CN111482613B - High-physical-activity aluminum-silicon spherical alloy powder and preparation method and application thereof - Google Patents

High-physical-activity aluminum-silicon spherical alloy powder and preparation method and application thereof Download PDF

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CN111482613B
CN111482613B CN201910072481.XA CN201910072481A CN111482613B CN 111482613 B CN111482613 B CN 111482613B CN 201910072481 A CN201910072481 A CN 201910072481A CN 111482613 B CN111482613 B CN 111482613B
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silicon
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CN111482613A (en
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焦清介
闫石
郭学永
杜风贞
刘大志
张碧
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Tangshan Weihao Magnesium Powder Co ltd
Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0848Melting process before atomisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/086Cooling after atomisation

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Abstract

The invention provides high-physical-activity aluminum-silicon spherical alloy powder and a preparation method and application thereof, belonging to the technical field of metal alloy powder preparation. The aluminum alloy comprises 95-60% of aluminum and 5-40% of silicon by mass; the high-physical activity aluminum-silicon spherical alloy powder has a long-range disordered structure and a non-equilibrium structure, and does not have crystal grains and crystal boundaries. According to the invention, silicon element is added into aluminum, and the melting boiling point of silicon is extremely high, so that the silicon is not easy to melt and volatilize and difficult to ignite; however, silicon has a higher enthalpy of combustion of 35kJ/mol, higher than 31.02kJ/mol for aluminum; therefore, the aluminum and the silicon are combined, the reaction process of the alloy fuel can be slowed down on the premise of not reducing the combustion heat value of the alloy fuel, the after-effect reaction time of explosive explosion is prolonged, the pressure attenuation of shock waves is slowed down, the overpressure of far-field shock waves is improved, and the requirement that the explosive is required to react mildly on some occasions is met.

Description

High-physical-activity aluminum-silicon spherical alloy powder and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal alloy powder preparation, in particular to high-physical-activity aluminum-silicon spherical alloy powder and a preparation method and application thereof.
Background
In recent decades, high power explosives have been studied and developed in various countries, and the general trend is to make explosive formulations with higher latent heat, heat of combustion, theoretical density and oxygen balance. Meanwhile, in order to adapt to the change of the high-strength battlefield environment, the explosive also needs to meet the requirements of low sensitivity, good thermal stability, high action reliability and the like. One effective way to improve the explosive power is metallization of the explosive, and the heat effect of the secondary reaction of the high-energy metal or metal alloy combustion agent and the explosive explosion product is utilized to improve the explosion heat of the explosive. Also, metal combustion agents have varying degrees of influence on the sensitivity and signature of the explosive.
Because the raw materials are rich, the aluminum is safe to use, has higher energy density, volume combustion heat and higher oxidation rate, is often used as a fuel additive and is widely applied to the fields of solid propellants, explosives and pyrotechnic agents. However, when aluminum particles are used as an alloy combustion agent, although the combustion heat value is high, the application of the aluminum particles is limited due to the short aftereffect time and large impact force.
Disclosure of Invention
When the high-physical-activity aluminum-silicon spherical alloy powder is used as an alloy combustion agent, the reaction process of the alloy fuel can be slowed down on the premise of not reducing the combustion heat value of the alloy fuel, the after-effect reaction time of explosive explosion is prolonged, the pressure attenuation of shock waves is slowed down, the overpressure of far-field shock waves is improved, and the requirement of explosive reaction moderation in some occasions is met.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides high-physical-activity aluminum-silicon spherical alloy powder, which comprises 95-60% of aluminum and 5-40% of silicon by mass; the high-physical activity aluminum-silicon spherical powder is pre-alloyed powder, has a long-range disordered structure and a non-equilibrium structure, does not have crystal grains and crystal boundaries, and silicon is uniformly distributed in aluminum without forming an alloy phase.
Preferably, the high-physical activity aluminum-silicon spherical alloy powder has the particle size of 0.5-200 mu m, the roundness value of not less than 0.88 and the density of 2.53-2.67 g/cm3
The invention also provides a preparation method of the high-physical activity aluminum-silicon spherical alloy powder, which comprises the following steps:
(1) melting and mixing an aluminum ingot and silicon particles in an inert atmosphere to obtain a molten liquid;
(2) atomizing and quickly condensing the smelting liquid obtained in the step (1) in an inert atmosphere to obtain the high-physical-activity aluminum-silicon spherical alloy powder;
the mass ratio of the aluminum ingot to the silicon particles is 95-60%: 5 to 40 percent.
Preferably, the purity of the aluminum ingot is 99.9% or more.
Preferably, the purity of the silicon particles is more than 98%, and the particle size is 5-30 μm.
Preferably, the temperature of the melt mixing is 800-860 ℃.
Preferably, the pressure of the inert atmosphere is 0.1-0.15 MPa.
Preferably, the device used for atomization is a butterfly atomizer; the rotating speed of the butterfly type atomizer is 2000-10000 r/min.
Preferably, the flash condensed purge gas temperature is below-80 ℃.
The invention also provides the application of the high-physical activity aluminum-silicon spherical alloy powder in the technical scheme in the field of explosives.
The invention provides high-physical-activity aluminum-silicon spherical alloy powder, which comprises 95-60% of aluminum and 5-40% of silicon by mass; the high-physical activity aluminum-silicon spherical powder is pre-alloyed powder, has a long-range disordered structure and a non-equilibrium structure, does not have crystal grains and crystal boundaries, and silicon is uniformly distributed in aluminum without forming an alloy phase. The aluminum and silicon components in the alloy powder of the invention exist independently, and do not react with each other, and do not form an alloy phase. Therefore, the respective characteristics of the two can be maintained during actual combustion and application. Generally, the prepared powder forms an alloy phase, most heat is released in the process of forming the alloy phase, and the heat release amount in practical application is greatly reduced. The prealloy prepared by the invention has the advantages that silicon is uniformly distributed in aluminum, the respective reactions release heat, and the effect that the heat release amount is not reduced is maintained. In addition, the metal fuel is generally used as a combustible agent in the explosive, and when only aluminum powder is added, the aluminum and detonation products (carbon dioxide and water) can generate secondary reaction to generate aluminum oxide, and a large amount of heat is released. The reaction process of the aluminum-silicon alloy added with the silicon is slower than that of pure aluminum powder, the reaction process can be divided into two steps in the actual detonation process, aluminum firstly reacts with detonation products, and then the silicon reacts with the detonation products. Therefore, the aftereffect reaction time is prolonged, and the impact breaking overpressure is delayed and attenuated, thereby realizing the application of the composite material. The data of the examples show that: the median diameter of the obtained powder is 25 μm; the TG curve shows that in the oxidation process in the air, the reaction degree and the reaction rate of the high-physical activity aluminum-silicon spherical alloy powder are smaller than those of pure aluminum; DSC is between 1000 and 1100 ℃, and the oxidation exothermic peak of the high-physical-activity aluminum-silicon spherical alloy powder is wider and shorter than that of pure aluminum, so that the reaction process of the high-physical-activity aluminum-silicon spherical alloy powder is slow and incomplete.
The preparation method of the high-physical-activity aluminum-silicon spherical alloy powder provided by the invention adopts an atomization method combined with a rapid condensation method, so that the alloy powder can be ensured to have excellent particle size and roundness value; meanwhile, the material has a long-range disordered structure and a non-equilibrium structure, and does not have crystal grains and crystal boundaries.
Drawings
FIG. 1 is a scanning electron microscope image of the high-physical-activity Al-Si spherical alloy powder obtained in example 1;
FIG. 2 is a particle size distribution diagram of the high physical activity Al-Si spherical alloy powder obtained in example 1;
FIG. 3 is a thermal analysis chart of 25 μm high physical activity Al-Si spherical alloy powder and pure Al particles obtained in example 2.
Detailed Description
The invention provides high-physical-activity aluminum-silicon spherical alloy powder, which comprises 95-60% of aluminum and 5-40% of silicon in mass fraction; the high-physical activity aluminum-silicon spherical powder is pre-alloyed powder, has a long-range disordered structure and a non-equilibrium structure, does not have crystal grains and crystal boundaries, and silicon is uniformly distributed in aluminum without forming an alloy phase.
The high-physical-activity aluminum-silicon spherical alloy powder provided by the invention preferably comprises 90-65% of aluminum by mass, more preferably 85-70% of aluminum by mass, and even more preferably 80-75% of aluminum by mass.
The high-physical-activity aluminum-silicon spherical alloy powder provided by the invention preferably comprises 10-35% by mass, more preferably 15-30% by mass, and even more preferably 20-35% by mass. According to the invention, silicon is added into aluminum, the melting point of silicon is 1414 ℃, the boiling point of silicon is 2900 ℃, and the melting point is extremely high, so that the silicon is not easy to melt and volatilize and difficult to ignite; however, silicon has a higher enthalpy of combustion of 35kJ/mol, higher than 31.02kJ/mol for aluminum; therefore, the combination of aluminum and silicon can slow down the reaction process of the fuel on the premise of not reducing the combustion heat value of the alloy fuel, thereby improving the insensitivity of the explosive.
In the invention, the particle size of the high-physical-activity aluminum-silicon spherical alloy powder is preferably 0.5-200 μm, and more preferably 10-180 μm; the circularity value is preferably not less than 0.88, and more preferably not less than 0.95; the density is preferably 2.5 to 2.8g/cm3More preferably 2.53 to 2.67g/cm3
According to the invention, the particle size of the high-physical-activity aluminum-silicon spherical alloy powder is controlled to be 0.5-200 mu m, and the smaller the particle size of the alloy powder, the faster the reaction rate is, the higher the reaction degree is.
The invention also provides a preparation method of the high-physical activity aluminum-silicon spherical alloy powder, which comprises the following steps:
(1) melting and mixing an aluminum ingot and silicon particles in an inert atmosphere to obtain a molten liquid;
(2) atomizing and quickly condensing the smelting liquid obtained in the step (1) in an inert atmosphere to obtain the high-physical-activity aluminum-silicon spherical alloy powder;
the mass ratio of the aluminum ingot to the silicon particles is 95-60%: 5 to 40 percent.
In the invention, under the inert atmosphere, an aluminum ingot and silicon particles are melted and mixed to obtain a smelting solution.
In the present invention, the purity of the aluminum ingot is preferably 99.9% or more; the purity of the silicon particles is preferably more than 98%, and the particle size is preferably 5-30 μm. In the invention, the mass ratio of the aluminum ingot to the silicon particles is 95-60%: 5 to 40 percent. In the present invention, the aluminum ingot and the silicon particles are preferably subjected to a pretreatment before melt-mixing; the pretreatment preferably comprises purging the aluminum ingot and silicon particles with a high temperature inert gas to remove surface adsorbed gases containing oxidizing atmospheres.
In the invention, the temperature of the melt mixing is preferably 800-860 ℃, more preferably 810-850 ℃, and even more preferably 820-830 ℃. In the present invention, the time for the melt mixing is not particularly limited as long as the aluminum ingot and the silicon particles can be uniformly mixed.
In the present invention, the inert gas preferably includes argon or helium having a purity of 99.99% or more. In the present invention, the pressure of the inert atmosphere is preferably 0.1 MPa. The apparatus for carrying out the melt-mixing is not particularly limited in the present invention, and a melting apparatus known to those skilled in the art may be used, specifically, a pre-melting furnace.
In the obtained smelting liquid, the high-physical activity aluminum-silicon spherical alloy powder is obtained by atomizing and quickly condensing the smelting liquid under the inert atmosphere.
In the invention, the device used for atomization is preferably a butterfly atomizer; the rotation speed of the butterfly type atomizer is preferably 2000-10000 r/min, more preferably 4000-8000 r/min, and even more preferably 5000-6000 r/min. In the invention, the flow rate of the purge gas for rapid condensation is preferably 2-20L/min, and more preferably 5-15L/min. In the present invention, the temperature of the purge gas for rapid condensation is preferably-80 ℃ or lower. In the present invention, the purge gas is preferably an inert gas; the inert gas is preferably condensed by cooling and purging with liquid nitrogen.
After the rapid cold condensation, the present invention preferably performs a classification treatment on the rapid condensation product. In the present invention, the classification treatment preferably includes vibratory screening or air classification. The alloy powder with the grain diameter of 0.5-200 mu m is obtained through grading treatment.
The invention combines atomization and rapid condensation, can quickly solidify the smelting liquid, further achieves the aim of effectively reducing the component segregation of the alloy, and obtains the alloy powder with fine microstructure and uniform components. In addition, by controlling the flow rate of the condensed gas, a powder having an amorphous, quasicrystalline, microcrystalline or supersaturated solid solution nonequilibrium structure can be obtained; crystal grains and crystal boundaries of the crystalline alloy do not exist; the aluminum and silicon components in the alloy powder exist independently, and do not react with each other, so that an alloy phase is not formed. Therefore, the respective characteristics of the two can be maintained during actual combustion and application. Generally, the prepared powder forms an alloy phase, most heat is released in the process of forming the alloy phase, and the heat release amount in practical application is greatly reduced. The prealloy prepared by the invention has the advantages that silicon is uniformly distributed in aluminum, the respective reactions release heat, and the effect that the heat release amount is not reduced is maintained.
The invention also provides the application of the high-physical activity aluminum-silicon spherical alloy powder in the technical scheme in the field of explosives.
In the invention, the mass content of the high-physical-activity aluminum-silicon spherical alloy powder in the explosive is preferably 15-30%.
The metal fuel is generally used as a combustible agent in the explosive, and the aluminum and detonation products (carbon dioxide and water) can generate secondary reaction to generate aluminum oxide under the condition of only adding aluminum powder, so that a large amount of heat is released. The reaction process of the aluminum-silicon alloy added with the silicon is slower than that of pure aluminum powder, the reaction process can be divided into two steps in the actual detonation process, aluminum firstly reacts with detonation products, and then the silicon reacts with the detonation products. Therefore, the aftereffect reaction time is prolonged, and the impact breaking overpressure is delayed and attenuated, thereby realizing the application of the composite material.
The high physical activity aluminum silicon spherical alloy powder provided by the present invention, the preparation method and the application thereof will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A high physical activity aluminum-silicon spherical alloy powder comprises 80 mass percent of aluminum and 20 mass percent of silicon;
the preparation method comprises the following steps:
(1) firstly, weighing 80 mass ratio: 20, and pretreating the surfaces of the aluminum ingot and the silicon particles; adding an aluminum ingot into a pre-melting furnace body under an inert atmosphere (the air pressure is 0.1Mpa), heating to 800-860 ℃, adding silicon particles for melting and mixing after aluminum is completely melted, and obtaining a melting liquid;
(2) atomizing the smelting liquid into small droplets in a butterfly type atomizer (the rotating speed is 2000r/min) under the inert atmosphere, then purging with inert gas at the temperature of-80 ℃ for rapid condensation, carrying out cyclone separation on the condensed product, sieving with a 325-mesh sieve, taking the undersize product, obtaining the high-physical activity aluminum-silicon spherical alloy powder, and sealing and packaging.
The granularity and the roundness value of the high-physical activity aluminum-silicon spherical alloy powder are tested by adopting a granularity meter and a roundness meter, the density is calculated, and the result is as follows: the particle size is 7-46 μm, the circularity value is 0.87, and the density is 2.62g/cm3
Fig. 1 is a scanning electron microscope image of the high-physical-activity aluminum-silicon spherical alloy powder obtained in the present example, and it can be seen from fig. 1 that: the alloy powder obtained in the embodiment has good dispersibility, is not agglomerated, is in a more regular spherical shape, and has a smaller particle size.
Fig. 2 is a particle size distribution diagram of the high-physical-activity aluminum-silicon spherical alloy powder obtained in this embodiment, and as can be seen from fig. 2, the particle size distribution of the alloy powder obtained in this embodiment is mostly 20 to 40 μm, the particle size distribution is concentrated, and the particle size distribution conforms to a log-normal distribution, wherein the normal distribution curve is as follows:
Figure BDA0001957703460000061
wherein y is0=-0.07,μ=31.33,σ=0.4,A=361.02。
Example 2
A high physical activity aluminum-silicon spherical alloy powder comprises 88 mass percent of aluminum and 12 mass percent of silicon;
the preparation method comprises the following steps:
(1) firstly, weighing 88 mass ratio: 12, and pretreating the surfaces of the aluminum ingot and the silicon particles; adding metal aluminum into a pre-melting furnace body under an inert atmosphere (the air pressure is 0.01Mpa), heating to 860 ℃, adding silicon particles for melting and mixing when the aluminum is completely melted, and obtaining a melting liquid;
(2) atomizing the smelting liquid into small droplets in a butterfly type atomizer (the rotating speed is 2000r/min) under the inert atmosphere, then purging with inert gas at the temperature of-80 ℃ for rapid condensation, carrying out cyclone separation on the condensed product, sieving with a 325-mesh sieve, taking the undersize product, obtaining the high-physical activity aluminum-silicon spherical alloy powder, and sealing and packaging.
The granularity and the roundness value of the high-physical activity aluminum-silicon spherical alloy powder are tested by adopting a granularity meter and a roundness meter, the density is calculated, and the result is as follows: the particle size is 6-45 μm, the circularity value is 0.89, and the density is 2.65g/cm3
The thermal analysis curves of the high physical activity aluminum-silicon spherical alloy powder with the particle size of 25 μm and the aluminum particles obtained in the present example were investigated under the condition that the temperature rise rate was 20k/min under the air atmosphere, and the results are shown in fig. 3; in FIG. 3, the arrows are exothermic, representing an exothermic peak in the DSC curve upward. Comparing the thermal analysis curve of the high-physical activity aluminum-silicon spherical alloy powder with pure aluminum with the same granularity, and the TG curve shows that the reaction degree and the reaction rate of the high-physical activity aluminum-silicon spherical alloy powder are smaller than those of the pure aluminum in the oxidation process in the air; DSC is between 1000 and 1100 ℃, and the oxidation exothermic peak of the high-physical-activity aluminum-silicon spherical alloy powder is wider and shorter than that of pure aluminum, so that the reaction process of the high-physical-activity aluminum-silicon spherical alloy powder is slow and incomplete.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The high-physical-activity aluminum-silicon spherical alloy powder is characterized by comprising 95-60 mass percent of aluminum and 5-40 mass percent of silicon; the high-physical activity aluminum-silicon spherical powder is pre-alloyed powder, has a long-range disordered structure and a non-equilibrium structure, does not have crystal grains and crystal boundaries, and silicon is uniformly distributed in aluminum without forming an alloy phase.
2. The Al-Si spherical alloy powder with high physical activity according to claim 1, wherein the Al-Si spherical alloy powder with high physical activity has a particle size of 0.5-200 μm, a circularity value of 0.88 or more, and a density of 2.53-2.67 g/cm3
3. The method for preparing the high-physical-activity aluminum-silicon spherical alloy powder according to any one of claims 1 to 2, comprising the following steps:
(1) melting and mixing an aluminum ingot and silicon particles in an inert atmosphere to obtain a molten liquid;
(2) atomizing and quickly condensing the smelting liquid obtained in the step (1) in an inert atmosphere to obtain the high-physical-activity aluminum-silicon spherical alloy powder;
the mass ratio of the aluminum ingot to the silicon particles is 95-60%: 5 to 40 percent.
4. A production method according to claim 3, wherein the purity of the aluminum ingot is 99.9% or more.
5. The method according to claim 3 or 4, wherein the silicon particles have a purity of 98% or more and a particle diameter of 5 to 30 μm.
6. The method according to claim 3, wherein the melt-mixing temperature is 800 to 860 ℃.
7. The method according to claim 3, wherein the inert atmosphere has a pressure of 0.1 to 0.15 MPa.
8. The method according to claim 3, wherein the device used for atomization is a butterfly atomizer; the rotating speed of the butterfly type atomizer is 2000-10000 r/min.
9. The method of claim 3, wherein the flash condensed purge gas temperature is-80 ℃ or less.
10. Use of the high-physical-activity aluminum-silicon spherical alloy powder according to any one of claims 1 to 2 or the high-physical-activity aluminum-silicon spherical alloy powder obtained by the preparation method according to any one of claims 3 to 9 in the field of explosives.
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