CN115612884B - MB (MB) 2 Preparation method and application of (M=Ti+V) particles - Google Patents
MB (MB) 2 Preparation method and application of (M=Ti+V) particles Download PDFInfo
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Abstract
The invention discloses an MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, stirring is carried out every 15 minutes, and the temperature is kept for one hour. MB of the present invention 2 The (m=ti+v) particles have excellent grain refining effect, and in the preparation, the ti+v element is matched with the B element, so that the rare earth modifier has excellent grain refining efficiency under the optimized coordination; the rare earth modifier adopts rare earth lanthanum and rare earth rubidium to be matched with the carbon nano tube modifier, and grains are further refined in the preparation of alloy products by the co-mixing effect of the carbon nano tube modifier and rare earth elements, so that the preparation efficiency of the products is improved.
Description
Technical Field
The invention relates to the technical field of Al-Si alloy, in particular to a method for generating MB by mixing Ti and V elements and B elements 2 Preparation method and application of (M=Ti+V) particles.
Background
Al-Si alloy is widely applied to transportation, but has poor mechanical properties due to coarse grains, and often limits the application of the Al-Si alloy. The method for industrially refining aluminum alloy grains is mainly by inoculating Al-5Ti-1B refiner, but the refining performance is lost in Al-Si alloy with Si content exceeding 5 wt%. The reason for this is because Si element is biased to the surface of TiB2 particles so that it is lost to the bonding of α -Al. Therefore, the development of a novel heterogeneous nuclear particle for refining Al-Si alloy is very important.
Al-Ti-Nb-B is a grain refiner effective for Al-Si alloys, in which Nb, ti elements and B elements form (Nb, ti) B 2 Has good refining effect on alpha-Al, and single TiB2 and NbB 2 The refining effect of the (Nb, ti) B2 particles is inferior to that of the mixed (Nb, ti) B2 particles, and the Al-Ti-Nb-B refiner can solve TiB 2 The problem of "Si poisoning", but due to NbB 2 The density (6.93 g/cm 3) is large, so that this (Nb, ti) B is caused 2 The particles sink and lose the nucleation effect. For NbB 2 The particle density is large, the Nb element is replaced by the V element, and the V element can generate VB with refining effect 2 But single VB 2 The refining effect is not good, but VB 2 Density is far lower than NbB 2 So TiB is to 2 With VB 2 Combined preparation of Ti and V mixture and B-formed MB 2 (m=ti+v) particles to solve TiB 2 "Si poisoning", VB 2 Poor refining action, (Nb, ti) B 2 The problem of particle subsidence. Based on the above, the invention provides a method for generating MB by mixing Ti and V elements and B elements 2 Preparation method and application of (M=Ti+V) particles.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a method for generating MB by mixing Ti and V elements and B elements 2 A preparation method and application of (m=ti+v) particles to solve the problems set forth in the background art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a method for generating MB by mixing Ti and V elements and B elements 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 10-20min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
Preferably, the MB 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
Preferably, the preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10-20% of the total weight of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 10-20% of the total chitosan and sodium alkyl sulfonate accounting for 2-6%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 1-3% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into modification treatment liquid which is 5-7 times of the rare earth complexing agent, stirring, washing with water and drying to obtain the rare earth modification agent.
Preferably, the mass fraction of the sodium alginate solution is 20-25%.
Preferably, the stirring treatment in the step S03 has a rotating speed of 550-650r/min, a stirring time of 30-40min and a stirring temperature of 65-75 ℃.
Preferably, the preparation method of the carbon nanotube additive comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 3 to 6 times, and then phosphoric acid buffer solution with the volume of 10 to 20 percent of the total volume of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 1-5% of the total amount of the carbon nano tube, continuously stirring and mixing thoroughly, and finally washing and drying to obtain the carbon nano tube additive.
Preferably, the rotation speed of ball milling in the ball mill is 1000-1500r/min, and the ball milling time is 20-30min.
Preferably, the specific operation steps of the thermal homogenization improvement treatment are:
s21: firstly, heating to 300-350 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-20min;
s22: then continuously heating to 650 ℃ at the speed of 5-10 ℃/min, and continuously preserving heat for 5-10min;
s23: finally, air cooling to room temperature.
Preferably, the air cooling is carried out by adopting air with the temperature of 1-10 ℃ and the air cooling flow rate is 5-10L/min.
The invention also provides a method for generating MB by mixing Ti and V elements and B elements 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Compared with the prior art, the invention has the following beneficial effects:
MB of the present invention 2 The (m=ti+v) particles have excellent grain refining effect, and in the preparation, the ti+v element is matched with the B element, so that the rare earth modifier has excellent grain refining efficiency under the optimized coordination; the rare earth modifier adopts rare earth lanthanum and rare earth rubidium to be matched with the carbon nano tube modifier, and grains are further refined in the preparation of alloy products by the co-mixing effect of the carbon nano tube modifier and rare earth elements, so that the preparation efficiency of the products is improved.
Drawings
FIG. 1 is a diagram of Al-7Si grains;
FIG. 2 is TiB 2 +TiAl 3 Refining an Al-7Si crystal grain diagram;
FIG. 3 is VB 2 Refining an Al-7Si crystal grain diagram;
FIG. 4 is MB 2 (m=ti+v) refinement of Al-7Si grain map;
FIG. 5 is MB 2 (m=ti+v) refining the polarized light golden phase diagram of Al-7 Si;
FIG. 6 is an SEM image of Al-Ti-V-B refiner of comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 10-20min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10-20% of the total weight of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 10-20% of the total chitosan and sodium alkyl sulfonate accounting for 2-6%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 1-3% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into modification treatment liquid which is 5-7 times of the rare earth complexing agent, stirring, washing with water and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution in the embodiment is 20-25%.
The stirring treatment in S03 of this example was carried out at a rotational speed of 550-650r/min, a stirring time of 30-40min and a stirring temperature of 65-75deg.C.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 3 to 6 times, and then phosphoric acid buffer solution with the volume of 10 to 20 percent of the total volume of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 1-5% of the total amount of the carbon nano tube, continuously stirring and mixing thoroughly, and finally washing and drying to obtain the carbon nano tube additive.
The ball milling speed in the ball mill of the embodiment is 1000-1500r/min, and the ball milling time is 20-30min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 300-350 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-20min;
s22: then continuously heating to 650 ℃ at the speed of 5-10 ℃/min, and continuously preserving heat for 5-10min;
s23: finally, air cooling to room temperature.
The air cooling of the embodiment adopts air at the temperature of 1-10 ℃ for air cooling, and the air cooling flow rate is 5-10L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Example 1.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 10min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10% of the total amount of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 10% of the total chitosan and sodium alkyl sulfonate accounting for 2%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 1% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into modification treatment liquid which is 5 times of the rare earth complexing agent, stirring, washing with water and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution of this example was 20%.
In the stirring treatment in S03 of this example, the rotation speed was 550r/min, the stirring time was 30min, and the stirring temperature was 65 ℃.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume being 3 times, and then phosphoric acid buffer solution with the volume being 10 percent of the total volume of the carbon nano tube is added, and the dispersion is uniform;
s12: and then adding sodium dodecyl sulfate accounting for 1% of the total amount of the carbon nano tube, continuously stirring and mixing fully, and finally washing and drying to obtain the carbon nano tube additive.
The ball mill in this example had a ball milling speed of 1000r/min and a ball milling time of 20min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 300 ℃ at a speed of 1 ℃/min, and preserving heat for 10min;
s22: then continuously heating to 650 ℃ at a speed of 5 ℃/min, and continuously preserving heat for 5min;
s23: finally, air cooling to room temperature.
The air cooling in this embodiment is performed by using air at 1℃at an air cooling flow rate of 5L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Example 2:
the element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 20min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10-20% of the total weight of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 20% of the total chitosan and sodium alkyl sulfonate accounting for 6%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 3% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into 7 times of modification treatment liquid for stirring treatment, and after the treatment is finished, washing and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution of this example was 25%.
The stirring treatment in S03 of this example was carried out at a rotation speed of 650r/min, a stirring time of 40min and a stirring temperature of 75 ℃.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 6 times, and then phosphoric acid buffer solution with the volume of 20 percent of the total volume of the carbon nano tube is added for uniform dispersion;
s12: and then adding sodium dodecyl sulfate accounting for 5% of the total amount of the carbon nano tube, continuously stirring and mixing fully, and finally washing and drying to obtain the carbon nano tube additive.
The ball mill in this example had a ball milling speed of 1500r/min and a ball milling time of 30min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 350 ℃ at a speed of 3 ℃/min, and preserving heat for 20min;
s22: then continuously heating to 650 ℃ at the speed of 10 ℃/min, and continuously preserving heat for 10min;
s23: finally, air cooling to room temperature.
The air cooling in this embodiment is performed by using air at 10℃at a flow rate of 10L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Example 3:
the element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 15min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 15% of the total amount of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 15% of the total chitosan and sodium alkyl sulfonate accounting for 4%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 2% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into a 6-time modification treatment liquid for stirring treatment, and after the treatment is finished, washing and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution of this example was 22.5%.
In the stirring treatment in S03 of this example, the rotation speed was 600r/min, the stirring time was 35min, and the stirring temperature was 70 ℃.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 4.5 times, and then phosphoric acid buffer solution with the total volume of 15 percent of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 3% of the total amount of the carbon nano tube, continuously stirring and mixing fully, and finally washing and drying to obtain the carbon nano tube additive.
The ball mill in this example had a ball mill rotation speed of 1250r/min and a ball mill time of 25min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 325 ℃ at a speed of 2 ℃/min, and preserving heat for 15min;
s22: then continuously heating to 650 ℃ at the speed of 7.5 ℃/min, and continuously preserving heat for 7.5min;
s23: finally, air cooling to room temperature.
The air cooling in this example was performed using 5.5℃air, and the air cooling flow rate was 7.5L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Example 4:
the element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 12min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10-20% of the total weight of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 12% of the total chitosan and sodium alkyl sulfonate accounting for 3%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 1.5% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into a 6-time modification treatment liquid for stirring treatment, and after the treatment is finished, washing and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution of this example was 22%.
In S03 of this example, the stirring treatment was carried out at a rotation speed of 580r/min, a stirring time of 32min and a stirring temperature of 69 ℃.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 4 times, and then phosphoric acid buffer solution with the total volume of 12 percent of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 2% of the total amount of the carbon nano tube, continuously stirring and mixing thoroughly, and finally washing and drying to obtain the carbon nano tube additive.
The ball mill in this example had a ball mill rotation speed of 1100r/min and a ball mill time of 22min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 310 ℃ at a speed of 1.2 ℃/min, and preserving heat for 12min;
s22: then continuously heating to 650 ℃ at the speed of 6 ℃/min, and continuously preserving heat for 6min;
s23: finally, air cooling to room temperature.
The air cooling in this embodiment is performed by using air at 2℃at a flow rate of 6L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Example 5:
the element mixture of Ti and V and the element B of the embodiment generate MB 2 A process for the preparation of (m=ti+v) particles comprising the steps of:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 18min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: and then carrying out heat homogenization improvement treatment.
MB of the present embodiment 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
The preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 18% of the total amount of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 18% of the total chitosan and sodium alkyl sulfonate accounting for 5%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 2.8% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into a 6-time modification treatment liquid for stirring treatment, and after the treatment is finished, washing and drying to obtain the rare earth modification agent.
The mass fraction of the sodium alginate solution of this example was 24%.
In the present example, the stirring treatment was carried out at a rotation speed of 620r/min, a stirring time of 38min and a stirring temperature of 73 ℃.
The preparation method of the carbon nanotube additive of the embodiment comprises the following steps:
s11: the carbon nano tube is sent into water with the volume of 3 to 6 times, and then phosphoric acid buffer solution with the volume of 18 percent of the total volume of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 1-5% of the total amount of the carbon nano tube, continuously stirring and mixing thoroughly, and finally washing and drying to obtain the carbon nano tube additive.
The ball mill in this example had a ball mill rotation speed of 1450r/min and a ball mill time of 28min.
The specific operation steps of the thermal homogenization improvement treatment of this embodiment are:
s21: firstly, heating to 345 ℃ at the speed of 2.8 ℃/min, and preserving heat for 18min;
s22: then continuously heating to 650 ℃ at the speed of 9 ℃/min, and continuously preserving heat for 8min;
s23: finally, air cooling to room temperature.
The air cooling in this embodiment is performed by air cooling at 9℃at an air cooling flow rate of 8L/min.
The element mixture of Ti and V and the element B of the embodiment generate MB 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
Inoculation experiment method: pure aluminum and pure Si melt (750 ℃) and an Al matrix with heterogeneous particles is added. Preserving the temperature for 30min, removing gas and impurities, and pouring the mixture into a steel mould preheated to 250 ℃.
FIGS. 1-4 are refinements to Al-7Si (adding 100ppm of the same B content): from a macroscopic view, via MB 2 (m=ti+v) the grain refinement size is much smaller than the other three.
FIG. 5 is a warp MB 2 (m=ti+v) grain refinement Al-7Si, grain size was statistically about 130 microns. Summarizing: an MB has been developed 2 The (M=Ti+V) particles can effectively refine Al-7Si to about 130 microns, are novel heterogeneous nuclear particles, and can be applied to actual industrial production.
Referring to fig. 6, comparative example 1: a high-performance Al-Ti-V-B alloy refiner, a preparation method and application thereof; the preparation method comprises the following steps: k (K) 2 TiF 6 (Potassium fluorotitanate) powder, KBF 4 Potassium (fluoroborate) powder, V powder. (the raw materials are different, the invention is intermediate alloy)
The preparation method of the Al-Ti-V-B comprises the following steps: melting pure aluminum (750-780 ℃), heating to 830 deg.C (800-900 deg.C), adding three mixed powders, stirring, and maintaining for 130min. (the reaction temperature is different, the reaction temperature is only 750 ℃, and the feeding sequence is that Al-V and Al-B are firstly added, and after heat preservation is carried out for 1h, al-Ti is added and heat preservation is carried out for 30 min);
the phase is VAl 3 ，TiAl 3 ，TiB 2 ，VB 2 ，AlB 2 . (TiB only in the present invention) 2 And VB 2 A mixture phase);
(TiB of comparative example 1) 2 With VB 2 Is separated into separate phases, the invention is MB formed by mixing Ti and V and B element 2 (m=ti+v) particles. )
(the refined size of comparative example 1 is less than 160. Mu.m, the invention is about 130. Mu.m, VB in Al-Ti-V-B of comparative example 1) 2 Particle size of 10 microns, tiB 2 And AlB 2 40 microns. MB of the present invention 2 (m=ti+v) particle sizes between 100-500 nm, much smaller than comparative example 1).
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. MB (MB) 2 A process for the preparation of (m=ti+v) particles, characterized in that it comprises the following steps:
step one: al-Ti and Al-V, al-B intermediate alloy is prepared by smelting, wherein the smelting temperature is 750 ℃, the feeding sequence is that Al-V and Al-B are firstly added into a graphite crucible for smelting, and the mixture is stirred once every 15 minutes and is kept for one hour;
step two: adding the Al-Ti alloy into the melt, stirring once every 15 minutes, and preserving heat for 30 minutes; removing air and impurities, and casting;
step three: then adding rare earth modification modifier, and continuing smelting for 10-20min;
step four: finally, cooling and shaping, and sending into a ball mill for ball milling;
step five: then the mixture is subjected to thermal homogenization improvement treatment;
the preparation method of the rare earth modification modifier comprises the following steps:
s01: mixing rare earth lanthanum and rare earth rubidium according to a weight ratio of 3:1, then adding a carbon nano tube additive accounting for 10-20% of the total weight of the rare earth lanthanum, and stirring and mixing fully to obtain a rare earth complexing agent;
s02: adding chitosan into a sodium alginate solution according to a weight ratio of 1:3, then adding hydrochloric acid accounting for 10-20% of the total chitosan and sodium alkyl sulfonate accounting for 2-6%, stirring and mixing uniformly, and then adding a silane coupling agent accounting for 1-3% of the total chitosan, stirring and mixing fully to obtain a modified treatment solution;
s03: and (3) sending the rare earth complexing agent into modification treatment liquid which is 5-7 times of the rare earth complexing agent, stirring, washing with water and drying to obtain the rare earth modification agent.
2. An MB according to claim 1 2 Process for the preparation of (m=ti+v) particles, characterized in that said MB 2 (m=ti+v) in ICP elemental analysis, the weight part of Ti was 0.45 part, V:0.85 parts, B:0.5 part of rare earth modification modifier 0.1 part, and 1.5 parts of Al as a matrix.
3. An MB according to claim 1 2 The preparation method of the (M=Ti+V) particles is characterized in that the mass fraction of the sodium alginate solution is 20-25%.
4. An MB according to claim 1 2 The preparation method of the (M=Ti+V) particles is characterized in that the rotation speed of the stirring treatment in the step S03 is 550-650r/min, the stirring time is 30-40min, and the stirring temperature is 65-75 ℃.
5. An MB according to claim 1 2 A method for preparing (m=ti+v) particles, characterized in that the method for preparing the carbon nanotube additive comprises:
s11: the carbon nano tube is sent into water with the volume of 3 to 6 times, and then phosphoric acid buffer solution with the volume of 10 to 20 percent of the total volume of the carbon nano tube is added for uniform dispersion;
s12: and adding sodium dodecyl sulfate accounting for 1-5% of the total amount of the carbon nano tube, continuously stirring and mixing thoroughly, and finally washing and drying to obtain the carbon nano tube additive.
6. An MB according to claim 1 2 The preparation method of the (M=Ti+V) particles is characterized in that the rotating speed of ball milling in the ball mill is 1000-1500r/min, and the ball milling time is 20-30min.
7. An MB according to claim 1 2 Process for the preparation of (m=ti+v) particles, characterized in that the thermal homogenization improves the specific operating steps of the treatmentThe method comprises the following steps:
s21: firstly, heating to 300-350 ℃ at a speed of 1-3 ℃/min, and preserving heat for 10-20min;
s22: then continuously heating to 650 ℃ at the speed of 5-10 ℃/min, and continuously preserving heat for 5-10min;
s23: finally, air cooling to room temperature.
8. An MB according to claim 7 2 The preparation method of the (M=Ti+V) particles is characterized in that the air cooling is carried out by adopting air with the temperature of 1-10 ℃ and the air cooling flow rate of 5-10L/min.
9. An MB as claimed in any one of claims 1 to 8 2 Use of a method for the preparation of (m=ti+v) particles for refining Al-Si alloys.
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