CN116174729A - Preparation process of manganese-phosphorus-iron-nitrogen alloy powder, manganese-phosphorus-iron-nitrogen alloy powder and application thereof - Google Patents
Preparation process of manganese-phosphorus-iron-nitrogen alloy powder, manganese-phosphorus-iron-nitrogen alloy powder and application thereof Download PDFInfo
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Abstract
The invention provides a preparation process of manganese-phosphorus-iron-nitrogen alloy powder, which comprises the following steps: s1, adding flaky electrolytic manganese and iron powder into an intermediate frequency furnace; s2, closing a furnace mouth protective cover of the intermediate frequency furnace, blowing nitrogen into the intermediate frequency furnace, starting the intermediate frequency furnace, and always keeping the pressure of the nitrogen to be 0.05MPa; s3, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat up to 1550-1650 ℃ and preserving heat; s4, controlling the head of the phosphorus conveyer to descend and to penetrate into the lower surface of the metal liquid; s5, controlling the liquid yellow phosphorus to be gasified in a graphite tube of the phosphorus conveyer and mixed with nitrogen, and then contacting with metal liquid for alloying reaction; s6, after the reaction is completed, pouring the mixture into a powder spraying device for powder preparation, and collecting manganese-phosphorus-iron-nitrogen alloy powder. According to the technical scheme, the prepared manganese phosphorus iron nitrogen alloy powder has high purity, is ultrafine, can be used as an element additive powder of an iron-based powder metallurgy material, and can also be used for refining hypereutectic aluminum silicon alloy materials.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a preparation process of manganese-phosphorus-iron-nitrogen alloy powder, the manganese-phosphorus-iron-nitrogen alloy powder and application thereof.
Background
The iron-based powder metallurgy product is widely applied to various industrial products, and when preparing some special purpose partial powder metallurgy products, a part of elements such as manganese, phosphorus, nitrogen and the like are required to be added so as to improve the performance of the powder metallurgy product and meet the special purposes such as corrosion resistance, gas filtration and the like. However, as the purity requirement of the iron-based powder metallurgy material on the added elements is very high, the impurity content of the composite alloy with various element components is too high at present, so that the use cannot be satisfied, most of the added elements in the iron-based powder metallurgy process can only be added in the form of elemental elements or simple binary alloys, and the development of the iron-based powder metallurgy material is seriously affected.
Near-eutectic and hypereutectic aluminum-silicon-based alloys are widely applied to engine pistons, air-conditioning pistons, die castings and other parts needing wear resistance and light weight. Because of the existence of coarse plate-shaped and needle-shaped positive iron phases, coarse primary crystal silicon and eutectic silicon in the aluminum-silicon-based alloy, the mechanical property of the alloy material is easy to be reduced, and manganese and phosphorus are required to be added for refining the iron phases and the silicon phases. At present, silicon phase refinement mainly adopts a mode of adding a phosphorus simple substance or a phosphorus-containing salt, and iron phase refinement mainly adopts manganese or a mixture of manganese, iron, phosphate and the like, so that the problems of low reaction speed, high burning loss, element segregation, slag inclusion brought to aluminum liquid and the like are easy to occur.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art or related art.
Therefore, an object of the present invention is to provide a process for preparing manganese-phosphorus-iron-nitrogen alloy powder, manganese-phosphorus-iron-nitrogen alloy powder and application thereof, wherein the process for preparing manganese-phosphorus-iron-nitrogen alloy powder is reliable, the purity is high, the impurity content is less than 0.5%, the manganese-phosphorus-iron-nitrogen alloy powder is ultrafine, the particle size of most of the powder is less than 400 meshes, and the manganese-phosphorus-iron-nitrogen alloy powder can be used as an element additive powder of an iron-based powder metallurgy material, can be added with various elements at one time, and is favorable for promoting the development of the iron-based powder metallurgy material. When the Mn-P-Fe-N alloy powder is added into hypereutectic aluminum-silicon alloy, P, mn and N elements can be released simultaneously, the P element can refine a silicon phase, the Mn element can refine an iron phase, the N element can be preferentially combined with a calcium element in alloy liquid, the influence of the calcium element on refining of primary crystal silicon and eutectic silicon is reduced, the refining effect is good, and the application is convenient.
In order to achieve the above object, the technical scheme of the first aspect of the present invention provides a process for preparing manganese-phosphorus-iron-nitrogen alloy powder, comprising the following steps:
s1, adding flaky electrolytic manganese and iron powder into a medium frequency furnace, wherein the iron powder is arranged at the bottom of a hearth of the medium frequency furnace, the flaky electrolytic manganese is arranged at the upper part of the hearth of the medium frequency furnace, and the weight ratio of the flaky electrolytic manganese to the iron powder is (6-30) 1;
s2, closing a furnace mouth protective cover of the intermediate frequency furnace, blowing nitrogen into the intermediate frequency furnace, starting the intermediate frequency furnace after pre-blowing for a certain time, and always keeping the pressure of the nitrogen to be 0.05MPa;
s3, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat up to 1550-1650 ℃ and preserving heat;
s4, controlling the head of the phosphorus conveyer to descend and penetrating 400-600 mm below the surface of the metal liquid;
s5, controlling the liquid yellow phosphorus to be gasified in a graphite tube of the phosphorus conveyer and mixed with nitrogen, and then contacting with metal liquid for alloying reaction;
s6, after the reaction is completed, pouring the mixed liquid obtained by the reaction into a powder spraying device for powder preparation, and collecting manganese-phosphorus-iron-nitrogen alloy powder after the powder is cooled.
Preferably, in step S5, the liquid yellow phosphorus is gasified in the graphite tube of the phosphorus conveyer and mixed with nitrogen, and then contacted with the metal liquid for alloying reaction, and the method specifically comprises the following steps:
s51, firstly, opening a nitrogen conveying pressure valve on the phosphorus conveying equipment, and after pre-conveying gas for a certain time, opening a liquid phosphorus conveying valve of the phosphorus conveying equipment to enable liquid yellow phosphorus to be gasified in a graphite pipe of a phosphorus conveyer and mixed with nitrogen, wherein the pressure of the nitrogen is set to be 0.2MPa-0.4MPa, the flow rate of the nitrogen is 15L/min-25L/min, and the flow rate of the liquid yellow phosphorus is 5L/min-8L/min;
s52, enabling the mixture of liquid yellow phosphorus and nitrogen to contact with metal liquid through the lower part of the graphite tube to carry out alloying reaction, wherein the reaction time of the alloying reaction is controlled to be 20-40 min.
Preferably, in step S2, the pre-blowing time of nitrogen is 10min to 15min.
Preferably, in step S51, the pre-gas delivery time of nitrogen is 2min to 5min.
Preferably, in the step S1, the purity of the adopted flaky electrolytic manganese is more than or equal to 99.9 percent, and the purity of the iron powder is more than or equal to 99 percent.
Preferably, step S6, after the reaction is completed, pouring the mixed liquid obtained by the reaction into a powder spraying device for powder preparation, and collecting manganese-phosphorus-iron-nitrogen alloy powder after the powder is cooled, specifically comprising the following steps:
s61, after the reaction is completed, closing a liquid phosphorus conveying valve on the phosphorus conveying equipment, and continuously purging nitrogen;
s62, controlling a furnace mouth protecting cover of the intermediate frequency furnace and lifting a graphite tube of the phosphorus conveyer;
s63, tilting the intermediate frequency furnace, and pouring the mixed liquid obtained by the reaction into a crucible of a powder spraying device;
s64, starting a powder spraying device to prepare powder;
s65, collecting manganese-phosphorus-iron-nitrogen alloy powder from a collecting tank at the bottom of the powder spraying device after the powder is cooled.
The technical scheme of the second aspect of the invention provides manganese-phosphorus-iron-nitrogen alloy powder prepared by adopting the preparation process of the manganese-phosphorus-iron-nitrogen alloy powder in the technical scheme, which comprises the following elements in percentage by mass: p:40% -50%, fe:2% -6%, N:2% -5%, the total content of impurities is less than 0.5%, and the balance is Mn.
The technical scheme of the third aspect of the invention provides application of the manganese phosphorus iron nitrogen alloy powder as element additive powder of an iron-based powder metallurgy material or for refining iron phases and/or silicon phases in a hypereutectic aluminum-silicon alloy material.
Preferably, the application of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps: melting the aluminum-silicon alloy, and heating the aluminum-silicon alloy liquid to 850-900 ℃; weighing manganese phosphorus iron nitrogen alloy powder according to 0.03% of the weight of the aluminum silicon alloy liquid, adding the manganese phosphorus iron nitrogen alloy powder into the aluminum silicon alloy liquid, keeping the temperature of the aluminum silicon alloy liquid at 850-900 ℃, and reacting for 50-60 min to obtain the refined aluminum silicon alloy material.
Preferably, the application of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps:
adding an aluminum ingot with the purity of 99% into a graphite crucible of an electric furnace, heating and melting, and heating the aluminum liquid to 1100-1300 ℃;
the graphite turbine rotor is deeply penetrated into the liquid surface of the aluminum liquid, a rotor motor is started, a nitrogen protection valve is opened, nitrogen is blown in, wherein the pressure of the nitrogen is set to be 0.2MPa-0.4MPa, and the rotating speed of the rotor is 500 revolutions per minute;
slowly adding manganese-phosphorus-iron-nitrogen alloy powder into aluminum liquid, keeping the temperature of the aluminum liquid at 1100-1300 ℃, and controlling a graphite turbine rotor to continuously stir for 15min, wherein the weight ratio of the manganese-phosphorus-iron-nitrogen alloy powder to an aluminum ingot is 3:20;
after the manganese-phosphorus-iron-nitrogen alloy powder is fully fused with the aluminum liquid, a graphite turbine rotor is put out, and an intermediate alloy ingot is cast;
melting the aluminum-silicon alloy, and heating the aluminum-silicon alloy liquid to 750-800 ℃;
and weighing the intermediate alloy ingot according to 0.2 percent of the weight of the aluminum-silicon alloy liquid, adding the intermediate alloy ingot into the aluminum-silicon alloy liquid, keeping the temperature of the aluminum-silicon alloy liquid at 750-800 ℃, and reacting for 8-10 min to obtain the refined aluminum-silicon alloy material.
The preparation process and application of the manganese-phosphorus-iron-nitrogen alloy powder provided by the invention have the following beneficial technical effects:
(1) The preparation process of the manganese-phosphorus-iron-nitrogen alloy powder provided by the invention has strong operability and high reliability, the purity of the prepared manganese-phosphorus-iron-nitrogen alloy powder is high, the impurity content is less than 0.5%, the manganese-phosphorus-iron-nitrogen alloy powder is superfine, and the granularity of most of the powder is less than 400 meshes. The mixture of gasified yellow phosphorus and nitrogen is input under the surface of the manganese and iron metal liquid by 400-600 mm, and the flow rates of the nitrogen and the liquid yellow phosphorus are controlled, so that the mixture can be subjected to alloying reaction with the manganese and iron metal liquid, and the manganese-phosphorus-iron-nitrogen alloy powder with high purity can be obtained.
(2) The manganese-phosphorus-iron-nitrogen alloy powder provided by the invention can be used as an element additive powder of an iron-based powder metallurgy material, can be added with a plurality of elements at one time, and is beneficial to promoting the development of the iron-based powder metallurgy material. The manganese phosphorus iron nitrogen alloy powder can be used for refining iron phases and/or silicon phases in hypereutectic aluminum silicon alloy materials, when the manganese phosphorus iron nitrogen alloy powder is added into hypereutectic aluminum silicon alloy, P, mn and N elements can be released simultaneously, the phosphorus elements can refine the silicon phases, the manganese elements can refine the iron phases, and the nitrogen elements can be preferentially combined with calcium elements in alloy liquid, so that the influence of the calcium elements on refining of primary crystal silicon and eutectic silicon is reduced, the refining effect is good, and the application is convenient.
(3) The manganese-phosphorus-iron-nitrogen alloy powder provided by the invention can be directly added into aluminum-silicon alloy liquid for dissolution, and can meet the refining requirement of alloy after the reaction time is more than 50 minutes at the temperature of more than 850 ℃, so that the reaction speed is high, and the problems of slag inclusion and the like are not easy to occur.
(4) The manganese-phosphorus-iron-nitrogen alloy powder provided by the invention can be added into a basic aluminum liquid for dissolution, P, mn, N and other elements are released, then an intermediate alloy ingot is cast, and then the intermediate alloy ingot is added into an aluminum-silicon alloy liquid for dissolution for use, and the intermediate alloy ingot can be added when the temperature is more than or equal to 750 ℃, so that the refining requirement of the alloy can be met within 8-10 min, the reaction speed is faster, the slag inclusion and other problems are not easy to occur, and the intermediate alloy ingot can be directly used in an aluminum-silicon alloy heat preservation furnace, and the production efficiency can be greatly improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a metallographic structure contrast electron microscope diagram of ZL109 aluminum-silicon alloy before the manganese-phosphorus-iron-nitrogen alloy powder is added;
FIG. 2 shows a metallographic structure contrast electron microscope image of ZL109 aluminum-silicon alloy after the manganese-phosphorus-iron-nitrogen alloy powder is added;
FIG. 3 shows a comparative electron microscope image of the metallographic structure of ZL109 aluminum-silicon alloy before adding the intermediate alloy ingot (with the manganese-phosphorus-iron-nitrogen alloy powder of the present invention);
fig. 4 shows a comparative electron microscope image of the metallographic structure of ZL109 aluminum-silicon alloy after adding an intermediate alloy ingot (to which the manganese-phosphorus-iron-nitrogen alloy powder of the present invention is added).
Detailed Description
The invention discloses a preparation process of manganese-phosphorus-iron-nitrogen alloy powder, manganese-phosphorus-iron-nitrogen alloy powder and application thereof, and the technical parameters can be properly improved by a person skilled in the art by referring to the content of the manganese-phosphorus-iron-nitrogen alloy powder. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The invention is further illustrated by the following examples:
example 1
The preparation process of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps:
s101, 58kg of flaky electrolytic manganese with the purity of more than or equal to 99.9% and 2kg of iron powder with the purity of more than or equal to 99% are weighed and added into an intermediate frequency furnace, wherein the iron powder is placed at the bottom of a hearth of the intermediate frequency furnace, and the flaky electrolytic manganese is arranged at the upper part of the hearth;
s102, closing a furnace mouth protecting cover of the intermediate frequency furnace, opening a nitrogen valve switch of the protecting gas, introducing nitrogen, pre-blowing for 10min, starting the intermediate frequency furnace, and keeping the nitrogen pressure at 0.05MPa;
s103, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat up to 1550 ℃, and adjusting the power of the intermediate frequency furnace to a heat preservation state;
s104, starting a lifting device at the upper part of a furnace cover of the intermediate frequency furnace to enable the head part of a graphite material hollow phosphorus conveyer of the phosphorus conveying equipment to descend and to be detected 400mm below the surface of the metal liquid;
s105, firstly, a nitrogen conveying pressure valve on the phosphorus conveying equipment is opened, after pre-conveying gas for 2min, a liquid phosphorus conveying valve of the phosphorus conveying equipment is opened, so that liquid yellow phosphorus is gasified in a graphite pipe of a phosphorus conveyer and mixed with nitrogen, alloying reaction is carried out by contacting the lower part of the graphite pipe with alloy liquid, the nitrogen pressure is set to be 0.2MPa, the nitrogen flow is 15L/min, the liquid yellow phosphorus flow is 5L/min, and the alloying reaction time is 20 min;
s106, after the reaction is completed, closing a liquid phosphorus conveying valve on the phosphorus conveying equipment, continuously purging for 2min by using nitrogen, and then lifting a furnace cover and a graphite pipe of the phosphorus conveyer;
s107, tilting the intermediate frequency furnace, pouring the mixed liquid obtained by the reaction into a crucible of a powder spraying device, starting the powder spraying device to prepare powder, and collecting manganese-phosphorus-iron-nitrogen alloy powder from a collecting tank at the bottom of the powder spraying device after the powder is cooled.
The collected manganese phosphorus iron nitrogen alloy powder is detected, and the detection result is as follows:
the granularity of the powder is 78% with 300-400 meshes, 10% with less than 300 meshes and 12% with more than 400 meshes;
component P:40.2%, fe:2.1%, N:2.2%, impurity content 0.33%, and balance Mn element.
The manganese-phosphorus-iron-nitrogen alloy powder has small granularity, ultra-fine and high purity, can be used as an element additive powder of an iron-based powder metallurgy material, can be added with a plurality of elements at one time, and is beneficial to promoting the development of the iron-based powder metallurgy material.
The manganese-phosphorus-iron-nitrogen alloy powder can also release P, mn and N elements simultaneously, can be used for refining iron phases and/or silicon phases in hypereutectic aluminum-silicon alloy materials, has high reaction speed, and is not easy to cause slag inclusion and other problems.
Example 2
The preparation process of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps:
s201, 49kg of flaky electrolytic manganese with the purity of more than or equal to 99.9% and 3.5kg of iron powder with the purity of more than or equal to 99% are weighed and added into an intermediate frequency furnace, wherein the iron powder is placed at the bottom of a hearth of the intermediate frequency furnace, and the flaky electrolytic manganese is arranged at the upper part of the hearth;
s202, closing a furnace mouth protecting cover of the intermediate frequency furnace, opening a nitrogen valve switch of the protecting gas, introducing nitrogen, pre-blowing for 10min, starting the intermediate frequency furnace, and keeping the nitrogen pressure at 0.05MPa;
s203, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat up to 1600 ℃, and adjusting the power of the intermediate frequency furnace to a heat preservation state;
s204, starting a lifting device at the upper part of a furnace cover of the intermediate frequency furnace to enable the head part of a graphite material hollow phosphorus conveyer of the phosphorus conveying equipment to descend and to be detected 400mm below the surface of the metal liquid;
s205, firstly, opening a nitrogen conveying pressure valve on the phosphorus conveying equipment, after pre-conveying gas for 2min, opening a liquid phosphorus conveying valve of the phosphorus conveying equipment, so that liquid yellow phosphorus is gasified in a graphite pipe of a phosphorus conveyer and mixed with nitrogen, and carrying out alloying reaction by contacting the lower part of the graphite pipe with alloy liquid, wherein the nitrogen pressure is set to be 0.3MPa, the nitrogen flow is 20L/min, the liquid yellow phosphorus flow is 6.5L/min, and the alloying reaction time is 30 min;
s206, after the reaction is completed, closing a liquid phosphorus conveying valve on the phosphorus conveying equipment, continuously purging for 2min by using nitrogen, and then lifting a furnace cover and a graphite pipe of the phosphorus conveyer;
s207, tilting the intermediate frequency furnace, pouring the mixed liquid obtained by the reaction into a crucible of a powder spraying device, starting the powder spraying device to prepare powder, and collecting manganese-phosphorus-iron-nitrogen alloy powder from a collecting tank at the bottom of the powder spraying device after the powder is cooled.
The collected manganese phosphorus iron nitrogen alloy powder is detected, and the detection result is as follows:
the granularity of the powder is 80% by 300-400 meshes, 10% by less than 300 meshes and 10% by more than 400 meshes;
component P:45.2%, fe:4.1%, N:3.6%, impurity content 0.31%, and balance Mn element.
The manganese-phosphorus-iron-nitrogen alloy powder has small granularity, ultra-fine and high purity, can be used as an element additive powder of an iron-based powder metallurgy material, can be added with a plurality of elements at one time, and is beneficial to promoting the development of the iron-based powder metallurgy material.
The manganese-phosphorus-iron-nitrogen alloy powder can also release P, mn and N elements simultaneously, can be used for refining iron phases and/or silicon phases in hypereutectic aluminum-silicon alloy materials, has high reaction speed, and is not easy to cause slag inclusion and other problems.
Example 3
S301, 39kg of flaky electrolytic manganese with the purity of more than or equal to 99.9% and 6kg of iron powder with the purity of more than or equal to 99% are weighed and added into an intermediate frequency furnace, wherein the iron powder is placed at the bottom of a hearth of the intermediate frequency furnace, and the flaky electrolytic manganese is arranged at the upper part of the hearth;
s302, closing a furnace mouth protecting cover of the intermediate frequency furnace, opening a nitrogen valve switch of the protecting gas, introducing nitrogen, pre-blowing for 10min, starting the intermediate frequency furnace, and keeping the nitrogen pressure at 0.05MPa;
s303, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat to 1650 ℃, and adjusting the power to a heat preservation state;
s304, starting a lifting device at the upper part of a furnace cover of the intermediate frequency furnace to enable the head part of a graphite material hollow phosphorus conveyer of the phosphorus conveying equipment to descend and to be detected 400mm below the surface of the metal liquid;
s305, firstly, opening a nitrogen conveying pressure valve on the phosphorus conveying equipment, after pre-conveying gas for 2min, opening a liquid phosphorus conveying valve of the phosphorus conveying equipment, so that liquid yellow phosphorus is gasified in a graphite pipe of a phosphorus conveyer and mixed with nitrogen, and carrying out alloying reaction by contacting the lower part of the graphite pipe with alloy liquid, wherein the nitrogen pressure is set to be 0.4MPa, the nitrogen flow is 25L/min, the liquid yellow phosphorus flow is 8L/min, and the alloying reaction time is 40 min;
s306, after the reaction is completed, closing a liquid phosphorus conveying valve on the phosphorus conveying equipment, continuously purging for 2min by using nitrogen, and then lifting a furnace cover and a graphite pipe of the phosphorus conveyer;
s307, tilting the intermediate frequency furnace, pouring the mixed liquid obtained by the reaction into a crucible of a powder spraying device, starting the powder spraying device to prepare powder, and collecting manganese-phosphorus-iron-nitrogen alloy powder from a collecting tank at the bottom of the powder spraying device after the powder is cooled.
The collected manganese phosphorus iron nitrogen alloy powder is detected, and the detection result is as follows:
the granularity of the powder is 81% by 300-400 meshes, 10% by less than 300 meshes and 9% by more than 400 meshes;
component P:49.5% of Fe;5.9%, N:4.9%, impurity content 0.41% and the balance of Mn element.
The manganese-phosphorus-iron-nitrogen alloy powder has small granularity, ultra-fine and high purity, can be used as an element additive powder of an iron-based powder metallurgy material, can be added with a plurality of elements at one time, and is beneficial to promoting the development of the iron-based powder metallurgy material.
The manganese-phosphorus-iron-nitrogen alloy powder can also release P, mn and N elements simultaneously, can be used for refining iron phases and/or silicon phases in hypereutectic aluminum-silicon alloy materials, has high reaction speed, and is not easy to cause slag inclusion and other problems.
Example 4
The application of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps:
s401, melting 100kg of ZL109 aluminum-silicon alloy in a power frequency furnace, and heating the aluminum-silicon alloy liquid to 850-900 ℃;
s402, weighing 0.03kg of manganese-phosphorus-iron-nitrogen alloy powder, wherein the manganese-iron-phosphorus alloy powder comprises the following components in percentage by measurement: p:49%, fe:2.1%, N:5%, impurity content 0.1%, balance Mn element;
s403, keeping the temperature of the aluminum-silicon alloy liquid at 850-900 ℃, adding the weighed manganese-phosphorus-iron-nitrogen alloy powder into the aluminum-silicon alloy liquid, reacting for 50min, sampling at intervals, measuring the phosphorus content in the aluminum-silicon alloy liquid by using a spectrum, and obtaining the refined aluminum-silicon alloy material through metallographic detection when the phosphorus content is 0.012%.
The metallographic structure electron microscope diagram before adding the manganese phosphorus iron nitrogen alloy powder is shown in figure 1, and the metallographic structure electron microscope diagram after adding the manganese phosphorus iron nitrogen alloy powder is shown in figure 2.
As shown in figures 1 and 2, primary silicon in a metallographic structure before adding manganese phosphorus iron nitrogen alloy powder is coarse, eutectic silicon is plate-shaped and the like, primary silicon in the metallographic structure after adding manganese phosphorus iron nitrogen alloy powder is refined, eutectic silicon is short rod-shaped, the manganese phosphorus iron nitrogen alloy powder can simultaneously release P, mn and N elements, the phosphorus element can refine silicon phase, the manganese element can refine iron phase, the nitrogen element can be preferentially combined with calcium element in alloy liquid, the influence of the calcium element on primary silicon and eutectic silicon refinement is reduced, and the refining effect is good. The manganese-phosphorus-iron-nitrogen alloy powder can be directly added into aluminum-silicon alloy liquid for dissolution, the refining requirement of the alloy can be met after the reaction time is more than 50 minutes at the temperature of more than 850 ℃, the reaction speed is high, and the problems of slag inclusion and the like are not easy to occur.
Example 5
The application of the manganese-phosphorus-iron-nitrogen alloy powder comprises the following steps:
s501, weighing 100kg of aluminum ingot with purity of 99%, and 15kg of manganese-phosphorus-iron-nitrogen alloy powder, wherein the manganese-iron-phosphorus alloy powder comprises the following components in percentage by measurement: p:48%, fe:3%, N:4.8%, impurity content 0.2%, and Mn element in balance;
s502, adding an aluminum ingot into a graphite crucible of an electric furnace, heating and melting, and heating aluminum liquid to 1100-1300 ℃;
s503, the graphite turbine rotor is deeply penetrated into the liquid surface of the aluminum liquid (at the position of 1/2 of the liquid surface height), a rotor motor is started, a nitrogen protection valve is opened, nitrogen is blown in, wherein the nitrogen pressure is set to be 0.2MPa-0.4MPa, and the rotor rotating speed is 500 revolutions per minute, so that vortex is generated on the surface of the aluminum liquid;
s504, slowly adding the weighed manganese-phosphorus-iron-nitrogen alloy powder into aluminum liquid by using an automatic feeder, keeping the temperature of the aluminum liquid at 1100-1300 ℃, controlling a graphite turbine rotor to continuously stir for 15min, extracting the graphite turbine rotor after the manganese-phosphorus-iron-nitrogen alloy powder is fully fused with the aluminum liquid, casting an intermediate alloy ingot by using an automatic ingot casting machine, sampling for component analysis, wherein the phosphorus content is 6.19%, the iron content is 0.42%, the nitrogen content is 0.6%, the manganese content is 5.7%, and the balance is aluminum;
s505, melting 100kg of ZL109 aluminum-silicon alloy in a heat preservation furnace, and heating the aluminum-silicon alloy liquid to 750-800 ℃;
s506, weighing 0.2kg of intermediate alloy ingot, adding the intermediate alloy ingot into ZL109 aluminum-silicon alloy liquid, keeping the temperature of the aluminum-silicon alloy liquid at 750-800 ℃, reacting for 8min, sampling at intervals, measuring the phosphorus content in the intermediate alloy ingot by using a spectrum, and obtaining the refined aluminum-silicon alloy material through metallographic detection, wherein the phosphorus content is 0.012%.
The electron microscope image of the metallographic structure before the intermediate alloy ingot is added is shown in figure 3, and the electron microscope image of the metallographic structure after the intermediate alloy ingot is added is shown in figure 4.
As shown in fig. 3 and 4, the primary silicon in the metallographic structure before the intermediate alloy ingot is added is coarse, the eutectic silicon plate-like, etc., and the primary silicon in the metallographic structure after the intermediate alloy ingot is added is refined, and the eutectic silicon is in a short rod shape. When the temperature is more than or equal to 750 ℃, the alloy can be added, the refining requirement of the alloy can be met within 8-10 min, the reaction speed is higher, the problems of slag inclusion and the like are not easy to occur, the alloy can be directly used in an aluminum-silicon alloy heat preservation furnace, and the production efficiency can be greatly improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation process of the manganese-phosphorus-iron-nitrogen alloy powder is characterized by comprising the following steps of:
s1, adding flaky electrolytic manganese and iron powder into a medium frequency furnace, wherein the iron powder is arranged at the bottom of a hearth of the medium frequency furnace, the flaky electrolytic manganese is arranged at the upper part of the hearth of the medium frequency furnace, and the weight ratio of the flaky electrolytic manganese to the iron powder is (6-30) 1;
s2, closing a furnace mouth protective cover of the intermediate frequency furnace, blowing nitrogen into the intermediate frequency furnace, starting the intermediate frequency furnace after pre-blowing for a certain time, and always keeping the pressure of the nitrogen to be 0.05MPa;
s3, after the flaky electrolytic manganese and iron powder are completely melted, controlling the intermediate frequency furnace to heat up to 1550-1650 ℃ and preserving heat;
s4, controlling the head of the phosphorus conveyer to descend and penetrating 400-600 mm below the surface of the metal liquid;
s5, controlling the liquid yellow phosphorus to be gasified in a graphite tube of the phosphorus conveyer and mixed with nitrogen, and then contacting with metal liquid for alloying reaction;
s6, after the reaction is completed, pouring the mixed liquid obtained by the reaction into a powder spraying device for powder preparation, and collecting manganese-phosphorus-iron-nitrogen alloy powder after the powder is cooled.
2. The process for preparing the manganese-phosphorus-iron-nitrogen alloy powder according to claim 1, wherein in the step S5, the liquid yellow phosphorus is gasified in a graphite tube of a phosphorus conveyer and mixed with nitrogen, and then the liquid yellow phosphorus is contacted with a metal liquid for alloying reaction, and the process specifically comprises the following steps:
s51, firstly, opening a nitrogen conveying pressure valve on the phosphorus conveying equipment, and after pre-conveying gas for a certain time, opening a liquid phosphorus conveying valve of the phosphorus conveying equipment to enable liquid yellow phosphorus to be gasified in a graphite pipe of a phosphorus conveyer and mixed with nitrogen, wherein the pressure of the nitrogen is set to be 0.2MPa-0.4MPa, the flow rate of the nitrogen is 15L/min-25L/min, and the flow rate of the liquid yellow phosphorus is 5L/min-8L/min;
s52, enabling the mixture of liquid yellow phosphorus and nitrogen to contact with metal liquid through the lower part of the graphite tube to carry out alloying reaction, wherein the reaction time of the alloying reaction is controlled to be 20-40 min.
3. The process for preparing manganese-phosphorus-iron-nitrogen alloy powder according to claim 1, wherein in the step S2, the pre-blowing time of nitrogen is 10-15 min.
4. The process for preparing manganese-phosphorus-iron-nitrogen alloy powder according to claim 2, wherein the pre-gas transmission time of nitrogen in step S51 is 2-5 min.
5. The process for preparing manganese-phosphorus-iron-nitrogen alloy powder according to claim 1, wherein in the step S1, the purity of the adopted flaky electrolytic manganese is more than or equal to 99.9%, and the purity of the iron powder is more than or equal to 99%.
6. The process for preparing manganese-phosphorus-iron-nitrogen alloy powder according to claim 1, wherein the step S6 is characterized in that after the reaction is completed, the mixed liquid obtained by the reaction is poured into a powder spraying device for powder preparation, and after the powder is cooled, manganese-phosphorus-iron-nitrogen alloy powder is collected, and the process specifically comprises the following steps:
s61, after the reaction is completed, closing a liquid phosphorus conveying valve on the phosphorus conveying equipment, and continuously purging nitrogen;
s62, controlling a furnace mouth protecting cover of the intermediate frequency furnace and lifting a graphite tube of the phosphorus conveyer;
s63, tilting the intermediate frequency furnace, and pouring the mixed liquid obtained by the reaction into a crucible of a powder spraying device;
s64, starting a powder spraying device to prepare powder;
s65, collecting manganese-phosphorus-iron-nitrogen alloy powder from a collecting tank at the bottom of the powder spraying device after the powder is cooled.
7. A manganese phosphorus iron nitrogen alloy powder prepared by the manganese phosphorus iron nitrogen alloy powder preparation process according to any one of claims 1 to 6, characterized by comprising the following elements in mass percent:
p:40% -50%, fe:2% -6%, N:2% -5%, the total content of impurities is less than 0.5%, and the balance is Mn.
8. Use of a manganese phosphorus iron nitrogen alloy powder according to claim 7, characterized in that the powder is added as an element of an iron-based powder metallurgical material or for refining of iron and silicon phases in a hypereutectic aluminium silicon alloy material.
9. The use of the manganese-phosphorus-iron-nitrogen alloy powder according to claim 8, comprising the steps of:
melting the aluminum-silicon alloy, and heating the aluminum-silicon alloy liquid to 850-900 ℃;
weighing manganese phosphorus iron nitrogen alloy powder according to 0.03% of the weight of the aluminum silicon alloy liquid, adding the manganese phosphorus iron nitrogen alloy powder into the aluminum silicon alloy liquid, keeping the temperature of the aluminum silicon alloy liquid at 850-900 ℃, and reacting for 50-60 min to obtain the refined aluminum silicon alloy material.
10. The use of the manganese-phosphorus-iron-nitrogen alloy powder according to claim 8, comprising the steps of:
adding an aluminum ingot with the purity of 99% into a graphite crucible of an electric furnace, heating and melting, and heating the aluminum liquid to 1100-1300 ℃;
the graphite turbine rotor is deeply penetrated into the liquid surface of the aluminum liquid, a rotor motor is started, a nitrogen protection valve is opened, nitrogen is blown in, wherein the pressure of the nitrogen is set to be 0.2MPa-0.4MPa, and the rotating speed of the rotor is 500 revolutions per minute;
slowly adding manganese-phosphorus-iron-nitrogen alloy powder into aluminum liquid, keeping the temperature of the aluminum liquid at 1100-1300 ℃, and controlling a graphite turbine rotor to continuously stir for 15min, wherein the weight ratio of the manganese-phosphorus-iron-nitrogen alloy powder to an aluminum ingot is 3:20;
after the manganese-phosphorus-iron-nitrogen alloy powder is fully fused with the aluminum liquid, a graphite turbine rotor is put out, and an intermediate alloy ingot is cast;
melting the aluminum-silicon alloy, and heating the aluminum-silicon alloy liquid to 750-800 ℃;
and weighing the intermediate alloy ingot according to 0.2 percent of the weight of the aluminum-silicon alloy liquid, adding the intermediate alloy ingot into the aluminum-silicon alloy liquid, keeping the temperature of the aluminum-silicon alloy liquid at 750-800 ℃, and reacting for 8-10 min to obtain the refined aluminum-silicon alloy material.
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