CN103074506A - Two-step charging method for preparing high-quality Al-Ti-B intermediate alloy refiner - Google Patents
Two-step charging method for preparing high-quality Al-Ti-B intermediate alloy refiner Download PDFInfo
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Abstract
The invention relates to a two-step charging method for preparing a high-quality Al-Ti-B intermediate alloy refiner. The method comprises the following steps: firstly, respectively and excessively weighing certain weight of K2TiF6 and KBF4 raw materials according to the stoichiometric ratio of the chemical equation 2KBF4+K2TiF6+10/3Al=TiB2+3KAlF4+1/3K3AlF6 or a small amount of K2TiF6, and uniformly mixing, and then adding the mixture of K2TiF6 and KBF4 into molten aluminum; stirring, standing, stirring again and performing grain slag pouring processing; adding the rest mixture of K2TiF6 and KBF4 into the molten aluminum again, and pouring grain slag after the reaction is completed; and directly casting the molten aluminum into the trapezoidal bulk material or producing wire rods through a continuous casting rolling mill after performing degasification and deslagging processing again. According to the invention, during the production for Al-Ti-B product, the TiB2 particles and TiAl3 phase are small in sizes and uniform in dispersing distribution, and the large-sized TiAl3 phase or strip-shaped TiAl3 phase does not exist in the metallographic structure completely, so that the requirements for refining processing of high-grade, precision and advanced and high-quality aluminium alloy material.
Description
Technical field
The invention belongs to material and metallurgical technology in new material technology field, relate to the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of a kind of two steps, is to add K by changing in traditional villiaumite method about two stages
2tiK
6and KBF
4the ratio difference of raw material improves a kind of production technique of Al-Ti-B master alloy fining agent quality.
Background technology
In recent years, aluminium and aluminium alloy are because quality is light, and cost performance is high, the Beauty, and good combination property, be widely used in high-tech areas such as mechanical industry, automotive industry, aviation and war industrys.Yet, along with the day by day raising of people to material requirements, especially at high-technology field, the over-all properties of conventional aluminum alloy can not be satisfied the demand.In order to improve aluminum alloy materials, the over-all properties of cast aluminium alloy especially, inner grain structure is structurally-modified becomes current main direction of studying.As everyone knows, cast aluminium alloy generally can produce the brilliant three kinds of tissues of equiax crystal, column crystal and featheriness in solidification and crystallization process by using, wherein column crystal and featheriness crystalline substance can cause the decline of mechanical property, particularly the performances such as processing characteristics, yield strength and unit elongation of cast aluminium alloy had to great effect, this crystalline tissue also easily causes in castingprocesses producing surface imperfection.Therefore, in aluminium alloy casting and processing industry, often need the solidification and crystallization tissue of adopting various measures to aluminium alloy to carry out refinement, to suppress thick column crystal and featheriness crystalline substance, thereby obtain more tiny and equally distributed equiaxed grain structure.
For cast aluminium alloy, can carry out crystal grain thinning by a lot of methods, mainly comprise following four aspects: (1) improves the aluminum alloy solidification speed of cooling.(2) mechanical-physical refinement method, comprise mechanical vibration, mechanical stirring etc.(3) physical field refinement method, as electric field, magnetic field, ultrasonication, particularly the pulse physical field becomes the new highlight of physical field crystal grain thinning.(4) superalloy method, as add various master alloy fining agents, promote forming core or suppress nuclei growth.Wherein, in the processing of cast aluminium alloy microstructure thinning, the most simple and effective method is to add a small amount of grain-refining agent in molten aluminium, thereby reaches the purpose of grain refining.
The development of aluminum grain refiner roughly is divided into following several stages: the forties in 20th century, use the salt fusant that contains Ti, B, Zr, Nb etc. as fining agent; The fifties, generally with the salt block agent that contains Ti, B element; The sixties, AlTi alloy block ingot (being 5%, 6% and 10% containing Ti per-cent) is as the fining agent generally used; Develop AlTiB silk (Al-5Ti-1B) seventies, the fining agent of this titaniferous, boron is compared the fining agent that contains separately titanium elements (AlTi) and is had better thinning effect; The eighties in 20th century, different component content (as Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.2B etc.) appearred in the Al-Ti-B silk so far.Current, the agent of Al-Ti-B alloy refinement has become the most general in the aluminum grain refinement industry and the most effective industrial fining agent, effect with the Al-5Ti-1B alloy is best, make grain refinement technology produce breakthrough, its Application Areas has comprised various section bars and the foundry goods such as aluminium and aluminium alloy plate, band, paper tinsel, pipe, rod.
The theoretical investigation prepared about the Al-Ti-B master alloy is very many, and various production technique is also very ripe.Can be divided into conventional ceramic technique, villiaumite method, pure titanium particle method etc. by feedstock property; Can be divided into again thermit reduction, electrolytic process, self propagating high temperature synthesis method etc. by preparation technology, be not an easy thing but produce high-quality Al-Ti-B master alloy fining agent.At present, the most widely used in industrial production is the villiaumite method, utilizes K
2tiF
6and KBF
4produce the Al-Ti-B alloy by thermite reaction.According to the addition sequence of raw material, mainly following chemical reaction can occur in the villiaumite method:
（2）
Particularly, first add KBF in melt
4the time, (1) formula chemical reaction will occur, at first form AlB in melt
2(because the solubleness of B in aluminium liquid is very low, it mainly is present in molten aluminium with compound form); Add again K
2tiF
6after, will mainly carry out the reaction of (2) formula, thereby generate TiAl in melt
3phase, also with a small amount of TiAl
3the dissolution process of phase, make increasing containing the Ti amount in molten aluminium, for condition has been created in the reaction of (5) formula.Therefore, first add KBF
4add again K
2tiF
6the time, in molten aluminium, formed with AlB
2, TiAl
3(Al
1-x, Ti) B
2deng compound, it is main master alloy solidified structure.Otherwise, first add K
2tiF
6the time, the chemical reaction of (2) formula will occur, will at first form TiAl in melt
3phase, and with a small amount of TiAl
3the dissolution process of phase, raise the Ti concentration in melt, then add KBF
4after, the reaction of (4) formula will occur, thereby generate TiB in melt
2phase.Therefore, first add K
2tiF
6add again KBF
4the time, in molten aluminium, formed with TiAl
3and TiB
2the solidified structure of the master alloy that is the master Deng compound.When two kinds of villiaumites mix, add fashionablely, chemical reaction will mainly be pressed (3) formula and carry out, because Ti/B is greater than TiB
2stoichiometric ratio, also will carry out the reaction of (2) formula simultaneously.Therefore, K
2tiF
6with KBF
4being mixed, it is fashionable to add, and mainly contains TiB in molten aluminium
2, TiAl
3with a small amount of (Al
1-x, Ti) B
2deng compound, and in the solidified structure that these are kept to the final mutually.Therefore, change the addition sequence of villiaumite, just changed chemical reaction process, thereby changed the Liquid Structure of master alloy, due to the Structure Heredity contact between liquid-solid-state, this structural state just is genetic in Solid State Structure, causes having different phase composites in solid-state Al-Ti-B master alloy tissue.
Numerous researchs show, although, aspect the Refining Mechanism of Al-Ti-B master alloy fining agent, everybody does not also reach unified understanding, be familiar with still more consistent for the effect of several compounds in the alloy heterogeneous microstructure: (1) AlB
2(or (Al
1-x, Ti) B
2) only can be distributed on the crystal boundary of Al, can not become effective nucleating center of fine aluminium, thus very limited to the refining effect of fine aluminium; (2) TiB
2phase and TiAl
3the form of phase, size and disperse distribution situation are the deciding factors that affects thinning effect.Therefore, the microstructure to the Al-Ti-B master alloy in " People's Republic of China's non-ferrous metal industry standard " (YS/T 447.1-2002) describes in detail, wherein in the microstructure of firsts and seconds, stipulates: TiB in tissue
2single particle diameter≤2 μ m's should be more than 90%, and the roughly even dispersion that distributes allows the TiB of size≤25 μ m
2loose agglomerate exists.TiAl
3the corresponding bulk or shaft-like that is, distribute roughly even, and mean sizes is 30 μ m * 50 μ m, TiAl
3phase size<150 μ m's should be more than 95%.And while appearing as three grades of microstructures in alloy, this product just is defined as defective.Therefore, how industrial, produce the TiB that size is tiny, disperse is evenly distributed
2phase and TiAl
3become mutually Al-Ti-B master alloy fining agent quality and improved the main problem faced.
Traditional villiaumite method production technique mainly is divided into once reinforced method and casings in twice method.Wherein, once reinforced method can be saved the production time, reduces manipulation strength, but, because this alloying reaction is an exothermic process, once in reinforced process, the melt temperature rising is more, easily produces strip TiAl
3phase, and, because grain slag amount in reaction is too large, cause the speed of response of later stage villiaumite to reduce, the Al-Ti-B master alloy fining agent finally obtained is second-rate.The secondary charging method can avoid temperature to raise too much and the excessive shortcoming of grain slag amount, therefore be subject at present the attention of industry member, but traditional secondary charging process is only required K
2tiF
6+ KBF
4compound is divided into two parts to be added.This traditional secondary charging method is owing in reinforced process, a large amount of TiAl being arranged for the first time
3generate mutually, reinforced for the second time after, except small part Ti atom can lean on self-energy to change to obtain motivating force and forming core grow up into undersized TiAl
3phase, most of Ti atom can be at the TiAl originally existed
3go up mutually continued growth, finally be grown to the TiAl of the larger and rectangular pattern of size
3phase.Therefore, the Al-Ti-B master alloy fining agent quality that this secondary charging method is produced is general, TiAl in alloy structure
3the phase size homogeneity is very poor, what have reaches 50 ~ 80 μ m, also have≤5 μ m, and pattern is also various, have plenty of particulate state, also have plenty of strip, the Polygons with regular edge also had, this product meets the industry standard of Al-Ti-B master alloy fining agent on the whole substantially, but also poor far from the specification of quality of high quality Al-Ti-B master alloy fining agent.
In view of above problem, we have invented the method that the reinforced method of a kind of two steps is produced high quality Al-Ti-B master alloy fining agent: the K that at first by special proportioning, takes respectively certainweight
2tiF
6and KBF
4raw material, and mix; Then at a certain temperature by this part K
2tiF
6+ KBF
4compound adds aluminium liquid by certain speed; Through stirring, standing, stir and after the pouring slag processes, again remaining K again
2tiF
6and KBF
4compound adds melt, and reaction is outwelled grain slag after finishing; Finally by degasification with after slagging-off is processed again, direct pouring becomes the trapezoidal bulk of Al-Ti-B or is produced into the Al-Ti-B wire rod by continuous casting and continuous rolling mill.Technique of the present invention is simple, convenient operation, the not only TiB that produces in the Al-Ti-B product
2phase and TiAl
3all size is tiny mutually, and disperse is evenly distributed, and there is no large size TiAl fully in metallographic structure
3phase or long strip shape TiAl
3occur mutually, that quality product can meet is high-grade, precision and advanced, the requirement of high-quality aluminum alloy material thinning processing.Therefore, this invention has fine industrial application value.
Summary of the invention
The objective of the invention is will be traditional the villiaumite method produce in addition improvement and bring new ideas of the shortcoming that exists in aluminum grain refiner technique and problem, a kind of method of producing high quality Al-Ti-B master alloy fining agent is provided.
The reinforced legal system of a kind of two steps, for the method for high-quality Al-Ti-B master alloy fining agent, at first takes respectively the K of certainweight according to the stoichiometric ratio of chemical equation (3)
2tiF
6and KBF
4raw material, and mix; Then at a certain temperature by this part K
2tiF
6+ KBF
4compound adds in aluminium liquid by certain speed; Stir also and after standing certain hour, the grain slag produced that feeds in raw material is for the first time outwelled, then remaining K
2tiF
6and KBF
4compound adds melt, again after stirring standing certain hour, that grain slag is clean; Finally by rare gas element Ar or N
2gas is to the liquation degasification and after slagging-off is processed again, and direct pouring becomes the trapezoidal bulk of Al-Ti-B or is produced into the Al-Ti-B wire rod by continuous casting and continuous rolling mill.This invented technology is simple, and convenient operation provides a kind of very effective industrial process for producing high quality Al-Ti-B master alloy fining agent.
Technical scheme provided by the invention is: the K added altogether for twice
2tiF
6amount and KBF
4amount is to determine according to the composition of Al-Ti-B master alloy fining agent, while it is characterized in that feeding in raw material for the first time, and K
2tiF
6and KBF
4according to chemical equation 2KBF
4+ K
2tiF
6+ 10/3Al=TiB
2+ 3KAlF
4+ 1/3K
3alF
6stoichiometric ratio or K
2tiF
6a small amount of excessive being added in aluminum melt arranged, guarantee not there will be AlB in alloying process for the first time
2phase, obtained only containing TiB
2mutually or also have few TiAl
3the melt of phase completes the operations such as slagging-off, degasification after the alloying of having fed in raw material for the second time in middle frequency furnace, and last direct pouring becomes the trapezoidal bulk of Al-Ti-B or is produced into the Al-Ti-B wire rod by continuous casting and continuous rolling mill, mainly comprises the following steps:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours into and subcontract in stove, prepare next step alloying process;
2) reinforced for the first time: as in reinforced process for the first time, by the mass ratio of 0.953:1 ~ 1:1, to take respectively a certain amount of K
2tiF
6and KBF
4raw material, and mix KBF in feeding in raw material for the first time in mixer
4weight be required KBF
460% ~ 90% of total amount, then by K
2tiF
6+ KBF
4compound is poured the conical hopper of charging machine into, by the feed rate of 30 ~ 40 rev/mins of charging machines, raw material is added in aluminum melt, and feed time is 5 ~ 8 minutes; To constantly stir in reinforced process, to guarantee raw material, be evenly distributed on reaction interface, also need after reinforced the end to continue to stir 3 ~ 5 minutes, can play thermolysis on the one hand, make on the other hand reactant TiB
2phase and TiAl
3be on good terms and be uniformly distributed, can also destroy rich B Huo Fu Ti district, avoid TiB
2phase and TiAl
3too growing up of phase; After stirring end, standing 5 ~ 8 minutes so that the interior various impurity of stove can form scum silica frost or gas is removed and pass through the elemental composition that the processes such as mass transfer, diffusion are adjusted regional in stoves; After standing end, again stir after 2 ~ 3 minutes and outwell grain slag;
3) reinforced for the second time: by K remaining in required villiaumite
2tiF
6and KBF
4after raw material mixes in mixer, also K
2tiF
6+ KBF
4compound is poured the conical hopper of charging machine into, by the feed rate of 20 ~ 30 rev/mins of charging machines, raw material is added in aluminum melt, and feed time is 6 ~ 10 minutes, and is accompanied by whipping process; After secondary charging finishes, the continuation stirring starts standing after 3 ~ 5 minutes, after standing 8 ~ 10 minutes, then stir 2 ~ 3 minutes, starts afterwards the pouring slag, and the slag operation that dewaters finally obtains clean aluminum melt after finishing;
4) insulation, degasification and slagging-off are processed: the molten aluminium that will subcontract in stove is poured in middle frequency furnace, and unlatching heating and heat-insulating device, promote in stove temperature to 760 ℃ ~ 800 ℃, carbon tube with an about 20mm aperture in temperature-rise period leads to argon gas or nitrogen, air flow is advisable to allow aluminium liquid roll continuously to seethe with excitement from bottom to up, residue meeting continuous emersion surface in melt, ventilate after 8 ~ 10 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 10 ~ 15 minutes of aluminum melt; Repeat again afterwards the ventilation, slagging-off of front and standing process 2 ~ 3 times, to guarantee that in molten aluminium, the content of slag is reduced to minimum level;
5) pour into a mould trapezoidal bulk or continuous casting and rolling and become wire rod: when the aluminum melt temperature reaches 760 ℃ ~ 800 ℃ in the intermediate frequency electric furnace, the operation that starts to release, the aluminum melt in stove flows into the casting machine direct production through chute and goes out the trapezoidal bulk of Al-Ti-B master alloy or flow into continuous casting and continuous rolling mill to produce Al-Ti-B master alloy wire rod.
In the present invention, core content is to control KBF in reinforced process
4and K
2tiF
6adding proportion.In technique, require only reacting generation TiB in alloying process for the first time
2phase, do not generate or only generate the seldom TiAl of amount basically
3phase, but definitely can not generate AlB
2phase.According to chemical equation 2KBF
4+ K
2tiF
6+ 10/3 Al=TiB
2+ 3KAlF
4+ 1/3K
3alF
6middle KBF
4and K
2tiF
6metering show that than relation this occurs in theory fully reacts required K
2tiF
6and KBF
4mass ratio be 0.953:1, but for fear of because reacting, not exclusively producing superfluous KBF
4, to such an extent as to AlB appears
2phase, the preferred K of the present invention
2tiF
6and KBF
4mass ratio be 1:1.
Add CaF while in the present invention, after reinforced end for the second time, removing grain slag
2in flux and grain slag, add-on is 0.4% ~ 0.8% of aluminium weight.
KBF while feeding in raw material for the first time in the present invention
4weight be preferably required KBF
470% of total amount.
The Al-Ti-B master alloy fining agent that the present invention can prepared composition is Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.5B, Al-5Ti-0.3B etc., also can prepare the Al-Ti-B master alloy fining agent of various patterns, comprise ingot casting, trapezoid block, wire rod, bar etc.
In the present invention in order to improve Al-Ti-B master alloy fining agent quality, fine aluminium is melted in to pour into subcontracts after stove impurity and the oxide compound that will dispose aluminium liquid surface.
Alloying process is in the present invention controlled temperature in 700 ℃ of-750 ℃ of scopes
.
the beneficial effect of the invention
In the reinforced method of two steps of the present invention for the first time in reinforced process owing to having adopted special mass ratio 1:1(K
2tiF
6: KBF
4) proportion scale, therefore, guaranteeing not there will be AlB in alloying process for the first time
2under the prerequisite of phase, obtained only containing TiB
2mutually or also have few TiAl
3the melt of phase.In this melt due to the TiB that has a large amount of fine size
2phase (≤3um), so when feeding in raw material for the second time, TiAl
3the nucleus of phase forms and grows up and all has been subject to very large impact.Particularly, due to TiB
2the heterogeneous forming core effect of phase, make TiAl
3the forming core merit of nucleus obviously reduces, and the formation of nucleus becomes very easy, so that nucleation rate is improved, and add the Ti atom total amount in melt, is certain, so each TiAl
3in the nuclei growth process, resulting Ti atomic quantity just can not be too many.In addition, due to TiAl
3just in subordinate phase, just start forming core and growth mutually, therefore adding K
2tiF
6under the constant prerequisite of raw material total amount, reduced TiAl
3the growth time of phase.And work as TiAl
3grow up mutually to also can be because of a large amount of TiB in surface after certain size
2the coating function of particle, slow down and even stop TiAl
3growing up of phase.The impact of above three factors just, TiAl in last gained Al-Ti-B alloy product
3phase size is tiny, and distribution of sizes is more even, there is no to occur the TiAl of large-sized especially or long strip shape
3phase.This technique can be produced the Al-Ti-B master alloy fining agent of various compositions, comprise Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.5B, Al-5Ti-0.3B etc., and the Al-Ti-B master alloy fining agent of various patterns, comprise ingot casting, trapezoid block, wire rod, bar etc., so the present invention provides a kind of extremely important method for industry member production high quality Al-Ti-B master alloy fining agent.
The invention has the advantages that:
1. technique is simple, easy to operate.Do not use complicated equipment in the present invention, loaded down with trivial details technical process also do not occur, therefore for enterprise, technique is simple, easy to operate;
2. level of automation is high, and labour intensity is low.In the present invention, most of flow process is all by the machinery equipment automatic operation, such as: raw material has been used automatic mixing machine in mixing; Used automatic charging equipment in reinforced process; Whipping process has transit mixer; The product final production has continuous casting and continuous rolling mill etc., and the workman only need to control various operating parameterss aside and get final product, so in this technical process, workman's labour intensity has obtained very large reduction;
3. constant product quality.In technological operation of the present invention, major part is all to be completed by machine automatization, as long as operating parameters, as temperature, feed rate, stirring intensity, churning time, charge weight, degasification time, pouring speed etc. are strict, control, just can products quality guarantee stablize;
4. quality product is high.Due to the reinforced process of two steps special in the present invention, not only increased TiAl
3the nucleation rate of phase, improved TiAl
3the quantity of phase, and reduced TiAl
3the growth time of phase, thereby guaranteed TiAl in the tissue of last gained alloy
3phase size is tiny, is evenly distributed.In addition, violent stirring has promoted mass transfer and the diffusion process of aluminum melt inside, has reduced the appearance in rich B Huo Fu Ti district, adds the TiB generated in the first step
2the effect of phase, thus large size or long strip shape TiAl effectively avoided
3the generation of phase, so gained Al-Ti-B master alloy fining agent quality of the present invention is high, can well meet requirement high-grade, precision and advanced, the high-quality aluminum alloy thinning processing;
5. product diversification.Technique of the present invention can adapt to the production of various composition Al-Ti-B master alloy products, as Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.5B, Al-5Ti-0.3B etc., and the Al-Ti-B master alloy fining agent of various patterns, comprise ingot casting, trapezoid block, wire rod, bar etc., therefore product diversification, can meet various clients' needs.
The accompanying drawing explanation
The macro morphology that Fig. 1 is Al-5Ti-1B master alloy wire rod in example 1.
The heterogeneous microstructure figure (metallograph) that Fig. 2 is example 1 interalloy: the heterogeneous microstructure of the final Al-5Ti-1B alloy wire of heterogeneous microstructure (b) of aluminium alloy after (a) reinforced for the first time.
Fig. 3 is the interior TiAl of Al-5Ti-1B master alloy wire rod in example 1
3the diameter Distribution figure of phase.
The macro morphology that Fig. 4 is Al-5Ti-0.5B master alloy wire rod in example 2.
The heterogeneous microstructure figure (metallograph) that Fig. 5 is example 2 interalloies: the heterogeneous microstructure of the final Al-5Ti-0.5B alloy wire of heterogeneous microstructure (b) of aluminium alloy after (a) reinforced for the first time.
Fig. 6 is the interior TiAl of Al-5Ti-0.5B master alloy wire rod in example 2
3the diameter Distribution figure of phase.
The macro morphology that Fig. 7 is the trapezoidal bulk of Al-5Ti-1B master alloy in example 3.
The heterogeneous microstructure figure (metallograph) that Fig. 8 is example 3 interalloies: the heterogeneous microstructure of the final trapezoidal bulk of Al-5Ti-1B alloy of heterogeneous microstructure (b) of aluminium alloy after (a) reinforced for the first time.
Fig. 9 is the interior TiAl of the trapezoidal bulk of Al-5Ti-1B master alloy in example 3
3the diameter Distribution figure of phase.
The macro morphology that Figure 10 is Al-5Ti-1B master alloy wire rod in Comparative Examples.
The heterogeneous microstructure figure (metallograph) that Figure 11 is the Comparative Examples interalloy: the heterogeneous microstructure of the final Al-5Ti-1B alloy wire of heterogeneous microstructure (b) of aluminium alloy after (a) reinforced for the first time.
Figure 12 is the interior TiAl of Al-5Ti-1B master alloy wire rod in Comparative Examples
3the diameter Distribution figure of phase.
Embodiment
The method of the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of special two steps provided by the invention is as follows:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours into and subcontract in stove, prepare next step alloying process.
2) reinforced for the first time: the mass ratio by 1:1 takes respectively a certain amount of K
2tiF
6and KBF
4raw material, and mix in mixer, wherein, KBF in feeding in raw material for the first time
4weight be required KBF
460% ~ 90% of total amount.Then by K
2tiF
6+ KBF
4compound is poured the conical hopper of charging machine into, by the feed rate of 30 ~ 40 rev/mins of charging machines, raw material is added in aluminum melt, and is accompanied by continuous stirring.Continue to stir 3 ~ 5 minutes after reinforced the end, then start standing.After standing 8 ~ 10 minutes, again stir 2 ~ 3 minutes, finally outwell the grain slag on aluminum melt surface.
3) reinforced for the second time: by K remaining in required villiaumite
2tiF
6and KBF
4after raw material mixes in mixer, also K
2tiF
6+ KBF
4compound is poured the conical hopper of charging machine into, by the feed rate of 20 ~ 30 rev/mins of charging machines, raw material is added in aluminum melt, and is accompanied by whipping process.After secondary charging finishes, continue stirring and start standing after 3 ~ 5 minutes.After standing 8 ~ 10 minutes, then stir 2 ~ 3 minutes, start afterwards the pouring slag, simultaneously, clean in order to remove grain slag, also need to add 0.4% ~ 0.8% CaF of aluminium weight
2during flux comes and grain slag.The slag operation that dewaters finally obtains clean aluminum melt after finishing.
4) insulation, degasification and slagging-off are processed: the molten aluminium that will subcontract in stove is poured in middle frequency furnace, and opens heating and heat-insulating device, promotes in stove temperature to 760 ℃ ~ 800 ℃.In temperature-rise period, with the logical argon gas of carbon tube or the nitrogen in an about 20mm aperture, air flow is advisable to allow aluminium liquid roll continuously to seethe with excitement from bottom to up, and the residue in melt can continuous emersion surface.Ventilate after 8 ~ 10 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 10 ~ 15 minutes of aluminum melt.Afterwards, ventilation, slagging-off and standing process are just now repeated 2 ~ 3 times again, to guarantee that in molten aluminium, the content of slag is reduced to minimum level.
5) pour into a mould trapezoidal bulk or continuous casting and rolling and become wire rod: when the aluminum melt temperature reaches 760 ℃ ~ 800 ℃ in the intermediate frequency electric furnace, the operation that starts to release, the aluminum melt in stove flows into the casting machine direct production through chute and goes out the trapezoidal bulk of Al-Ti-B master alloy or flow into continuous casting and continuous rolling mill to produce Al-Ti-B master alloy wire rod.
Below in conjunction with drawings and Examples, the present invention is further set forth, but within therefore not limiting the present invention to described scope of embodiments.Under the prerequisite that does not break away from design philosophy of the present invention; various modification and improvement that in this area, engineering technical personnel make technical scheme of the present invention; all should fall into protection scope of the present invention, the technology contents that the present invention asks for protection, all be documented in claims.
Embodiment 1: the manufacture of high quality Al-5Ti-1B alloy wire
The 1028kg99.7% aluminium ingot is melted in molten aluminium stove, and be heated to 745 ℃, then pour into and subcontract in stove, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide compound.Control is subcontracted temperature in stove and, at 700 ℃-750 ℃, is taken the K of 84kg purity 98%
2tiF
6with 84kg(be required KBF
4total amount 70%) KBF of purity 98%
4raw material mixes in mixer.The K just now weighed up
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 33 rev/mins to aluminum melt, and the reinforced material time is 6 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 5 minutes for the first time, then standing 8 minutes, then stir 2 minutes, finally the grain slag on aluminium liquid surface is outwelled.Again take the K of 156kg purity 98%
2tiF
6kBF with 36kg purity 98%
4raw material mixes in mixer.The K weighed up for the second time
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 25 rev/mins to aluminum melt, and the reinforced material time is 8 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 5 minutes for the second time, then standing 10 minutes, then stir 3 minutes, afterwards the grain slag on aluminium liquid surface is outwelled, add the CaF of 5kg
2in powder and the grain slag of remained on surface, and the slag that this process is produced is also removed clean together.Afterwards the aluminum melt of subcontracting in stove is poured into to middle frequency furnace, open heating and heat-insulating device, make melt temperature rise to 770 ℃ of left and right.In the middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to the aluminum melt bottom, and start to pass into nitrogen, air flow rolls continuously to seethe with excitement from bottom to up with aluminum melt and is advisable, and the residue of melt inside can continuous emersion surface.Ventilate after 6 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 12 minutes of aluminum melt.Afterwards, then ventilate 8 minutes, remove after residue standing 10 minutes.Ventilate for the third time 10 minutes, remove after residue standing 15 minutes.Measure temperature of aluminum liquid and reach 772 ℃, then start to release.Aluminum melt is flowed directly into to continuous casting and continuous rolling mill through chute and produce Al-5Ti-1B master alloy wire rod (Φ 9.5mm), as shown in Figure 1.
After embodiment 1 production process is reinforced for the first time, the metallographic structure of gained aluminum alloy sample as shown in Figure 2 (a) shows.Can see almost there is no TiAl in tissue
3the generation of phase, only have the very uniform black TiB of distribution
2particle exists.The metallographic structure of the final Al-5Ti-1B alloy wire through obtaining after continuous casting and rolling is as shown in Fig. 1 (b), except the TiB of black
2outside particle, can also clearly see a large amount of TiAl
3the existence of phase.TiAl in figure
3not only be evenly distributed mutually, and size is tiny, after the automatic detection analysis of distortion aluminium and the Al-alloy products microstructure method of inspection (GB-T-3246-1-2000) in " metallographic examination software system ", gained diameter Distribution situation is as shown in table 1, and obtains diameter Distribution figure (Fig. 3) according to data in table.Wherein, TiAl
3phase average diameter 7.08 μ m, the per-cent of diameter≤15 μ m reaches 93.59%, and maximum diameter is only 26.24 μ m, and standard deviation is 7.56 μ m, and at 1 * 2cm
2size king-sized (>50 μ m do not appear in scope) or the TiAl of long strip shape
3phase.In addition, TiB
2size distribution is very even, does not have agglomeration to occur.After laser particle analyzer detects analysis, TiB
2the distribution of sizes situation of particle is as shown in table 2: the TiB of size≤1.97 μ m
2the per-cent of particle is 92.26%, and overall dimension is 4.24 μ m.
TiAl in Al-5Ti-1B master alloy wire rod in table 1 example 1
3the diameter statistic data of phase
TiB in Al-5Ti-1B master alloy wire rod in table 2 example 1
2the statistic data of particle size
| Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% |
| 0.20 | 0.00 | 0.00 | 2.89 | 1.93 | 99.82 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.01 | 0.01 | 3.50 | 0.17 | 99.99 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.06 | 0.07 | 4.24 | 0.01 | 100.00 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.38 | 0.45 | 5.13 | 0.00 | 100.00 | 74.2 | 0.00 | 100.00 |
| 0.43 | 1.45 | 1.90 | 6.21 | 0.00 | 100.00 | 89.8 | 0.00 | 100.00 |
| 0.52 | 3.35 | 5.26 | 7.51 | 0.00 | 100.00 | 108.6 | 0.00 | 100.00 |
| 0.63 | 8.41 | 13.66 | 9.09 | 0.00 | 100.00 | 131.5 | 0.00 | 100.00 |
| 0.76 | 12.87 | 26.53 | 11.00 | 0.00 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 15.36 | 41.89 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 15.01 | 56.89 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 13.68 | 70.57 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 12.31 | 82.88 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 9.38 | 92.26 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 5.63 | 97.89 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
Embodiment 2: the manufacture of high quality Al-5Ti-0.5B alloy wire
The 1012kg99.7% aluminium ingot is melted in molten aluminium stove, and be heated to 749 ℃, then pour into and subcontract in stove, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide compound.Control is subcontracted temperature in stove and, at 700 ℃-750 ℃, is taken the K of 44.1kg purity 98%
2tiF
6with 44.1kg(be required KBF
4total amount 70%) KBF of purity 98%
4raw material mixes in mixer.The K just now weighed up
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 33 rev/mins to aluminum melt, and the reinforced material time is 5 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 3 minutes for the first time, then standing 8 minutes, then stir 2 minutes, finally the grain slag on aluminium liquid surface is outwelled.Again take the K of 195.9kg purity 98%
2tiF
6kBF with 18.9kg purity 98%
4raw material mixes in mixer.The K weighed up for the second time
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 25 rev/mins to aluminum melt, and the reinforced material time is 10 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 6 minutes for the second time, then standing 10 minutes, then stir 3 minutes, afterwards the grain slag on aluminium liquid surface is outwelled, add the CaF of 5kg
2in powder and the grain slag of remained on surface, and the slag that this process is produced is also removed clean together.Afterwards the aluminum melt of subcontracting in stove is poured into to middle frequency furnace, open heating and heat-insulating device, make melt temperature rise to 770 ℃ of left and right.In the middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to the aluminum melt bottom, and start to pass into nitrogen, air flow rolls continuously to seethe with excitement from bottom to up with aluminum melt and is advisable, and the residue of melt inside can continuous emersion surface.Ventilate after 6 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 12 minutes of aluminum melt.Afterwards, then ventilate 8 minutes, remove after residue standing 10 minutes.Ventilate for the third time 10 minutes, remove after residue standing 15 minutes.Measure temperature of aluminum liquid and reach 770 ℃, then start to release.Aluminum melt is flowed directly into to continuous casting and continuous rolling mill through chute and produce Al-5Ti-0.5B master alloy wire rod (Φ 9.5mm), as shown in Figure 4.
After embodiment 2 production processes are reinforced for the first time, the metallographic structure of gained aluminum alloy sample is as shown in Fig. 5 (a).Can see also almost there is no TiAl in tissue
3the generation of phase, only have the very uniform black TiB of distribution
2particle exists.The metallographic structure of the final Al-5Ti-0.5B alloy wire through obtaining after continuous casting and rolling is as shown in Fig. 5 (b), except the TiB of black
2outside particle, can also clearly see a large amount of TiAl
3the existence of phase.TiAl in figure
3not only be evenly distributed mutually, and size is tiny, after the automatic detection analysis of distortion aluminium and the Al-alloy products microstructure method of inspection (GB-T-3246-1-2000) in " metallographic examination software system ", gained diameter Distribution situation is as shown in table 3, and obtains diameter Distribution figure (Fig. 6) according to data in table.Wherein, TiAl
3phase average diameter 6.84 μ m, the per-cent of diameter≤15 μ m reaches 94.04%, and maximum diameter is only 31.37 μ m, and standard deviation is 4.94 μ m, and at 1 * 2cm
2size king-sized (>50 μ m do not appear in scope) or the TiAl of long strip shape
3phase.In addition, TiB
2size distribution is very even, does not have agglomeration to occur.After laser particle analyzer detects analysis, TiB
2the distribution of sizes situation of particle is as shown in table 4: the TiB of size≤1.97 μ m
2the per-cent of particle is 88.15%, and overall dimension is 4.24 μ m.
TiAl in Al-5Ti-0.5B master alloy wire rod in table 3 example 2
3the diameter statistic data of phase
TiB in Al-5Ti-0.5B master alloy wire rod in table 4 example 2
2the statistic data of particle size
| Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% |
| 0.20 | 0.00 | 0.00 | 2.89 | 2.92 | 99.62 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.06 | 0.06 | 3.50 | 0.36 | 99.99 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.01 | 0.07 | 4.24 | 0.01 | 100.00 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.01 | 0.08 | 5.13 | 0.00 | 100.00 | 74.2 | 0.00 | 100.00 |
| 0.43 | 0.13 | 0.21 | 6.21 | 0.00 | 100.00 | 89.8 | 0.00 | 100.00 |
| 0.52 | 0.64 | 0.85 | 7.51 | 0.00 | 100.00 | 108.6 | 0.00 | 100.00 |
| 0.63 | 3.75 | 4.60 | 9.09 | 0.00 | 100.00 | 131.5 | 0.00 | 100.00 |
| 0.76 | 7.50 | 12.10 | 11.00 | 0.00 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 11.01 | 23.11 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 13.72 | 36.82 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 17.92 | 54.75 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 19.00 | 73.74 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 14.41 | 88.15 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 8.55 | 96.70 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
Embodiment 3: the manufacture of the trapezoidal bulk of high quality Al-5Ti-1B alloy
The 1021kg99.7% aluminium ingot is melted in molten aluminium stove, and be heated to 741 ℃, then pour into and subcontract in stove, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide compound.Control is subcontracted temperature in stove and, at 700 ℃-750 ℃, is taken the K of 84kg purity 98%
2tiF
6with 84kg(be required KBF
4total amount 70%) KBF of purity 98%
4raw material mixes in mixer.The K weighed up
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 33 rev/mins to aluminum melt, and the reinforced material time is 8 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 5 minutes for the first time, then standing 8 minutes, then stir 2 minutes, finally the grain slag on aluminium liquid surface is outwelled.Again take the K of 156kg purity 98%
2tiF
6kBF with 36kg purity 98%
4raw material mixes in mixer.The K weighed up for the second time
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound with the rotating speed of 25 rev/mins to aluminum melt, and the reinforced material time is 6 minutes, the vigorous stirring of simultaneous stirrer.After reinforced the end, continue to stir 5 minutes for the second time, then standing 10 minutes, then stir 3 minutes, afterwards the grain slag on aluminium liquid surface is outwelled, add the CaF of 5kg
2in powder and the grain slag of remained on surface, and the slag that this process is produced is also removed clean together.Afterwards the aluminum melt of subcontracting in stove is poured into to middle frequency furnace, open heating and heat-insulating device, make melt temperature rise to 770 ℃ of left and right.In the middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to the aluminum melt bottom, and start to pass into nitrogen, air flow rolls continuously to seethe with excitement from bottom to up with aluminum melt and is advisable, and the residue of melt inside can continuous emersion surface.Ventilate after 6 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 12 minutes of aluminum melt.Afterwards, then ventilate 8 minutes, remove after residue standing 10 minutes.Ventilate for the third time 10 minutes, remove after residue standing 15 minutes.Measure the aluminum melt temperature and reach 768 ℃, then start to release.Aluminum melt is flowed directly into to continuous caster through chute and produce the trapezoidal bulk of Al-5Ti-1B master alloy (upper wide 18cm, bottom width 30mm), as shown in Figure 7.
After embodiment 3 production processes are reinforced for the first time, the metallographic structure of gained aluminum alloy sample is as shown in Fig. 8 (a).Can see also almost there is no TiAl in tissue
3the generation of phase, only have the very uniform black TiB of distribution
2particle exists.The metallographic structure of the final trapezoidal bulk of Al-5Ti-1B alloy obtained after continuous caster as shown in Figure 8 (b) shows, except the TiB of black
2outside particle, can also clearly see a large amount of TiAl
3the existence of phase.TiAl in figure
3not only be evenly distributed mutually, and size is tiny, after the automatic detection analysis of distortion aluminium and the Al-alloy products microstructure method of inspection (GB-T-3246-1-2000) in " metallographic examination software system ", gained diameter Distribution situation is as shown in table 5, and obtains diameter Distribution figure (Fig. 9) according to data in table.Wherein, TiAl
3phase average diameter 7.19 μ m, the per-cent of diameter≤15 μ m reaches 94.29%, and maximum diameter is only 30.31 μ m, and standard deviation is 3.54 μ m, and at 1 * 2cm
2size king-sized (>50 μ m do not appear in scope) or the TiAl of long strip shape
3phase.In addition, TiB
2size distribution is very even, does not have agglomeration to occur.After laser particle analyzer detects analysis, TiB
2the distribution of sizes situation of particle is as shown in table 6: the TiB of size≤1.97 μ m
2the per-cent of particle is 81.24%, and overall dimension is 11.00 μ m.
TiAl in the trapezoidal bulk of Al-5Ti-1B master alloy in table 5 example 3
3the diameter statistic data of phase
TiB in the trapezoidal bulk of Al-5Ti-1B master alloy in table 6 example 3
2the statistic data of particle size
| Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% |
| 0.20 | 0.00 | 0.00 | 2.89 | 1.90 | 87.39 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.00 | 0.00 | 3.50 | 0.71 | 88.10 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.04 | 0.04 | 4.24 | 1.47 | 89.57 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.46 | 0.50 | 5.13 | 3.07 | 92.64 | 74.2 | 0.00 | 100.00 |
| 0.43 | 1.80 | 2.30 | 6.21 | 3.52 | 96.16 | 89.8 | 0.00 | 100.00 |
| 0.52 | 3.93 | 6.23 | 7.51 | 2.79 | 98.96 | 108.6 | 0.00 | 100.00 |
| 0.63 | 9.23 | 15.46 | 9.09 | 1.03 | 99.98 | 131.5 | 0.00 | 100.00 |
| 0.76 | 13.31 | 28.76 | 11.00 | 0.02 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 14.60 | 43.37 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 12.65 | 56.01 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 9.83 | 65.84 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 8.73 | 74.57 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 6.67 | 81.24 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 4.24 | 85.49 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
comparative Examples:conventional two-step is produced the Al-5Ti-1B alloy wire
The 1015kg99.7% aluminium ingot is melted in molten aluminium stove, and be heated to 748 ℃, then pour into and subcontract in stove, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide compound.Control is subcontracted temperature in stove and, at 700 ℃-750 ℃, is taken the K of 120kg purity 98%
2tiF
6with 60kg(be required KBF
4total amount 70%) KBF of purity 98%
4raw material mixes in mixer.The K just now weighed up
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound to aluminum melt, the vigorous stirring of simultaneous stirrer with the rotating speed of 33 rev/mins.After reinforced the end, continue to stir 5 minutes for the first time, then standing 8 minutes, then stir 2 minutes, finally the grain slag on aluminium liquid surface is outwelled.Again take the K of 120kg purity 98%
2tiF
6kBF with 60kg purity 98%
4raw material mixes in mixer.The K weighed up for the second time
2tiF
6+ KBF
4compound is poured the charging machine conical hopper into, and charging machine adds compound to aluminum melt, the vigorous stirring of simultaneous stirrer with the rotating speed of 33 rev/mins.After reinforced the end, continue to stir 5 minutes for the second time, then standing 8 minutes, then stir 2 minutes, afterwards the grain slag on aluminium liquid surface is outwelled, add the CaF of 5kg
2in powder and the grain slag of remained on surface, and the slag that this process is produced is also removed clean together.Afterwards the aluminum melt of subcontracting in stove is poured into to middle frequency furnace, open heating and heat-insulating device, make melt temperature rise to 770 ℃ of left and right.In the middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to the aluminum melt bottom, and start to pass into nitrogen, air flow rolls continuously to seethe with excitement from bottom to up with aluminum melt and is advisable, and the residue of melt inside can continuous emersion surface.Ventilate after 6 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 12 minutes of aluminum melt.Afterwards, then ventilate 8 minutes, remove after residue standing 10 minutes.Ventilate for the third time 10 minutes, remove after residue standing 15 minutes.Measure temperature of aluminum liquid and reach 770 ℃, then start to release.Aluminum melt is flowed directly into to continuous casting and continuous rolling mill through chute and produce Al-5Ti-1B master alloy wire rod (Φ 9.5mm), as shown in figure 10.
comparative Examplesin production process, the metallographic structure of reinforced rear gained aluminum alloy sample for the first time as shown in Figure 11 (a) shows.Can see that TiB is arranged in tissue
2the generation of particle, also have TiAl
3the generation of phase.TiAl
3the pattern of phase is various, has particulate state that rod-short is also arranged, and size is very tiny, mean diameter 3.74 μ m.The metallographic structure of the final Al-5Ti-1B alloy wire through obtaining after continuous caster is as shown in Figure 11 (b), although Al
3the distribution of Ti phase is also more even, but size obviously increases, and distribution of sizes is extremely inhomogeneous, and some sizes are very large, and the size also had is very little.This is mainly because after feeding in raw material for the second time, the automatic forming core growth of a part of Ti atom, and a part of Ti atom is at the TiAl of original reduced size
3growth mutually, some is at the TiAl of original large-size
3growth mutually, therefore cause TiAl in last tissue
3the distribution of sizes of phase presents the state of this inequality.After the automatic detection analysis of distortion aluminium and the Al-alloy products microstructure method of inspection (GB-T-3246-1-2000) in " metallographic examination software system ", gained diameter Distribution situation is as shown in table 7, and obtains diameter Distribution figure (Figure 12) according to data in table.Wherein, TiAl
3phase average diameter 7.80 μ m, the per-cent of diameter≤15 μ m only has 89.86%, and maximum diameter can reach 76.95 μ m, and standard deviation is 19.14 μ m.In addition, TiB
2size distribution is very even, does not have agglomeration to occur.After laser particle analyzer detects analysis, TiB
2the distribution of sizes situation of particle is as shown in table 8: the TiB of size≤1.97 μ m
2the per-cent of particle is 67.07%, and overall dimension is 7.51 μ m.
TiAl in Al-5Ti-1B master alloy wire rod in table 7 Comparative Examples
3the diameter statistic data of phase
TiB in Al-5Ti-1B master alloy wire rod in table 8 Comparative Examples
2the statistic data of particle size
| Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% | Particle diameter/μ m | Differential/% | Accumulation/% |
| 0.20 | 0.00 | 0.00 | 2.89 | 7.35 | 84.89 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.18 | 0.18 | 3.50 | 4.72 | 89.61 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.02 | 0.20 | 4.24 | 3.34 | 92.95 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.10 | 0.30 | 5.13 | 3.32 | 96.28 | 74.2 | 0.00 | 100.00 |
| 0.43 | 0.45 | 0.75 | 6.21 | 2.51 | 98.79 | 89.8 | 0.00 | 100.00 |
| 0.52 | 1.23 | 1.98 | 7.51 | 1.21 | 100.00 | 108.6 | 0.00 | 100.00 |
| 0.63 | 3.47 | 5.45 | 9.09 | 0.00 | 100.00 | 131.5 | 0.00 | 100.00 |
| 0.76 | 5.68 | 11.13 | 11.00 | 0.00 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 7.75 | 18.88 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 9.36 | 28.23 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 12.17 | 40.40 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 13.96 | 54.36 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 12.72 | 67.07 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 10.46 | 77.54 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
With the Al-5Ti-1B alloy wire that traditional technology is produced, compare, the Al-5Ti-1B alloy wire that the present invention produces is TiAl not only
3the per-cent high (93.59%>89.86%) of the mean diameter of phase little (7.08 μ m<7.80 μ m), diameter≤15 μ m, and TiB
2the size of particle is per-cents very little, size≤1.97 μ m very high (92.26%>67.07%) also, the more important thing is the TiAl that there is no to generate large-sized especially or long strip shape in tissue
3phase, thus TiAl guaranteed
3the homogeneity of phase diameter (standard deviation 7.56<19.14 μ m).We ascribe this characteristics to proportion scale for the first time special in the present invention, all generate TiB in the rear aluminium liquid that makes to feed in raw material for the first time
2particle, and do not generate TiAl
3therefore phase, after reinforced for the second time, Ti atom or spontaneous nucleation are grown up or at TiB
2under the effect of particle, forming core is grown up, and TiAl
3grow up mutually to also can be because of surperficial TiB after certain size
2the coating function of particle, slow down and even stop TiAl
3growing up of phase, therefore final TiAl
3the size of phase is reduced, and the refining effect of Al-5Ti-1B master alloy fining agent is improved.
Embodiment of the present invention is only the description that the preferred embodiment of the present invention is carried out; not design of the present invention and scope are limited; under the prerequisite that does not break away from design philosophy of the present invention; various modification and improvement that in this area, engineering technical personnel make technical scheme of the present invention; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection, all be documented in claims.
Claims (7)
1. the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of a step, the K added altogether for twice
2tiF
6amount and KBF
4amount is to determine according to the composition of Al-Ti-B master alloy fining agent, while it is characterized in that feeding in raw material for the first time, and K
2tiF
6and KBF
4according to chemical equation 2KBF
4+ K
2tiF
6+ 10/3Al=TiB
2+ 3KAlF
4+ 1/3K
3alF
6stoichiometric ratio or K
2tiF
6a small amount of excessive being added in aluminum melt arranged, guarantee not there will be AlB in alloying process for the first time
2phase, obtained only containing TiB
2mutually or also have few TiAl
3the melt of phase, preparation process comprises the steps:
(1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours into and subcontract in stove, prepare next step alloying process;
(2) reinforced for the first time: the mass ratio by 0.953:1 ~ 1:1 takes respectively a certain amount of K
2tiF
6and KBF
4raw material, and mix in mixer, wherein, KBF in feeding in raw material for the first time
4weight be required KBF
460% ~ 90% of total amount; Then by K
2tiF
6+ KBF
4compound is poured the conical hopper of charging machine into, by the feed rate of 30 ~ 40 rev/mins of charging machines, raw material is added in aluminum melt, and the reinforced material time is 5 ~ 8 minutes, and is accompanied by continuous stirring; Continue to stir 3 ~ 5 minutes after reinforced the end, then start standingly, after standing 8 ~ 10 minutes, again stir 2 ~ 3 minutes, finally outwell the grain slag on aluminum melt surface;
(3) reinforced for the second time: by K remaining in required villiaumite
2tiF
6and KBF
4raw material is poured the conical hopper of charging machine into after mixing in mixer, by the feed rate of 20 ~ 30 rev/mins of charging machines, raw material is added in aluminum melt, and feed time is 6 ~ 10 minutes, and is accompanied by whipping process; After secondary charging finishes, the continuation stirring starts standing after 3 ~ 6 minutes, after standing 8 ~ 10 minutes, then stir 2 ~ 3 minutes, starts afterwards, except grain slag, finally to obtain clean aluminum melt;
(4) insulation, degasification and slagging-off are processed: the molten aluminium that will subcontract in stove is poured in middle frequency furnace, and unlatching heating and heat-insulating device, promote in stove temperature to 760 ℃ ~ 800 ℃, carbon tube with an about 20mm aperture in temperature-rise period leads to argon gas or nitrogen, air flow is advisable to allow aluminum melt roll continuously to seethe with excitement from bottom to up, residue meeting continuous emersion surface in melt, ventilate after 8 ~ 10 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then by standing 10 ~ 15 minutes of aluminum melt; Afterwards, then repeat the ventilation, slagging-off of front and standing process 2 ~ 3 times, to guarantee that in molten aluminium, the content of slag is reduced to minimum level;
(5) pour into a mould trapezoidal bulk or continuous casting and rolling and become wire rod: when the aluminum melt temperature reaches 760 ℃ ~ 800 ℃ in the intermediate frequency electric furnace, the operation that starts to release, the aluminum melt in stove flows into the casting machine direct production through chute and goes out the trapezoidal bulk of Al-Ti-B master alloy or flow into continuous casting and continuous rolling mill to produce Al-Ti-B master alloy wire rod.
2. the reinforced legal system of two steps according to claim 1 is for the method for high quality Al-Ti-B master alloy fining agent, K while it is characterized in that feeding in raw material for the first time
2tiF
6and KBF
4mass ratio be 1:1.
3. the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of two steps according to claim 1, add CaF while after the end that it is characterized in that feeding in raw material for the second time, removing grain slag
2in flux and grain slag, add-on is 0.4% ~ 0.8% of aluminium weight.
4. the reinforced legal system of two steps according to claim 1 is for the method for high quality Al-Ti-B master alloy fining agent, KBF while it is characterized in that feeding in raw material for the first time
4weight be required KBF
470% of total amount.
5. the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of two steps according to claim 1, is characterized in that described Al-Ti-B master alloy fining agent composition is Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.5B, Al-5Ti-0.3B.
6. the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of two steps according to claim 1, is characterized in that described fine aluminium is melted in to pour into to subcontract after stove impurity and the oxide compound that will dispose aluminium liquid surface.
7. the method for the standby high quality Al-Ti-B master alloy fining agent of the reinforced legal system of two steps according to claim 1, is characterized in that described alloying process temperature is controlled in 700 ℃ of-750 ℃ of scopes
.
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| CN103952602A (en) * | 2014-05-04 | 2014-07-30 | 遵义智鹏高新铝材有限公司 | Aluminum-titanium-boron production process |
| CN104561619A (en) * | 2015-01-28 | 2015-04-29 | 南通昂申金属材料有限公司 | Preparation method of aluminum-titanium-boron wire grain refiner |
| CN104831096A (en) * | 2015-04-09 | 2015-08-12 | 昌吉市吉日光有色金属合金制造有限公司 | Aluminium titanic boron intermediate alloy refinement agent and preparation technology thereof |
| CN105463223A (en) * | 2015-12-01 | 2016-04-06 | 永城金联星铝合金有限公司 | Manufacturing method of Al-B-RE intermediate alloy |
| CN105925854A (en) * | 2016-05-23 | 2016-09-07 | 沈阳工业大学 | High quality aluminum titanium boron refiner and preparation method thereof |
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| CN103952602B (en) * | 2014-05-04 | 2018-03-16 | 遵义智鹏高新铝材有限公司 | A kind of aluminium titanium boron production technology |
| CN104561619B (en) * | 2015-01-28 | 2016-09-21 | 南通昂申金属材料有限公司 | A kind of preparation method of aluminium titanium boron wire grain refiner |
| CN104561619A (en) * | 2015-01-28 | 2015-04-29 | 南通昂申金属材料有限公司 | Preparation method of aluminum-titanium-boron wire grain refiner |
| CN104831096A (en) * | 2015-04-09 | 2015-08-12 | 昌吉市吉日光有色金属合金制造有限公司 | Aluminium titanic boron intermediate alloy refinement agent and preparation technology thereof |
| CN105463223A (en) * | 2015-12-01 | 2016-04-06 | 永城金联星铝合金有限公司 | Manufacturing method of Al-B-RE intermediate alloy |
| CN105925854A (en) * | 2016-05-23 | 2016-09-07 | 沈阳工业大学 | High quality aluminum titanium boron refiner and preparation method thereof |
| CN108118169A (en) * | 2017-12-29 | 2018-06-05 | 西南铝业（集团）有限责任公司 | A kind of thinning method of fining agent and 2124 alloy cast ingots |
| CN108118205A (en) * | 2017-12-29 | 2018-06-05 | 西南铝业（集团）有限责任公司 | A kind of thinning method of fining agent and 7050 alloy cast ingots |
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| CN112048629A (en) * | 2020-01-17 | 2020-12-08 | 上海大学 | Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy |
| CN113637880A (en) * | 2021-07-07 | 2021-11-12 | 上海大学 | High-strength high-plasticity aluminum-silicon-magnesium alloy and preparation method thereof |
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