CN116815005A - Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite - Google Patents
Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite Download PDFInfo
- Publication number
- CN116815005A CN116815005A CN202310792897.5A CN202310792897A CN116815005A CN 116815005 A CN116815005 A CN 116815005A CN 202310792897 A CN202310792897 A CN 202310792897A CN 116815005 A CN116815005 A CN 116815005A
- Authority
- CN
- China
- Prior art keywords
- melt
- temperature
- reaction
- weight
- aluminum matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011159 matrix material Substances 0.000 title claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000155 melt Substances 0.000 claims abstract description 81
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000006023 eutectic alloy Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 26
- 229910052700 potassium Inorganic materials 0.000 claims description 26
- 239000011591 potassium Substances 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 21
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 19
- 229910033181 TiB2 Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000007664 blowing Methods 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 238000010612 desalination reaction Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910020261 KBF4 Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 229910020491 K2TiF6 Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 44
- 238000000746 purification Methods 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910018125 Al-Si Inorganic materials 0.000 abstract description 3
- 229910018520 Al—Si Inorganic materials 0.000 abstract description 3
- 238000004364 calculation method Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 12
- 239000010936 titanium Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007528 sand casting Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite, which has the following characteristics: (1) By adopting the calculation method, the initial melting quantity of the alloy and the size of the crucible are reasonably selected, and the depth of a molten salt layer in the reaction process is controlled to be not more than 3cm; (2) Taking Al-Si eutectic alloy as a base melt, adding mixed salt at 600 ℃, wherein the temperature of the melt is not more than 650 ℃ in the whole reaction process; (3) And after the reaction is finished, sequentially carrying out vacuum purification treatment and heating to add alloy elements. The invention adopts reasonable crucible diameter and extremely low reaction temperature, effectively reduces the reaction speed, inhibits the growth speed of reaction products, and solves the problems of large particle size distribution range and more byproducts of the reaction products in the traditional in-situ synthesis method. By strictly controlling the depth of the metal melt and the molten salt, the reaction interface of the alloy-molten salt is increased, the reaction product is easier to disperse, the residual molten salt in the melt is obviously reduced, and the melt purification difficulty is reduced.
Description
Technical Field
The invention belongs to the field of preparation of aluminum-based composite materials, and particularly relates to a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum-based composite material.
Background
The nanoparticle reinforced aluminum matrix composite material not only has excellent mechanical properties, but also has the advantages of high wear resistance, good thermal conductivity, low thermal expansion coefficient, strong designability and the like, and has wide application prospect in the field of manufacturing of advanced equipment. The in situ synthesis method can directly react in the melt to produce the enhanced particles with thermodynamic stability. The reinforced particles are nucleated and grow up in the melt, and have natural wettability with the melt. The interface between the reinforced particles and the matrix is pure, and the bonding strength is high. Therefore, in-situ synthesis of particle reinforced aluminum matrix composites is considered to be the most promising composite preparation technique. The fluoride salt method has the advantages of simple process, low cost and the like, and is the most engineering potential method for synthesizing the nanoparticle reinforced aluminum matrix composite in situ.
However, the in-situ synthesis of the nanoparticle reinforced aluminum matrix composite material by the fluoride salt method still does not realize large-scale engineering application, and the main reason is that the bottleneck technical problem still exists but is not solved yet:
first, the size distribution of the reinforcing particles is wide, and varies from hundreds of nanometers to micrometers, and the presence of large-size particles limits the reinforcing effect of the nanoparticles; secondly, the uniformity of the dispersion of the nano particles in the matrix is poor, and the agglomerated nano particles reduce the mechanical properties of the matrix material instead; thirdly, residual molten salt in the melt is difficult to completely discharge, the purity of the melt is poor, and the effect of particle reinforcement is greatly reduced (Hu Dongfu. Preparation of high-cleanliness in-situ TiB2 reinforced aluminum-based composite material [ D ]. Dalian university of Dalian chemical industry, 2014.).
In order to obtain the reinforced particles with high size concentration and good dispersion, technicians at home and abroad generally choose lower reaction temperature and simultaneously implement strong stirring (including electromagnetic stirring and mechanical stirring).
Chinese patent 202011306962.1 discloses a method for preparing an in-situ nanoparticle reinforced aluminum matrix composite material at a low temperature, wherein the temperature of a melt is controlled to 660-670 ℃, high-speed mechanical stirring is applied to the upper surface of the melt to form a vortex, and mixed salt is added into the vortex on the surface of the melt to react for 15min. The reaction of the mixed salt with Al is exothermic, resulting in a rise in the melt temperature of about 90 ℃, and the technique does not take into account the effect of the rise in the melt temperature on the reaction process. In addition, the surface swirl rotating at high speed can cause mixed salt and air to be entrained into the melt, and a large amount of residual emulsified salt and a large amount of oxide are formed in the melt, so that the viscosity of the melt is increased, and difficulties are brought to the melt purification treatment. The method does not involve purification techniques of residual emulsifying salts and oxide inclusions. Liu Zhengcai et al (Liu Zhengcai, iso Mixed salt TiB) 2 Particle reinforced aluminum matrix composites research status [ J]Studies of thermal processing techniques, 2021, 12 (50) pp. 17-21) have shown that mechanical agitation is effective in promoting melt flow and melt homogenization. However, the clusters cannot be effectively broken by low-speed stirring, and the absorption and oxidation of hydrogen are increased by high-speed stirring, and surface impurities are introduced, so that the mechanical properties of the composite material are reduced.
Wang Haowei group presents a system and method for preparing in situ autogenous aluminum matrix composites using pulsed magnetic fields. Adding mixed salt at 700-760 ℃ while vacuumizing (a method for controlling in-situ self-generated aluminum-based composite material by using melt with electromagnetic stirring, china patent 202011571152.9, a systematic Chinese patent 202011571153.3 for controlling in-situ self-generated aluminum-based composite material by using melt with electromagnetic stirring, and a method for controlling in-situ self-generated aluminum-based composite material by using permanent magnet stirring, china patent 202011571141.0). The technology does not relate to the study of the influence of reaction exotherm and melt temperature rise on the reaction process, and does not relate to the study related to the residual molten salt purification technology.
In order to avoid the problem that residual molten salt in aluminum melt is difficult to discharge caused by the temperature rise and stirring of the melt in the fluorine method reaction process, chinese patent 202111585762.9 proposes adjustable TiB 2 A preparation method of an in-situ reinforced aluminum-based composite material. The method takes boron alloy and aluminum-titanium alloy or pure titanium as raw materials, reacts at 800-850 ℃, and adopts argon refining and degassing. The technology has higher reaction temperature, does not relate to mixed salt reaction, and does not relate to residual molten salt purification technology.
Chinese patent 200510029902.9 discloses a preparation method of an in-situ particle reinforced high temperature resistant aluminum matrix composite. The reaction temperature range disclosed by the method is 680-800 ℃, and after the reaction is completed, alloy elements are added, and vacuumizing and standing are carried out. The reaction temperature of the method is higher, and the influence of the rising of the reaction temperature on the reaction process is not involved; after the reaction is completed, the residual salt in the melt is not treated in time, and the addition of the alloy element causes further increase in the viscosity of the melt, so that the melt is more difficult to purify.
Wang et al used mechanical stirring during the reaction at 850℃to obtain TiB 2 (2.2 vol%)/A356 composite had a tensile strength of 375.3MPa, a yield strength of 304.7MPa, an elongation of 4.88% (Wang, mechanical properties of in-site TiB2/A356 composites [ J)].Materials Science&Engineering A,590 (2014) 246-254). He Yongsheng et al employ C 2 Cl 6 After refining, adding mixed salt at 720 ℃, fully stirring, and sand casting to obtain the 5wt%/ZL114A composite material with 300MP of tensile strength and 2.5% of elongation (He Yongsheng, etc. endogenous TiB) 2 Particle reinforced TiB 2 Tissue and mechanical Properties of the Al-7% Si-05% Mg composite [ J]Casting, 2000 (07): 396-397.). The reaction temperatures studied above are all relatively high and do not involve the exothermic reaction and the effect of the rise in melt temperature on the reaction process.
The inventors have found from experimental studies that the melt temperature increases by about 80-100 ℃ during the reaction at a melt level of hundreds of kilograms to tons. The great rise in melt temperature results in an increase in reaction rate, while the convection or diffusion rate (constant mechanical stirring or an equal power acousto-magnetic coupling field) remains unchanged, which tends to cause the growth or aggregation of the size of the reinforcing particles, ultimately resulting in a large span of the size range of the reinforcing particles and uneven dispersion.
The reaction releases a large amount of gas (K)BF 4 ＝KF+BF 3 ↑，K 2 TiF 6 ＝2KF+TiF 4 ∈) is responsible for TiB 2 One of the important reasons for low particle yield is that the higher the reaction temperature, the higher the reaction (KBF 4 ＝KF+BF 3 ↑，K 2 TiF 6 ＝2KF+TiF 4 ∈) is more intense, resulting in TiB 2 The lower the yield of (c).
In the reaction process, molten salt inevitably enters the interior of the melt to increase the viscosity of the melt, and the disclosed technical scheme generally adopts a traditional mode to carry out melt purification treatment before casting. In practice, alloying causes a further increase in melt viscosity, which results in increased difficulties in melt purging.
Further improving the controllable degree of the reaction process, obtaining nano reinforced particles with consistent size and morphology, uniform dispersion and pure melt is a problem which is solved by scientific research technicians in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite.
The technical scheme adopted for solving the technical problems is as follows:
the invention provides a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite, which specifically comprises the following steps:
s1: charging a raw material AlSi12 eutectic alloy with the weight of m1 into a crucible with the diameter of D for melting, heating to a certain temperature after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding potassium fluotitanate and potassium fluoborate mixed salt into a melt for reaction, and slowly adding an AlSi12 eutectic alloy block with the weight of m2 into the melt after the mixed salt is completely melted;
s3: after the reaction is completed, slag skimming is carried out, and vacuum desalting treatment is carried out on the melt;
s4: heating the melt, adding pure aluminum ingot with the weight of m3, and then controlling the temperature and adding pure magnesium with the weight of m 4;
s5: and (3) carrying out melt refining treatment by adopting an argon rotary blowing method, adjusting the temperature and casting.
Preferably, the crucible diameter D, the total weight m of the composite material prepared and the TiB contained in the composite material prepared 2 The mass fraction of the nanoparticles corresponds to the following relationship:
wherein:
d is the diameter of the crucible;
m is the total weight of the prepared composite material, and the unit is g;
w t is TiB 2 The design content of (2) is a percentage;
γ Ti for K 2 TiF 6 The preset yield of Ti is 100 percent;
γ B for KBF 4 The preset yield of B in the step (a), 100% is taken in the invention;
W K2TiF6 for K 2 TiF 6 Is a relative molecular weight of (2);
W TiB2 is TiB 2 Molecular weight of (2);
W KBF4 for KBF 4 Molecular weight of (2);
ρ salt The density of the molten mixed salt is given in g/cm 3 ；
h Salt For the depth of the molten mixed salt, this value is not more than 3cm depending on the actual production.
Preferably, in step S1, the temperature is increased to 590 to 610 ℃.
Preferably, in the step S2, the mixed salt of potassium fluotitanate and potassium fluoborate is subjected to heat preservation at 400 ℃ for 2 hours for preheating treatment; adding mixed salt of potassium fluotitanate and potassium fluoborate into the melt for reaction, slowly adding AlSi12 eutectic alloy blocks with the weight of m2 into the melt in the reaction process, and controlling the temperature of the melt in the reaction process to be not more than 650 ℃; the weight m2 of the added AlSi12 eutectic alloy blocks is 5-10% of the weight of the added mixed salt.
Preferably, in step S3, the conditions for the vacuum desalination treatment are as follows: the temperature of the melt is 600-630 ℃, the pressure is not more than 500Pa, and the vacuum desalination treatment time is 15-30 min.
Preferably, in the step S4, the temperature of the melt is raised to 760-780 ℃ before pure aluminum ingots are added; before adding pure magnesium, the temperature of the melt is controlled to 700-720 ℃.
Preferably, in step S5, the rotation speed of the argon gas rotary blowing method is 300-600 r/min, the pressure of the argon gas is 1-2 MPa, and the refining time of the argon gas rotary blowing method is 15-25 min.
The invention also provides a nanoparticle reinforced aluminum matrix composite material, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention firstly discloses that the depth of molten salt in the reaction process is limited to be not more than 3cm, and in order to meet the requirement, the crucible diameter needs to be designed according to the content of reinforced particles in the composite material and the total weight of the prepared composite material. According to the calculation method provided by the invention, on the premise of the same initial melting quantity, the cross section area of the crucible used by the method is 4-9 times that of the traditional crucible, and the diameter is about 2-3 times that of the traditional crucible. Increasing the diameter of the crucible has three benefits: firstly, the contact area between the metal melt and molten salt is increased, and the reaction efficiency is improved; secondly, the diffusion distance of the reaction product is increased, which is beneficial to the dispersion of the reaction product; and thirdly, the heat dissipation area is increased, the heat conduction released by the reaction is facilitated, the abrupt rise of the reaction temperature is avoided, and the reinforced particles with high shape and size consistency are facilitated to be obtained.
(2) According to the invention, by utilizing the characteristic of low melting point of the AlSi12 eutectic alloy, the AlSi12 with the weight of m1 is melted and then is controlled to be at the temperature of about 600 ℃, compared with the temperature in the prior art, the reaction speed is effectively inhibited, and the problem of poor consistency of reaction products caused by rapid local temperature rise of a melt due to rapid reaction is avoided. After the added mixed salt is melted, slowly adding an AlSi12 eutectic alloy block with the weight of m2 into the melt, further improving the controllability of the temperature of the melt in the reaction process, and being beneficial to continuous and stable reaction, thereby obtaining reinforced particles with uniform morphology and size;
(3) After the reaction is completed, the invention carries out vacuum desalination treatment under the reasonable electromagnetic stirring condition, and the free K in the melt + 、H + 、F - Ions can be quickly separated from the melt, so that the purpose of removing residual molten salt in the melt is achieved, and the effects of degassing and deslagging are achieved. Residual molten salt is removed firstly, and then the melt is heated for alloying, so that the melt purification difficulty can be reduced, and the problem that reinforcing particles continue to grow up due to further reaction of the residual molten salt after the temperature is raised is avoided, thereby being beneficial to obtaining nano reinforcing particles with uniform and fine size and pure alloy melt.
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 TiB with a TiB2 mass fraction of 3% obtained in example I 2 SEM (scanning electron microscope) detection result graphs of particle size and morphology of nano reinforced particles of the ZL101A composite material.
FIG. 2 shows TiB with a TiB2 mass fraction of 5% obtained in example two 2 SEM (scanning electron microscope) detection result graphs of particle size and morphology of nano reinforced particles of the ZL114A composite material.
FIG. 3 shows TiB with 3% TiB2 mass fraction prepared in example III 2 SEM (scanning electron microscope) detection result graphs of particle size and morphology of nano reinforced particles of the ZL101A composite material.
FIG. 4 shows TiB with a TiB2 mass fraction of 5% obtained in example four 2 SEM (scanning electron microscope) detection result graphs of nano enhanced granularity and morphology of the ZL114A composite material.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
Example 1
This example proposes a low temperature in situ synthesized nanoparticle reinforced aluminum matrix composite (ZL 101A-3wt.% TiB) 2 ) The preparation method specifically comprises the following steps:
s1: the crucible diameter D is calculated according to the following formula:
wherein:
m is the total weight of the composite material prepared;
w t is TiB 2 Is 3%;
γ Ti for K 2 TiF 6 The preset yield of Ti in the process is 100 percent;
γ B for KBF 4 The preset yield of B in the step (a) is 100 percent;
W K2TiF6 for K 2 TiF 6 Is 240.07;
W TiB2 is TiB 2 Is 69.49;
W KBF4 for KBF 4 Is 125.91;
ρ salt is the density of the molten mixed salt of 2.2g/cm 3 ；
h salt is the depth of the molten mixed salt, which is not more than 3cm depending on the actual production, here taken as 3cm.
This example produces 100kg of ZL101A-3wt.% TiB 2 Composite material, thus m=100 kg=1×10 5 g, preparing ZL101A-3wt.% TiB 2 The composite material needs 11.4kg of potassium fluotitanate, 11.0kg of potassium fluoborate, 58.4kg (m) of AlSi12, 38.0kg (m 3) of pure Al and 0.45kg (m 4) of pure Mg. m2 is 5% by weight of the mixed salt, i.e. m2=1.1 kg. M1=m-m2=57.3 kg.
Substituting the parameters into the above formula, and calculating to obtain the crucible with the diameter of 65cm. Charging a raw material AlSi12 eutectic alloy with the weight of 57.3kg into a crucible with the diameter of 65cm for melting, heating to 600 ℃ after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding potassium fluotitanate and potassium fluoborate mixed salt which are preheated at 400 ℃ for 2 hours into a melt, slowly adding AlSi12 eutectic alloy blocks with the weight of 1.1kg into the melt after the mixed salt is completely dissolved in the melt, and controlling the temperature of the melt to be not more than 650 ℃;
s3: after the reaction is finished, slag skimming is carried out, and vacuum desalination treatment is carried out on the melt for 20min, wherein the temperature of the melt is controlled to be 615 ℃ and the pressure is controlled to be 500Pa in the treatment process;
s4: heating the melt to 770 ℃, adding 38.0kg of pure aluminum ingot, then controlling the temperature to 710 ℃ and adding 0.45kg of pure magnesium;
s5: carrying out melt refining treatment by adopting an argon rotary blowing method, wherein the rotating speed is 450r/min, the pressure of argon is 1.5MPa, and the refining time by adopting the argon rotary blowing method is 20min; regulating the temperature and pouring to obtain TiB with the mass fraction of TiB2 of 3 percent 2 The morphology of the nano reinforced particles of the ZL101A composite material is shown in figure 1.
TiB prepared in this example 2 (3 wt.%)/ZL 101A aluminum matrix composite, tiB 2 The particle size is concentrated at 90-100 nm, after T6 heat treatment regulated by HB 962-2001 and a room temperature tensile test method of GB/T228-2002 are adopted, the average tensile strength of the composite material prepared once is 340MPa, the average yield strength is 260MPa, and the average elongation is 7%.
Example two
The embodiment provides a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite (ZL 114A-5wt.% TiB 2), which specifically comprises the following steps:
s1: the crucible diameter D is calculated according to the following formula:
wherein:
m is the total weight of the composite material prepared;
w t is TiB 2 Is 5wt%;
γ Ti for K 2 TiF 6 The preset yield of Ti in the process is 100 percent;
γ B for KBF 4 The preset yield of B in the step (a) is 100 percent;
W K2TiF6 for K 2 TiF 6 Is 240.07;
W TiB2 is TiB 2 Is 69.49;
W KBF4 for KBF 4 Is 125.91;
ρ salt is the density of the molten mixed salt of 2.2g/cm 3 ；
h salt is the depth of the molten mixed salt, which is not more than 3cm depending on the actual production, here taken as 2.5cm.
This example produces 100kg of ZL114A-5wt.% TiB 2 Composite material, thus m=100 kg=1×10 5 g, preparation of 100kg ZL114A-5wt.% TiB 2 17.3kg of potassium fluotitanate, 18.1kg of potassium fluoborate, 58.4kg (m) of AlSi12, 36.0kg (m 3) of pure Al and 0.7kg (m 4) of pure Mg are needed for the composite material. m2 is 10% by weight of the mixed salt, i.e. m2=3.5 kg. M1=m-m2=54.9 kg.
From the above equation, the crucible diameter was calculated to be 90cm. Charging a raw material AlSi12 eutectic alloy with the weight of 54.9kg into a crucible with the diameter of 90cm for melting, heating to 600 ℃ after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding potassium fluotitanate and potassium fluoborate mixed salt which are preheated at 400 ℃ for 2 hours into a melt, slowly adding AlSi12 eutectic alloy blocks with the weight of 3.5kg into the melt after the mixed salt is completely dissolved in the melt, and controlling the temperature of the melt to be not more than 650 ℃;
s3: after the reaction is finished, slag skimming is carried out, and vacuum desalination treatment is carried out on the melt for 20min, wherein the temperature of the melt is controlled to be 615 ℃ and the pressure is controlled to be 500Pa in the treatment process;
s4: heating the melt to 770 ℃, adding 36.0kg of pure aluminum ingot, then controlling the temperature to 710 ℃ and adding 0.7kg of pure magnesium;
s5: carrying out melt refining treatment by adopting an argon rotary blowing method, wherein the rotating speed is 450r/min, the pressure of argon is 1.5MPa, and the refining time by adopting the argon rotary blowing method is 20min; regulating the temperature and pouring to obtain TiB with the mass fraction of TiB2 of 5 percent 2 The morphology of the nano reinforced particles of the ZL114A composite material is shown in figure 2.
TiB prepared in this example 2 (5 wt.%)/ZL 114A aluminum-based composite, tiB 2 The particle size is concentrated at 90-100 nm, after T6 heat treatment regulated by HB 962-2001 and the room temperature tensile test method of GB/T228-2002, the average tensile strength of the composite material prepared once is 395MPa, the average yield strength is 325MPa, and the average elongation is 6%.
Example III
The embodiment provides a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite (ZL 101A-3wt.% TiB 2), which specifically comprises the following steps:
s1: charging a raw material AlSi12 eutectic alloy with the weight of 57.3kg into a crucible with the diameter of 30cm for melting, heating to 600 ℃ after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding potassium fluotitanate and potassium fluoborate mixed salt which are preheated at 400 ℃ for 2 hours into a melt, slowly adding AlSi12 eutectic alloy blocks with the weight of 1.1kg into the melt after the mixed salt is completely dissolved in the melt, and controlling the temperature of the melt to be not more than 650 ℃;
s3: after the reaction is finished, slag skimming is carried out, and vacuum desalination treatment is carried out on the melt for 20min, wherein the temperature of the melt is controlled to be 615 ℃ and the pressure is controlled to be 500Pa in the treatment process;
s4: heating the melt to 770 ℃, adding 38kg of pure aluminum ingot, then controlling the temperature to 710 ℃ and adding 0.45kg of pure magnesium;
s5: carrying out melt refining treatment by adopting an argon rotary blowing method, wherein the rotating speed is 450r/min, the pressure of argon is 1.5MPa, and the refining time by adopting the argon rotary blowing method is 20min; regulating the temperature and pouring to obtain TiB with the mass fraction of TiB2 of 3 percent 2 The morphology of the nano reinforced particles of the ZL101A composite material is shown in figure 3.
TiB prepared in this example 2 (3 wt.%)/ZL 101A aluminum matrix composite, tiB 2 The particle size is concentrated at 90-100 nm, and a large number of large grain TiB with the size close to 2 mu m is observed on SEM photo 2 And (3) phase (C). After T6 heat treatment prescribed by HB 962-2001 and a room temperature tensile test method of GB/T228-2002, the average tensile strength of the composite material prepared once is 315MPa, the average yield strength is 240MPa, and the average elongation is 4%.
TiB2 prepared in example one and example three has a TiB2 mass fraction of 3% 2 The nano reinforced particles of the ZL101A composite material are prepared under the same experimental conditions except the diameter of a crucible, and compared with the figures 1 and 3, the nano reinforced particles prepared in the figure 1, namely the first embodiment, obviously have better dispersibility; and the size of the particles is more uniform, because the increase of the cross-sectional area of the crucible is beneficial to the dispersion of the reaction products; meanwhile, the heat dissipation area is increased, heat conduction released by the reaction is facilitated, and the reinforced particles with high shape and size consistency are obtained.
Example IV
The embodiment provides a preparation method of a low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite (ZL 114A-5wt.% TiB 2), which specifically comprises the following steps:
s1: the crucible diameter D is calculated according to the following formula:
wherein:
d is the diameter of the crucible;
m is the total weight of the composite material prepared;
w t is TiB 2 Is 5wt%;
γ Ti for K 2 TiF 6 The preset yield of Ti in the process is 100 percent;
γ B for KBF 4 The preset yield of B in the step (a) is 100 percent;
W K2TiF6 for K 2 TiF 6 Is 240.7;
W TiB2 is TiB 2 Is 69.49;
W KBF4 a molecular weight of KBF4 of 125.91;
ρ salt is the density of the molten mixed salt of 2.2g/cm 3 ；
h salt is the depth of the molten mixed salt, which is not more than 3cm depending on the actual production, here taken as 2.5cm.
This example prepares 100kg of ZL114A-5wt.% TiB2 composite material, so m=100 kg=1×10 5 g, preparation of 100kg ZL101A-5wt.% TiB 2 17.3kg of potassium fluotitanate, 18.1kg of potassium fluoborate, 58.4kg (m) of AlSi12, 36.0kg (m 3) of pure Al and 0.7kg (m 4) of pure Mg are needed for the composite material.
From the above equation, the crucible diameter was calculated to be 90cm. Charging raw material AlSi12 eutectic alloy with the weight of 58.4kg into a crucible with the diameter of 90cm for melting, heating to 600 ℃ after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding mixed salt of potassium fluotitanate and potassium fluoborate preheated at 400 ℃ for 2 hours into the melt, and waiting for the mixed salt to be completely dissolved in the melt;
s3: after the reaction is finished, slag skimming is carried out, and vacuum desalination treatment is carried out on the melt for 20min, wherein the temperature of the melt is controlled to be 615 ℃ and the pressure is controlled to be 500Pa in the treatment process;
s4: heating the melt to 770 ℃, adding 36.0kg of pure aluminum ingot, then controlling the temperature to 710 ℃ and adding 0.7kg of pure magnesium;
s5: carrying out melt refining treatment by adopting an argon rotary blowing method, wherein the rotating speed is 450r/min, the pressure of argon is 1.5MPa, and the refining time by adopting the argon rotary blowing method is 20min; regulating the temperature and pouring to obtain TiB with the mass fraction of TiB2 of 5 percent 2 The morphology of the nano reinforced particles of the ZL114A composite material is shown in figure 4.
TiB prepared in this example 2 (5 wt.%)/ZL 114A aluminum-based composite, tiB 2 The particle size is largely 400-800 nm, and T6 heat treatment prescribed by HB 962-2001 is adoptedAfter that, and the room temperature tensile test method of GB/T228-2002, the average tensile strength of the composite material prepared once is 360MPa, the average yield strength is 315MPa, and the average elongation is 4%.
TiB2 prepared in example four was 5% TiB by mass 2 Compared with the nano reinforced particles prepared in the second embodiment, the nano reinforced particles of the ZL114A composite material are prepared under the same experimental conditions except that the Al-Si eutectic alloy blocks are not added into the melt for cooling in the fourth embodiment, and compared with the FIG. 2 and the FIG. 4, the nano reinforced particles prepared in the fourth embodiment form a large number of clusters, and the dispersing effect and uniformity are far lower than those of the nano reinforced particles prepared in the second embodiment, because the controllability of the melt temperature in the reaction process is further improved in the cooling process of adding the Al-Si eutectic alloy blocks, the reaction is continuously and stably carried out, so that the reinforced particles with uniform morphology and uniform size are obtained.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. The preparation method of the low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite material is characterized by comprising the following steps of:
s1: charging a raw material AlSi12 eutectic alloy with the weight of m1 into a crucible with the diameter of D for melting, heating to a certain temperature after melting, preserving heat, and uniformly stirring the preserved eutectic alloy melt;
s2: adding potassium fluotitanate and potassium fluoborate mixed salt into a melt for reaction, and slowly adding an AlSi12 eutectic alloy block with the weight of m2 into the melt after the mixed salt is completely melted;
s3: after the reaction is completed, slag skimming is carried out, and vacuum desalting treatment is carried out on the melt;
s4: heating the melt, adding pure aluminum ingot with the weight of m3, and then controlling the temperature and adding pure magnesium with the weight of m 4;
s5: and (3) carrying out melt refining treatment by adopting an argon rotary blowing method, adjusting the temperature and casting.
2. The method for preparing a low-temperature in-situ synthesized nanoparticle-reinforced aluminum matrix composite material according to claim 1, wherein the crucible diameter D, the total weight m of the prepared composite material and TiB contained in the prepared composite material 2 The mass fraction of the nanoparticles corresponds to the following relationship:
wherein:
d is the diameter of the crucible;
m is the total weight of the composite material prepared;
w t is TiB 2 Is a design content of (2);
γ Ti for K 2 TiF 6 The preset yield of Ti in the process;
γ B for KBF 4 The preset yield of B;
W K2TiF6 for K 2 TiF 6 Is a relative molecular weight of (2);
W TiB2 is TiB 2 Is a relative molecular weight of (2);
W KBF4 for KBF 4 Is a relative molecular weight of (2);
ρ salt Is the density of the molten mixed salt;
h salt For the depth of the molten mixed salt, this value is not more than 3cm depending on the actual production.
3. The method for preparing a low-temperature in-situ synthesized nanoparticle-reinforced aluminum matrix composite according to claim 1, wherein in the step S1, the temperature is increased to 590-610 ℃.
4. The method for preparing the low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite according to claim 1, wherein in the step S2, the mixed salt of potassium fluotitanate and potassium fluoborate is subjected to heat preservation at 400 ℃ for 2h for preheating treatment; adding mixed salt of potassium fluotitanate and potassium fluoborate into the melt for reaction, slowly adding AlSi12 eutectic alloy blocks with the weight of m2 into the melt in the reaction process, and controlling the temperature of the melt in the reaction process to be not more than 650 ℃; the weight m2 of the added AlSi12 eutectic alloy blocks is 5-10% of the weight of the added mixed salt.
5. The method for preparing the low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite according to claim 1, wherein in the step S3, conditions for vacuum desalting treatment are as follows: the temperature of the melt is 600-630 ℃, the pressure is not more than 500Pa, and the vacuum desalination treatment time is 15-30 min.
6. The method for preparing the low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite material according to claim 1, wherein in the step S4, the temperature of a melt is raised to 760-780 ℃ before pure aluminum ingots are added; before adding pure magnesium, the temperature of the melt is controlled to be 700-720 ℃.
7. The method for preparing the low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite according to claim 1, wherein in the step S5, the rotation speed of the argon gas rotary blowing method is 300-600 r/min, the pressure of the argon gas is 1-2 MPa, and the refining time of the argon gas rotary blowing method is 15-25 min.
8. A nanoparticle reinforced aluminum matrix composite prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310792897.5A CN116815005A (en) | 2023-06-30 | 2023-06-30 | Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310792897.5A CN116815005A (en) | 2023-06-30 | 2023-06-30 | Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116815005A true CN116815005A (en) | 2023-09-29 |
Family
ID=88142647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310792897.5A Pending CN116815005A (en) | 2023-06-30 | 2023-06-30 | Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116815005A (en) |
-
2023
- 2023-06-30 CN CN202310792897.5A patent/CN116815005A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109530468B (en) | In-situ nano reinforced aluminum alloy extrusion material for light vehicle body and isothermal variable-speed extrusion preparation method | |
| CN110257655B (en) | High-dispersion-distribution nano titanium diboride particle reinforced aluminum-based composite material and preparation method thereof | |
| WO2021114967A1 (en) | Method for preparing aluminum-based composite material reinforced in situ by ternary nanoparticles | |
| WO2016184237A1 (en) | 6x82 aluminium-based composite material for use in automobile control arm and preparation method thereof | |
| WO2022105453A1 (en) | Preparation method for high-strength and high-toughness a356.2 aluminum matrix composite for hub | |
| CN109692964A (en) | A kind of reinforced aluminum matrix composites and preparation method thereof | |
| CN114672686B (en) | Preparation method of additional nano-particle reinforced cast aluminum-lithium alloy | |
| CN115786784A (en) | High-strength and high-toughness cast aluminum-silicon-copper-magnesium alloy, and preparation method and application thereof | |
| CN107952966A (en) | The preparation method at spherical titanium aluminium-based alloyed powder end | |
| CN110229979B (en) | Intragranular grain boundary distribution micro-nano complex phase particle reinforced aluminum matrix composite material and preparation method thereof | |
| CN110004316B (en) | Preparation method of in-situ nano ceramic particle reinforced aluminum-based composite material | |
| CN115896509B (en) | Preparation method for constructing superfine crystal structure in magnesium alloy | |
| CN116815005A (en) | Preparation method of low-temperature in-situ synthesized nanoparticle reinforced aluminum matrix composite | |
| CN114990390B (en) | Preparation method of in-situ synthesized binary nanoparticle reinforced aluminum matrix composite | |
| CN112662909B (en) | Carbide nanoparticle modified die-casting aluminum alloy and preparation method thereof | |
| CN112941358B (en) | Preparation method of graphene-reinforced Mg-Al-Zn alloy | |
| CN113373367A (en) | Aluminum intermediate alloy containing multi-scale mixed particles and preparation method thereof | |
| CN219079617U (en) | System for in situ synthesis of nanoparticle reinforced aluminum matrix composite | |
| CN112195358A (en) | Aluminum-based alloy, aluminum-based composite material, and preparation method and application thereof | |
| CN116179884B (en) | Vacuum induction smelting method for preparing titanium-coated NbB2Method for reinforcing TiAl alloy by nano particles | |
| CN113528910A (en) | Graphene reinforced rare earth magnesium-based composite material and preparation method thereof | |
| CN116024452A (en) | Method for in-situ synthesis of nanoparticle reinforced aluminum matrix composite | |
| CN116815006A (en) | Method for preparing in-situ synthesized nano-particle reinforced aluminum matrix composite material by centrifugal reaction | |
| CN116200625B (en) | Nanoparticle modified aluminum alloy and preparation method thereof | |
| CN114369742B (en) | BaB6Preparation method of/Al composite material inoculant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |