the dried composite oxide powder in a hydrogen atmosphere to prepare Mo-Re-La prealloy powder.
Preferably, the Re raw material is ammonium perrhenate.
Preferably, the La raw material is lanthanum nitrate hexahydrate.
Preferably, in the step 1, the prepared Re and La raw material aqueous solution has the mass concentration W of 20-30%, the heating temperature of 60-80 ℃, and the pH value regulation range of 8-9.
Preferably, in step 1, ammonium rhenate and lanthanum nitrate hexahydrate are adopted to react to prepare lanthanum rhenate suspension with particles of 100-500 nanometers.
Preferably, in step 2, the degree of vacuum is 10 under heating and vacuum stirring-1pa, the stirring and drying temperature is 70-80 ℃, the mixing and drying time is not less than 6h, and the stirring speed is 30-40 r/min.
Preferably, in the step 3, two stages of hydrogen reduction are carried out, wherein the first stage reduction temperature is 300-600 ℃, the reduction time is 4-6 h, and the hydrogen flow is 4-6 m3/h；
The second-stage reduction temperature is 850-1000 ℃, the reduction time is 2-4 h, and the hydrogen flow is 4-6 m3/h。
Preferably, the temperature of the first-stage reduction is increased from 300 ℃ to 600 ℃, the temperature is gradually increased by a temperature gradient of 50-100 ℃, and the temperature is kept for 1 hour in each temperature stage.
In another aspect of the invention, a molybdenum-rhenium-lanthanum prealloyed powder is provided by the above method.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
through mixing ammonium rhenate and lanthanum nitrate liquid-liquid, and through controlling the mass concentration and the PH value of the ammonium rhenate and lanthanum nitrate liquid-liquid, lanthanum in suspension can be separated out by lanthanum rhenate compound nano-scale particles, so that the Re and La elements are mixed at the atomic level, and the La-containing secondary phase particles are guaranteed to be in the range of 100-500 nanometers.
And (3) carrying out solid-liquid mixing on the suspension and solid molybdenum trioxide, and controlling a mixing and drying process to ensure the uniform distribution of nano suspension particles in the molybdenum matrix.
By the aid of a gradient-rich first-stage reduction process and second-stage reduction temperature control, oxygen elements in Re and Mo can be alternately reduced and eliminated by hydrogen gradually in the same temperature range, mutual diffusion behavior of Mo and Re element powder at relatively low temperature can be accelerated, Re elements can be reduced from an oxidation state to a metal state and then can be dissolved in Mo powder particles in an atomic state, and the purpose of uniform mixing of Mo and Re element atomic levels is achieved.
Due to the adoption of the gradient temperature design, the reduction time at high temperature is short, the granularity of the powder is fine, and the aim of atomic-level mixing of three elements of Mo, Re and La is finally achieved by matching with Re and La which are already realized in the previous suspension process.
In the preparation process of the precursor, the Re and La elements are mixed in a compound mode to realize high uniformity. In the subsequent crystallization and reduction process, the step reduction characteristic is reasonably utilized to promote Mo and Re elements to reach atomic level mixing in the hydrogen reduction process, so that the problem of element mixing nonuniformity caused by element density and content difference during solid-solid mixing of oxides is well solved. Meanwhile, because the liquid form is only introduced into the alloying elements (Re and La elements), the main element molybdenum is still added in the form of solid molybdenum oxide, so that the problems of large water evaporation amount and crystallization segregation of different element compounds in the crystallization process after full liquid-liquid mixing can be solved. The whole preparation process is simple, low in energy consumption, green and environment-friendly, and suitable for industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a process flow diagram of the method of the present invention;
FIG. 2 is a diagram showing the morphology and microscopic element distribution of the powder prepared by the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
As shown in fig. 1, the preparation method of the molybdenum-rhenium-lanthanum prealloying powder provided by the invention comprises the following steps:
step 1, weighing raw materials including ammonium perrhenate and lanthanum nitrate hexahydrate to prepare an aqueous solution with the mass concentration of 20-30% according to a general formula Mo-xRe-yLa, wherein x is 3-40% and y is 0.1-1%, and heating to 60-80 ℃ for full dissolution; and adding ammonia water to adjust the pH value of the solution to be 8-9, and reacting ammonium rhenate with lanthanum nitrate hexahydrate to prepare lanthanum rhenate suspension with particles of 100-500 um.
In the step, the ammonium rhenate and the lanthanum nitrate hexahydrate are adopted to react to prepare the ultrafine-particle lanthanum rhenate suspension, and through controlling the pH value and the mass concentration, the smooth crystallization of lanthanum rhenate in the solution can be guaranteed, and the generated lanthanum rhenate compound particles are guaranteed to be in the size range of 100-500 nm. Because Re and La are in the form of fine-particle lanthanum rhenate compound, the size of lanthanum-containing particles is controlled, and the atomic-level mixing of La and Re elements is achieved.
Step 2, according to the mass ratio (1-x-y) of Mo to Re and La, 59-96.9% of MoO3Mixing with 3.01-41% of suspension liquid solid-liquid containing lanthanum rhenate particles, heating, stirring and vacuum drying, wherein the vacuum degree is 10-1pa, the stirring and drying temperature is 70-80 ℃, the mixing and drying time is not less than 6h, and the stirring speed is 30-40 r/min.
In this step, because the solid is mixed with the turbid liquid, the stirring speed and the drying temperature are controlled, so that the liquid and the solid can be fully and uniformly mixed, and the caking phenomenon is avoided. And drying the crystals in a liquidIn-process, MoO in solid form3The powder can be used as nucleation particles of crystals, and the dried oxide powder Re, La and molybdenum elements are fully and uniformly mixed.
Step 3, carrying out two-stage reduction on the dried composite oxide powder in a hydrogen atmosphere, wherein the first-stage reduction temperature is 300-600 ℃, the first-stage reduction temperature is increased from 300 ℃ to 600 ℃, the temperature is gradually increased by a temperature gradient of 50-100 ℃, the temperature of each temperature stage is kept for 1h, the reduction time is 4-6 h, and the hydrogen flow is 4-6 m3H; the second-stage reduction temperature is 850-1000 ℃, the reduction time is 2-4 h, and the hydrogen flow is 4-6 m3/h。
In the step, two-stage reduction plays an important role in powder alloying and granularity control. Because the targeted temperature interval setting can ensure that all the Re in the powder is reduced when the first-stage reduction is finished, and MoO3Is only reduced into MoO2The purpose of (1). The temperature gradient is set to ensure that the process of reducing molybdenum oxide and ammonium rhenate by hydrogen is gradually and alternately carried out, and the alternate reduction process can promote the mutual diffusion behavior between elements, thereby ensuring that Re metal in the powder can be dissolved in MoO after the first-stage reduction is finished2In (3), atomic level mixing is achieved. On the basis, MoO is matched with a proper two-stage reduction process2The oxygen element in the alloy is fully reduced by hydrogen under the condition of metal Re element atom mixing, the high-temperature mutual diffusion effect of Mo and Re metal is further accelerated, and the atomic-level mixing of Re, Mo and La elements in the powder stage is realized while the aggregation and the growth of powder particles are avoided.
The invention is further illustrated by the following specific examples.
Example 1
The preparation method of the Mo-3Re-0.1La composite powder comprises the following steps:
step 1, preparing lanthanum rhenate suspension
4.322g of ammonium rhenate and 0.311g of lanthanum nitrate hexahydrate are weighed respectively according to the preparation of 100g of composite powder, 18.532g of water is added according to the solution mass concentration of 20%, the mixture is heated to 80 ℃, stirred and dissolved, and then cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 8, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, solid-liquid vacuum drying
145.430g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 96.9 percent of MoO is added3Mixing with 3.01% suspension liquid containing lanthanum rhenate particles, heating at 70 deg.C under 30r/min and 10 deg.C under vacuum-1pa, stirring and drying for 6 h.
Step 3, two-step hydrogen reduction
Performing two-stage reduction on the prepared oxide mixture in a hydrogen atmosphere, wherein the one-stage reduction is performed by stages in a tubular furnace, the temperature is respectively maintained for 1h at 300 ℃, 400 ℃, 500 ℃ and 600 ℃, and the hydrogen flow is 4m3H is used as the reference value. The two-stage reduction adopts a tube furnace, the reduction is carried out for 4 hours at 900 ℃, and the hydrogen flow is 4m3And h, cooling and discharging after reduction.
The morphology and element distribution of the prepared powder are subjected to TEM characterization as shown in FIG. 2 (a: powder micro-morphology, b: Mo element distribution, c: Re element distribution, d: La element distribution). The primary particles of the powder are fine, and between 100 and 200nm, Re and La elements are mixed into the molybdenum substrate in an atomic level mode to achieve atomic level mixing. The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 1. The distribution of chemical elements is very uniform from macro analysis and micro analysis, and the Re element is completely dissolved in Mo matrix particles in the powder in a solid manner, but not exists in a simple substance form, so that the generation of a Mo-Re intermediate phase in the sintering process can be well avoided, and the size of La-containing particles can be controlled.
TABLE 1 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 2.98 | 3.01 | 3.02 | 2.99 | 3.01 | 3.01 |
| La，wt％ | 0.099 | 0.098 | 0.101 | 0.100 | 0.100 | 0.101 |
Example 2
The preparation method of the Mo-40Re-1La composite powder comprises the following steps:
step 1, preparing lanthanum rhenate suspension
57.636g of ammonium rhenate and 3.115g of lanthanum nitrate hexahydrate are weighed respectively according to the preparation of 100g of composite powder, 141.75g of water is added according to the solution concentration of 30%, stirring and heating are carried out until the solution is dissolved at 70 ℃, and then the solution is cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 9, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, stirring and vacuum drying
88.549g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 59 percent of MoO is added3Mixing with 41% suspension liquid containing lanthanum rhenate particles, heating at 80 deg.C under 40r/min and 10 deg.C under vacuum-1pa, stirring and drying for 7 h.
Step 3, two-step hydrogen reduction
Performing two-stage reduction on the prepared oxide mixture in a hydrogen atmosphere, wherein the first-stage reduction is performed by stages in a tubular furnace, the temperature is respectively maintained at 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃ for 1h, the total reduction time is 6h, and the hydrogen flow rate is 6m3H is the ratio of the total weight of the catalyst to the total weight of the catalyst. The second-stage reduction adopts a tubular furnace, the reduction is carried out for 6 hours at 1000 ℃, and the hydrogen flow is 6m3And h, cooling and discharging after reduction.
The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 2. The micro distribution of the Re and La elements is very uniform and is consistent with the designed addition amount.
TABLE 2 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 39.86 | 40.32 | 40.11 | 39.97 | 39.89 | 40.21 |
| La，wt％ | 0.998 | 0.999 | 1.010 | 1.005 | 1.003 | 1.002 |
Example 3
The Mo-20Re-0.5La composite powder is prepared by the following specific steps:
step 1, preparing lanthanum rhenate suspension
28.818g of ammonium rhenate and 1.558g of lanthanum nitrate hexahydrate are weighed respectively according to 100g of composite powder, 91.128g of water is added according to the concentration of 25 percent of the solution, the solution is stirred and heated to 80 ℃ for dissolution, and then the solution is cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 8.5, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, stirring and vacuum drying
119.315g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 79.5 percent of MoO is added3Mixing with 20.5% suspension liquid containing lanthanum rhenate particles, heating at 75 deg.C under stirring speed of 35r/min and vacuum degree of 10-1pa, stirring and drying for 7 h.
Step 3, two-step hydrogen reduction
Performing two-stage reduction on the prepared oxide mixture in a hydrogen atmosphere, wherein the first-stage reduction is performed by stages in a tubular furnace, the temperature is respectively maintained at 300 ℃, 380 ℃, 460 ℃, 540 ℃ and 600 ℃ for 1h, the total reduction time is 5h, and the hydrogen flow is 5m3H is used as the reference value. The two-stage reduction adopts a tube furnace, the reduction is carried out for 4 hours at 900 ℃, and the hydrogen flow is 5m3And h, cooling and discharging after reduction.
The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 3. The micro distribution of the Re and La elements is very uniform and is consistent with the designed addition amount.
TABLE 3 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 20.11 | 20.13 | 20.22 | 19.97 | 19.88 | 20.03 |
| La，wt％ | 0.496 | 0.498 | 0.503 | 0.505 | 0.499 | 0.501 |
Example 4
The preparation method of the Mo-10Re-0.3La composite powder comprises the following steps:
step 1, preparing lanthanum rhenate suspension
14.409g of ammonium rhenate and 0.935g of lanthanum nitrate hexahydrate are weighed respectively according to 100g of prepared composite powder, 61.376g of water is added according to the solution concentration of 20%, and the mixture is stirred, heated to 60 ℃ for dissolution and then cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 8.0, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, stirring and vacuum drying
134.624g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 89.7 percent of MoO is added3Mixing with 10.3% suspension liquid containing lanthanum rhenate particles, heating at 60 deg.C under 40r/min and 10% vacuum degree-1pa, stirring and drying for 8 h.
Step 3, two-step hydrogen reduction
Performing two-stage reduction on the prepared oxide mixture in a hydrogen atmosphere, wherein the first-stage reduction is performed by stages in a tubular furnace, the temperature is respectively maintained at 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃ for 1h, the total reduction time is 5h, and the hydrogen flow is 6m3H is used as the reference value. The two-stage reduction adopts a tubular furnace, the reduction is carried out for 2 hours at 850 ℃, and the hydrogen flow is 5m3And h, cooling and discharging after reduction.
The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 4. The micro distribution of the Re and La elements is very uniform and is consistent with the designed addition amount.
TABLE 4 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 10.03 | 10.02 | 9.98 | 9.95 | 10.01 | 10.03 |
| La，wt％ | 0.303 | 0.298 | 0.301 | 0.301 | 0.299 | 0.304 |
Example 5
The preparation method of the Mo-30Re-0.5La composite powder comprises the following steps:
step 1, preparing lanthanum rhenate suspension
43.228g of ammonium rhenate and 1.558g of lanthanum nitrate hexahydrate are respectively weighed according to 100g of prepared composite powder, 179.144g of water is added according to the solution concentration of 20%, and the mixture is stirred, heated to 80 ℃ for dissolution and then cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 8.5, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, stirring and vacuum drying
104.608g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 69.5 percent of MoO is added3Mixing with 30.5% suspension liquid containing lanthanum rhenate particles, heating at 65 deg.C under stirring speed of 35r/min and vacuum degree of 10-1pa, stirring and drying for 7 h.
Step 3, two-step hydrogen reduction
The prepared oxide mixture is subjected to two-stage reduction in hydrogen atmosphere, wherein the first-stage reduction is carried out by stages in a tubular furnace, the temperature is respectively kept at 300 ℃, 400 ℃, 500 ℃ and 600 ℃ for 1h, the total reduction is 4h, and the hydrogen flow is 6m3H is used as the reference value. The two-stage reduction adopts a tube furnace, the reduction is carried out for 3 hours at 900 ℃, and the hydrogen flow is 6m3And h, cooling and discharging after reduction.
The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 5. The micro distribution of the Re and La elements is very uniform and is consistent with the designed addition amount.
TABLE 5 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 30.23 | 30.12 | 29.98 | 29.90 | 30.01 | 30.03 |
| La，wt％ | 0.501 | 0.498 | 0.501 | 0.503 | 0.499 | 0.504 |
Example 6
The preparation method of the Mo-5Re-1La composite powder comprises the following steps:
step 1, preparing lanthanum rhenate suspension
According to the preparation of 100g of composite powder, 7.205g of ammonium rhenate and 1.661g of lanthanum nitrate hexahydrate are respectively weighed, 20.687g of water is added according to the solution concentration of 30%, stirring and heating are carried out until the solution is dissolved at 70 ℃, and then the solution is cooled to room temperature. And then adding ammonia water to adjust the pH value of the solution to 8.5, and preparing a lanthanum rhenate suspension with particles of 100-500 nanometers.
Step 2, stirring and vacuum drying
141.078g of molybdenum trioxide is weighed according to the mass ratio (1-x-y) of Mo to Re and La, and 94 percent of MoO is added3Mixing with 6% suspension liquid containing lanthanum rhenate particles, heating at 75 deg.C under stirring speed of 35r/min and vacuum degree of 10-1pa, stirring and drying for 7 h.
Step 3, two-step hydrogen reduction
Performing two-stage reduction on the prepared oxide mixture in a hydrogen atmosphere, wherein the first-stage reduction is performed by stages in a tubular furnace, the temperature is respectively maintained for 1h at 300 ℃, 370 ℃, 440 ℃, 510 ℃ and 600 ℃, the total reduction time is 5h, and the hydrogen flow is 6m3H is used as the reference value. The two-stage reduction adopts a tube furnace, the reduction is carried out for 5 hours at 1000 ℃, and the hydrogen flow is 6m3And h, cooling and discharging after reduction.
The powder macro-regions were sampled for 6 batches each and tested for the chemical composition of each region as shown in table 6. The micro distribution of the Re and La elements is very uniform and is consistent with the designed addition amount.
TABLE 6 chemical element analysis of different sampled regions
| Element(s) | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 |
| Re，wt％ | 5.05 | 5.02 | 4.98 | 4.95 | 5.01 | 5.03 |
| La，wt％ | 1.003 | 1.012 | 1.003 | 0.998 | 0.993 | 0.990 |
The embodiment shows that the invention can fundamentally solve the difficult problems that the density and the addition amount of three elements in the Mo-Re-La alloy are greatly different, uniform mixing cannot be realized, and the alloy performance is difficult to give full play.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (9)
1. The preparation method of the molybdenum-rhenium-lanthanum prealloying powder is characterized by comprising the following steps of:
step 1, weighing Re and La raw materials according to a general formula Mo-xRe-yLa, wherein x is 3-40% and y is 0.1-1%, preparing the raw materials into an aqueous solution with the mass concentration of W, and heating for full dissolution; adding ammonia water to adjust the pH value of the solution to form suspension containing lanthanum rhenate particles;
step 2, according to the mass ratio (1-x-y) of Mo to Re and La, 59-96.9% of MoO3Mixing the solid-liquid mixture with 3.01-41% of suspension liquid containing lanthanum rhenate particles, heating, stirring, and drying in vacuum to obtain composite oxide powder;
and 3, carrying out two-stage reduction on the dried composite oxide powder in a hydrogen atmosphere to prepare Mo-Re-La prealloy powder.
2. The method for preparing molybdenum-rhenium-lanthanum prealloying powder according to claim 1, wherein the Re raw material is ammonium perrhenate.
3. The method of claim 1, wherein the La raw material is lanthanum nitrate hexahydrate.
4. The method for preparing molybdenum-rhenium-lanthanum prealloying powder according to claim 1, characterized in that in the step 1, the mass concentration of the prepared Re and La raw material aqueous solution is 20-30%, the heating temperature is 60-80 ℃, and the pH value is controlled within 8-9.
5. The method for preparing molybdenum-rhenium-lanthanum prealloying powder according to claim 1, characterized in that in step 1, ammonium rhenate and lanthanum nitrate hexahydrate are used to react to prepare lanthanum rhenate suspension with particles of 100-500 nm.
6. The method for preparing Mo-Re-La prealloyed powder of claim 1 wherein in step 2, the vacuum degree of heating and stirring is 10-1pa, the stirring and drying temperature is 70-80 ℃, the mixing and drying time is not less than 6h, and the stirring speed is 30-40 r/min.
7. The method for preparing the molybdenum-rhenium-lanthanum prealloying powder as claimed in claim 1, wherein in the step 3, two-stage hydrogen reduction is performed, and the temperature of the first reduction is 300-6The reduction time is 4-6 h at 00 ℃, and the hydrogen flow is 4-6 m3/h；
The second-stage reduction temperature is 850-1000 ℃, the reduction time is 2-4 h, and the hydrogen flow is 4-6 m3/h。
8. The method for preparing the molybdenum-rhenium-lanthanum prealloying powder as claimed in claim 7, wherein the temperature of the first reduction stage is raised from 300 ℃ to 600 ℃, the temperature gradient is gradually increased from 50 ℃ to 100 ℃, and the temperature is kept for 1 hour in each temperature stage.
9. A molybdenum rhenium lanthanum prealloyed powder prepared in accordance with the method of any of claims 1-8.
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