CN103173663A - Preparation method of high-quality Al-Ti-B-Sr master alloy composite refining modifier - Google Patents
Preparation method of high-quality Al-Ti-B-Sr master alloy composite refining modifier Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-quality Al-Ti-B-Sr master alloy composite refining modifier. The preparation method comprises the following steps: firstly melting a pure aluminum ingot in an aluminum melting furnace, and then pouring into a medium-frequency induction furnace to be ready for alloying; then weighing K2TiF6 and KBF4 raw materials, uniformly mixing, and pouring into the molten aluminum to be alloyed in the medium-frequency furnace; performing reaction for a certain period of time, then pouring the remaining mixture of K2TiF6 and KBF4 into an aluminum melt, and pouring away water granulated slag after the end of the reaction; performing degassing and re-deslagging treatment, and then gradually adding a certain weight of Al-20Sr alloy wires; performing stirring, re-deslagging and degassing treatment, and directly pouring to form Al-Ti-B-Sr alloy rods; and then sending the alloy rods onto an extruding machine to perform sectional area large-deformation thermal extrusion treatment and finally obtaining the Al-Ti-B-Sr master alloy composite refining modifier wires with the diameter of 9.5mm. The preparation method is characterized by combining a three-step charging method and a thermal extrusion molding process.
Description
Technical field
The invention belongs to material and metallurgical technology in new material technology field, the preparation method who relates to a kind of high quality Al-Ti-B-Sr master alloy composite refining alterant, specifically by improving traditional processing technology, utilize " three reinforced methods of step " and " hot extrusion molding " technique to prepare high quality Al-Ti-B-Sr master alloy composite refining alterant.
Background technology
The Al-Si alloy is little owing to having density, the advantages such as specific tenacity is high, good welding performance, thermal expansivity is low and anti-corrosion, heat-resisting and wear resisting property is good are widely used in high-tech areas such as mechanical industry, automotive industry, aviation and war industrys.Particularly aluminum alloy casting and die casting, almost be associated gold manufacturing with Al-Si more than 90%.In castingprocesses, the general dendritic α-Al phase that generates of Al-Si alloy, thick faller gill shape eutectic Si and block primary crystal Si mutually, and other precipitated phase on a small quantity is as Mg
2Si, AlFeSi equate.Wherein, thick primary crystal Si is mutually hard and crisp with eutectic Si, and the serious matrix that isolated easily produces tiny crack, thereby falls low-alloyed mechanical property and processing characteristics in deformation process, and especially plasticity descends more.Therefore, generally need to carry out mutually thinning processing to Si in actual applications, namely pass through to change form, size and the distribution situation of Si phase, thereby reduce it to the weakening effect of α-Al matrix, to reach the purpose that improves the alloy casting performance.At present, the method of improving silicon from aluminum-silicon alloy phase morphology and size has a lot, as mechanical/electrical magnetic field stir process, add alterant method, ultrasonication, semi-solid casting and Temperature Treatment method etc., wherein, using maximum also the most simple and effective method in industrial production is to add the alterant method.Alterant element commonly used has Na, Sr, Sb, RE etc., adds with the form of its Al master alloy.Na is as far back as the industrial alterant element that is employed, but Na process on the turn in oxidation, scaling loss fierce, easily corrode crucible, and deteriorating time is short; Sb is subjected to the impact of speed of cooling very large in process on the turn, and can not use together with Na or Sr; Although the RE modification effect is good, exist equally scaling loss large, easily produce the shortcoming of high-melting-point segregation thing sedimentation.Sr not only modification effect is good, and oxidization burning loss is few, and effectively deteriorating time is long, and is little to corrosion of crucible, and free from environmental pollution.When adding the Sr alterant in the Al-Si alloy, except eutectic Si can be transformed into by thick faller gill shape tiny spherical or fibrous, the size of primary crystal Si and quantity also reducing to a certain extent, thereby improved greatly the mechanical property of alloy, particularly unit elongation is significantly improved.Therefore, the Sr alterant becomes the rotten Main Means of processing of casting Al-Si alloy gradually.
In addition, along with the continuous increase in Al-Si Alloyapplication field, the performance of various follow-up deep processing technology alloy materials is had higher requirement again.In order further to improve the over-all properties of casting Al-Si alloy, except continue refinement Si mutually, α-Al crystal grain is carried out thinning processing has become current very important approach.When α-Al grain-size hour, not only can obviously improve the mechanical property of foundry goods, reduce segregation, reduce hot cracking tendency, can also improve the feeding in casting solidification process, the resistance to air loss that improves foundry goods and surface quality etc.Although pattern and size that the interpolation of Sr can refinement Si phase, but impact impact in other words is not little on the dentrite α-Al in tissue yet according in the past result of study as can be known.Therefore, in Al-Si alloy casting and processing industry, in order to obtain tiny α-Al tissue, often need to take the solidification and crystallization tissue of other measure alloy to carry out thinning processing, such as: rapid solidification method, mechanical-physical refinement method, physical field refinement method and superalloy method etc.Wherein, 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.Be mainly with containing the salt fusant of Ti, B, Zr, Nb etc. as fining agent the forties in 20th century; The fifties is generally with the salt block agent that contains Ti, B element; The sixties, produced AlTi alloy block ingot (containing Ti per-cent is 5%, 6% and 10%); Develop the Al-5Ti-1B silk seventies; 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.At present, 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, and is especially best with the effect of Al-5Ti-1B alloy.
Therefore, in order to put forward heavy alloyed over-all properties, generally all need casting Al-Si alloy is carried out refinement and rotten two kinds for the treatment of process in actual industrial.Common way is first to add alterant to the processing of going bad of Al-Si alloy, and then adds fining agent to carry out refinement to α-Al.α after these two step process in the Al-Si alloy structure-Al crystal grain has all obtained refinement mutually with Si, thereby has promoted the performance of material.Yet this treatment process mesometamorphism and thinning process separately carry out, and have extended technical process on the one hand, have increased the operating time, have promoted production cost; Due to the problem in treatment time, sometimes can cause unavoidably the decline of refinement or modification effect on the other hand.Therefore, can carry out simultaneously refinement and become very important studying a question with rotten these two processes.At present, there has been the people to successfully synthesize the Al-Ti-B-Sr master alloy by the way of directly adding metal Sr in the Al-Ti-B intermediate alloy melt.After the Al-Ti-B-Sr master alloy is processed, both had good thinning effect in the Al-Si alloy structure, has again good modification effect, and after processing, the mechanical properties such as intensity, unit elongation of Al-Si alloy all are greatly improved, and this studies show that the Al-Ti-B-Sr master alloy can well solve refinement simultaneously and rotten problem.But traditional Al-Ti-B-Sr master alloy production technique is at first finished product Al-Ti-B master alloy to be melted, and then metal Sr directly is added to melt.This technique has obvious shortcoming: at first, because the temperature of reaction of Sr and Al liquid is high, need a large amount of energy of consume to be used for the rising melt temperature; Secondly, the activity of metal Sr is very high, directly adds in the reaction of metal Sr scaling loss under high temperature very large, has reduced the interior Al of alloy
4The quantity of Sr phase increases rotten cost; Again, because the Al-Ti-B alloy is the finished product remelting, thereby uncontrollable its Al in preparation Al-Ti-B-Sr master alloy
3Ti and TiB
2The pattern of phase and size, and then affected its refinement and modification effect.
In view of above problem, we have invented a kind of employing " three step reinforced method " and " hot extrusion " technique and have combined and prepare the method for high quality Al-Ti-B-Sr master alloy wire rod composite refining alterant: at first in molten aluminium stove, the fine aluminium ingot is melted at a certain temperature, then pour the interior preparation of medium-frequency induction furnace alloying into; Take K by certain proportion scale afterwards
2TiF
6And KBF
4Raw material mixes, and drops into by certain speed and treat in intermediate frequency furnace among the aluminum melt of alloying; After the reaction certain hour again remaining K
2TiF
6And KBF
4Compound also drops into molten aluminium, and reaction is outwelled grain slag after finishing; Through degasification with after slagging-off is processed again, progressively add the Al-20Sr alloy wire of certainweight; Through stirring and again after slagging-off, degassing processing, directly pouring into the Al-Ti-B-Sr alloy bar material; These alloy bars are delivered to again and carried out sectional area gross distortion extrusion process on extrusion machine, obtaining at last diameter is the Al-Ti-B-Sr master alloy wire rod of 9.5mm.Technique of the present invention is simple, convenient operation, TiB not only in the Al-Ti-B-Sr master alloy product of producing
2Phase and TiAl
3All size is tiny mutually, and disperse is evenly distributed, and Al
4The Sr phase size is also smaller.The Al-Ti-B-Sr master alloy of this microstructure features has well guaranteed refinement and the modification effect of product, can satisfy α in the Al-Si alloy-Al phase and Si thinning processing requirement mutually fully.Therefore, this invention extremely is adapted at industrial applying.
Summary of the invention
The present invention seeks to the shortcoming that to exist in traditional processing technology and problem improvement and bring new ideas in addition, a kind of preparation method of high quality Al-Ti-B-Sr master alloy composite refining alterant is provided for refinement/alterant industry, that is: at first in molten aluminium stove, the fine aluminium ingot is melted at a certain temperature, then pour into and prepare alloying in medium-frequency induction furnace; Again according to equation 2KBF
4+ K
2TiF
6+ 10/3Al → TiB
2+ 3KAlF
4+ 1/3K
3AlF
6In stoichiometric ratio take respectively the K of certainweight
2TiF
6And KBF
4Raw material mixes, and drops in intermediate frequency furnace by certain speed under the intensively stirred effect of aluminium liquid; After the reaction certain hour again remaining K
2TiF
6And KBF
4Compound adds molten aluminium, etc. after the total overall reaction end, that grain slag is clean; Then the temperature of aluminum liquid that raises passes into inert nitrogen gas/argon gas simultaneously liquation is carried out degasification and slagging-off processing again in temperature-rise period; Temperature rises to a certain degree and afterwards Al-20Sr master alloy wire rod is progressively added melt by a certain percentage, and carry out mechanical stirring and mix after all melting, then carry out degas operation with rotary degassing machine, and the content of dynamic measurement hydrogen; After hydrogen content is up to standard (≤0.2ml/100gAl), melt is cast into the bar of certain size; With the hot extrusion deformation processing at a certain temperature of this bar, make the wire rod of diameter 9.5mm at last.This invented technology is simple, and convenient operation provides a kind of very effective industrial process for producing high quality Al-Ti-B-Sr master alloy composite refining alterant.
A kind of method of producing high quality Al-Ti-B-Sr master alloy composite refining alterant: at first use special " three reinforced methods of step " to complete the operating process such as alloying, slagging-off, degasification, then be cast into Al-Ti-B-Sr master alloy bar, extrude Al-Ti-B-Sr master alloy wire rod by " hot extrusion molding " technique at last.
Mainly comprise the following steps:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours in medium-frequency induction furnace, prepare next step alloying process;
2) the first step is reinforced: the reinforced process of first two steps of " three reinforced methods of step " is for the tiny TiAl of preparation
3Phase and TiB
2Phase, for reaching this target, adopted special KBF
4And K
2TiF
6Proportion scale: namely, require reaction only to generate TiB in the first step alloying process
2Phase does not generate or only generates 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 than relation draw occur fully in theory this reaction required K
2TiF
6And KBF
4Mass ratio be 0.953:1, but for fear of because reacting the KBF that not exclusively produces surplus
4, to such an extent as to AlB appears
2Phase, the ratio of this process using 1:1; Therefore, in the reinforced process of the first step, take respectively a certain amount of K by the mass ratio of 1:1
2TiF
6And KBF
4Raw material mixes, wherein, and KBF during the first step is reinforced
4Weight be required KBF
460% ~ 90% of total amount is then with K
2TiF
6+ KBF
4Compound adds in aluminum melt by the feed rate of 20 ~ 30kg/min, wants violent stirring in reinforced process, is evenly distributed on reaction interface to guarantee raw material, avoids causing the problems such as local superheating, resultant segregation because of the accumulation of villiaumite reactant.Continue to stir 5-15 minute after reinforced the end, can play thermolysis on the one hand, prevent that excess Temperature is to TiB
2And TiAl
3The growth of phase causes bad impact; Make on the other hand resultant TiB
2And TiAl
3Evenly distribute mutually, prevent that agglomeration from occuring; Can also destroy rich B or rich Ti district, avoid TiB
2And TiAl
3Too growing up of phase; In addition, stirring can also promote the carrying out that react, and promotes the casting yield of Ti and B in molten aluminium.It should be noted that the variation that needs composition in not timing sampling analysis molten aluminium in whipping process, whether complete to confirm the alloying reaction process;
3) second step is reinforced: after the first step reaction finishes, with K remaining in required villiaumite
2TiF
6And KBF
4Raw material mixes, then the feed rate by 20 ~ 30kg/min adds molten aluminium, also be accompanied by strong stirring action, after the reinforced end of second step, continue to stir 5-15 minute, until the qualified rear beginning pouring slag of sampling analysis composition, clean in order to remove grain slag, also need to add a certain amount of CaF
2During flux comes and grain slag, CaF
2Main purpose be the grain slag layer on neutralization surface, addition is to determine according to what that are finished down aluminium liquid top layer residue grain slag amount after grain slag, generally add 5-8kg, the slag operation that dewaters obtains clean Al-Ti-B liquation after finishing at last.
4) heating, degasification and slagging-off are processed: open medium-frequency induction furnace power supply heating molten aluminium to 850 ℃ ~ 900 ℃ and insulation, in heating with one approximately the carbon tube in 20mm aperture lead to argon gas or nitrogen, air flow is advisable to allow aluminium liquid roll continuously to seethe with excitement from bottom to up, the continuous emersion of residue meeting surface in melt, ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then with standing 5 ~ 10 minutes of aluminum melt.Afterwards, just now ventilation, slagging-off and standing process repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: when temperature is increased to 850 ℃ ~ 900 ℃, progressively add the Al-20Sr master alloy wire rod of certainweight in melt, in induction furnace, melt temperature descends too many for fear of too much causing because of a feeding quantity when adding Al-20Sr master alloy wire rod, so that melt viscosity is too large, and then mass transfer and diffusion process after having influence on, divide and add aequum 1-3 time, and the time of repose of 10-15 minute arranged after adding at every turn, the temperature so that medium-frequency induction furnace raises has if having time again also promoted simultaneously Al
4The diffusion of Sr phase is uniformly dispersed it; Although do not use mechanical stirring in the process of adding Al-20Sr master alloy wire rod, because this melting process is carried out in medium-frequency induction furnace, so melt is subject to the stirring action of electromagnetic field all the time, and this stirring action makes TiB on the one hand
2, TiAl
3And Al
4Sr is evenly distributed mutually, prevents from reuniting; Can also fragmentation fall some large-sized TiAl on the other hand
3And Al
4The Sr phase.After all Al-20Sr master alloy wire rods add end, mechanical stirring 5-10 minute, when melt temperature returns to 850 ℃ ~ 900 ℃, utilize the high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in the dynamic measurement melt;
6) cast bar: in melt hydrogen content up to standard (≤0.2ml/100gAl), and after disposing simultaneously surperficial slag blanket, the Al-Ti-B-Sr alloy melt is poured into diameter 100mm, be cast as the Al-Ti-B-Sr bar in the cylindrical iron mould of high 450mm;
7) hot extrusion molding: the Al-Ti-B-Sr alloy bar material that obtains is heated to 400 ℃-500 ℃ carries out sectional area gross distortion hot extrusion, finally obtaining diameter is the Al-Ti-B-Sr master alloy wire rod of 9.5mm.
Be accompanied by strong function composite by electromagnetic stirring when in the present invention's " three reinforced methods of step ", the 3rd step was added Al-20Sr master alloy wire rod.
Al-Ti-B-Sr master alloy composite refining alterant of the present invention comprises Al-5Ti-1B-10Sr, Al-5Ti-1B-5Sr, Al-3Ti-1B-10Sr, Al-3Ti-1B-5Sr, Al-5Ti-0.5B-10Sr master alloy.
Described K in the present invention
2TiF
6And KBF
4Add-on is to calculate to determine according to the ratio of Ti and B in prepared Al-Ti-B-Sr master alloy.
The violent stirring of the described the first step and second step is to adopt machine mixer in the present invention, and rotating speed is 100-120 rev/min.
Adopted 1:1(K when feeding in raw material due to the first step in technique of the present invention
2TiF
6: KBF
4) proportion scale, therefore, in guaranteeing alloying process, AlB does not appear
2Under the prerequisite of phase, obtained only containing TiB
2Mutually or also have few TiAl
3The melt of phase.Owing to having strengthened stirring action in reaction process, fresh aluminium liquid constantly is exposed to reaction interface and has destroyed rich B zone, thereby has affected TiB
2The growth of phase makes the TiB of last generation
2Particle size is tiny.When second step is reinforced, be subject to just these tiny TiB
2The impact of phase, TiAl
3The nucleus of phase forms and grows up also obvious difference.Particularly, (1) is due to TiB
2The heterogeneous forming core effect of phase makes TiAl
3The forming core merit of nucleus obviously reduces, and it is very easy that nucleation becomes, so that TiAl
3Nucleation rate is improved; (2) work as TiAl
3Grow up after certain size mutually, because a large amount of TiB in surface
2The coating function of particle slows down and even stops TiAl
3Growing up of phase.The impact of above two factors just, TiB in last gained Al-Ti-B-Sr alloy product
2And TiAl
3Phase size is all less, and it is very even to distribute.In reinforced in the 3rd step, the temperature of reaction when directly alloying occuring due to the temperature in stove lower than metal Sr and aluminium liquid on the one hand; Be Al-20Sr alloy wire rather than metal Sr due to what adopt in this step on the other hand, wherein Sr is with Al
4The form of Sr phase exists in melt, so the decline of the oxidizing reaction degree of Sr element, and burn out rate is significantly reduced.In other words, the casting yield of Sr is improved, thereby has reduced the cost of product.In addition, due to Al in Al-20Sr master alloy wire rod
4Sr presents particulate state or bulk mutually, and size is tiny, according to the principle in the genetics of casting metal, and Al after remelting
4Sr still keeps mutually original pattern constant, adds finally by having crossed the sectional area gross distortion hot extrusion course of processing, so Al
4The Sr phase size is got back and is further reduced.The Al that these are tiny
4It is fast that Sr has guaranteed to discharge the Sr atomic velocity in metamorphic process mutually, and deterioration latency stage is short, the advantage that modification effect is good.This technique can be produced the Al-Ti-B-Sr master alloy wire rod of various compositions, comprise Al-5Ti-1B-10Sr, Al-5Ti-1B-5Sr, Al-3Ti-1B-10Sr, Al-3Ti-1B-5Sr, Al-5Ti-0.5B-10Sr etc., so the present invention provides a kind of extremely important method for industry member production high quality Al-Ti-B-Sr master alloy composite refining alterant.
The invention has the advantages that:
1. detailed performance is high.In traditional Al-Ti-B-Sr alloying process, the temperature higher (900 ℃-1000 ℃) owing to adding metal Sr and aluminium liquid and react, and the temperature of this part rising can be to TiAl
3And TiB
2Produce mutually important impact, wherein the most significantly changing is exactly the large and partial strip shaped TiAl of the change of size
3The generation of phase.But in the present invention, one side is owing to having adopted special K
2TiF
6And KBF
4Feed ratio makes TiAl
3And TiB
2Be evenly distributed mutually, size is tiny; On the other hand due to the temperature not high (850 ℃-900 ℃) of the 3rd step when reinforced, avoided Yin Wendu to raise and the negative impact that brings.So TiAl in the Al-Ti-B-Sr master alloy wire rod tissue of final production
3And TiB
2Be evenly distributed mutually, size is tiny, has improved greatly the detailed performance of alloy.
2. modification effect is good.What in the present invention, the interpolation of Sr was adopted is Al-20Sr master alloy wire rod, in the past studies show that Al in this wire rod
4Sr exists with particulate state or bulk morphologies, and size is very tiny.According to cast structure's heredity principle, after the remelting of Al-20Sr master alloy wire rod, Al
4Sr also can inherit this shape characteristic mutually, so Al in the Al-Ti-B-Sr master alloy wire rod of final production
4Sr also presents particulate state or bulk mutually, and under the processing of sectional area gross distortion hot extrusion technique, its size is further dwindled, this tiny Al
4Sr has improved the modification effect of alloy mutually greatly.
3. energy efficient.Directly add in metal Sr production technique in tradition, the alloying process that complete Sr need to be elevated to 900 ℃-1000 ℃ to melt temperature, and the rising of this part temperature all relies on external energy, thereby causes the energy consumption of whole production technique to increase.But well utilized liberated heat in " villiaumite method " reaction process in technique of the present invention.Particularly, the initial temperature of aluminum liquid of the present invention is only 700 ℃-750 ℃, complete first two steps reinforced after, in reaction, liberated heat can make melt temperature rise to 800 ℃-900 ℃, temperature required basic identical or gap is little when this and the 3rd step are reinforced, be raised to default 850 ℃ of-900 ℃ of required energy consumptions thereby saved intermediate frequency furnace.In other words, whole alloying process has well utilized liberated heat in reaction process, turns waste into wealth;
4. the casting yield of Sr is high.Traditional technique is owing to being directly to add the process that metal Sr completes alloying, so the oxidizing reaction of Sr is violent, and scaling loss is very large, and this content that also makes Sr in the finished product is well below stoichiometric, thereby has increased the production cost of enterprise.But in the present invention owing to having adopted Al-20Sr master alloy wire rod, except the fusing speed that can promote the Al-20Sr master alloy, the more important thing is and weakened oxidation and the evaporative process of Sr in melt, thereby reduced the scaling loss of Sr, the casting yield of last Sr can reach more than 95%;
5. technique is simple, and is easy to operate.Do not use complicated equipment in the present invention, loaded down with trivial details technical process also do not occur, therefore technique is simple, easy to operate for manufacturing enterprise;
6. product diversification.Technique of the present invention can be by controlling K
2TiF
6, KBF
4And thereby the addition of Al-20Sr master alloy wire rod reaches the purpose of producing Multiple components Al-Ti-B-Sr master alloy wire rod, as Al-5Ti-1B-10Sr, Al-5Ti-1B-5Sr, Al-3Ti-1B-10Sr, Al-3Ti-1B-5Sr, Al-5Ti-0.5B-10Sr etc., therefore product diversification can be satisfied various clients' needs.
Description of drawings
Fig. 1 is the macro morphology of Al-5Ti-1B-10Sr master alloy wire rod in example 1.
Fig. 2 is the heterogeneous microstructure figure of Al-5Ti-1B-10Sr master alloy in example 1.
Fig. 3 is the interior Al of Al-5Ti-1B-10Sr master alloy wire rod in example 1
4The size distribution plot of Sr phase: (a) length distribution; (b) width distribution.
Fig. 4 is the interior TiAl of Al-5Ti-1B-10Sr master alloy wire rod in example 1
3The diameter Distribution figure of phase.
Fig. 5 is the interior TiB of Al-5Ti-1B-10Sr master alloy wire rod in example 1
2The size distribution plot of particle.
Fig. 6 is the macro morphology of Al-5Ti-1B-5Sr master alloy wire rod in example 2.
Fig. 7 is the heterogeneous microstructure figure of Al-5Ti-1B-5Sr master alloy in example 2.
Fig. 8 is the interior Al of Al-5Ti-1B-5Sr master alloy wire rod in example 2
4The size distribution plot of Sr phase: (a) length distribution; (b) width distribution.
Fig. 9 is the interior TiAl of Al-5Ti-1B-5Sr master alloy wire rod in example 2
3The diameter Distribution figure of phase.
Figure 10 is the interior TiB of Al-5Ti-1B-5Sr master alloy wire rod in example 2
2The size distribution plot of particle.
Embodiment
" three reinforced methods of step " provided by the invention and the method for " heat pressurization " explained hereafter high quality Al-Ti-B-Sr master alloy composite refining alterant are as follows:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours in medium-frequency induction furnace, prepare next step alloying process;
2) the first step is reinforced: the mass ratio by 1:1 takes respectively a certain amount of K
2TiF
6And KBF
4Raw material mixes, wherein, and KBF during the first step is reinforced
4Weight be required KBF
460% ~ 90% of total amount.Then with K
2TiF
6+ KBF
4Whether compound adds in aluminum melt by the feed rate of 20 ~ 30kg/min, and is accompanied by strong stirring action, continues to stir 5-15 minute after reinforced the end, and timing sampling is not analyzed the variation of composition in molten aluminium, complete to confirm the alloying reaction process;
3) second step is reinforced: after the first step reaction finishes, with K remaining in required villiaumite
2TiF
6And KBF
4Raw material mixes, and then the feed rate by 20 ~ 30kg/min adds in molten aluminium, also is accompanied by strong stirring action, after the reinforced end of second step, continues to stir 5-15 minute, until the qualified rear beginning pouring slag of sampling analysis composition.In order to remove grain slag totally, also need to add the CaF of 5 ~ 8kg
2During flux comes and grain slag.The slag operation that dewaters obtains clean Al-Ti-B liquation after finishing at last;
4) heating, degasification and slagging-off are processed: open medium-frequency induction furnace power supply and melt heating to 850 ℃ ~ 900 ℃, in heating with one approximately the carbon tube in 20mm aperture lead to argon gas or nitrogen, air flow is advisable to allow aluminium liquid roll continuously to seethe with excitement from bottom to up, the continuous emersion of the residue meeting surface in melt; Ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then with standing 5 ~ 10 minutes of aluminum melt.Afterwards, just now ventilation, slagging-off and standing process repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: when temperature is increased to 850 ℃ ~ 900 ℃, progressively add the Al-20Sr master alloy wire rod of certainweight in melt; Wherein, Al-20Sr master alloy wire rod divides and adds aequum 1-3 time, and the time of repose of 10-15 minute is arranged after adding at every turn, until all Al-20Sr master alloy wire rods add finish after, mechanical stirring 5-10 minute.When melt temperature returns to 850 ℃ ~ 900 ℃, utilize the high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in the dynamic measurement melt;
6) cast bar: in melt hydrogen content up to standard (≤0.2ml/100gAl), and after disposing simultaneously surperficial slag blanket, the Al-Ti-B-Sr alloy melt is poured into diameter 100mm, be cast as the Al-Ti-B-Sr bar in the cylindrical iron mould of high 450mm;
7) hot extrusion molding: the Al-Ti-B-Sr alloy bar material that obtains is heated to 400 ℃-500 ℃ carries out sectional area gross distortion hot extrusion, finally obtaining diameter is the Al-Ti-B-Sr master alloy wire rod of 9.5mm.
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 is documented in claims.
Embodiment 1: the manufacturing of high quality Al-5Ti-1B-10Sr master alloy wire rod
The aluminium ingot of 522kg purity 99.7% is melted in molten aluminium stove, and be heated to 736 ℃, then pour in medium-frequency induction furnace, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide film.Take the K of 100kg purity 98%
2TiF
6With 100kg(be required KBF
4 Total amount 80%) KBF of purity 98%
4Raw material mixes.The K that just now weighed up
2TiF
6+ KBF
4Compound adds aluminium liquid with the speed of 24kg/min, the stirring action that simultaneous is strong.The first step is reinforced finish after, continue to stir, until the sampling analysis composition qualified after again the K that takes for the second time 161kg purity 98%
2TiF
6KBF with 25kg purity 98%
4Mixing raw material adds aluminum melt with the speed of 22kg/min, also is accompanied by strong stirring action simultaneously.After the reinforced end of second step, continue to stir, until the sampling analysis composition is qualified.Afterwards the grain slag on aluminium liquid surface is outwelled, added the CaF of 5kg left and right
2In powder and the grain slag of remained on surface, and also remove the slag that this process produces together clean.Afterwards, open medium-frequency induction furnace power supply and melt heating to 870 ℃, in the middle frequency furnace heating, one approximately the carbon tube in 20mm aperture insert the aluminum melt bottom, and begin to pass into nitrogen, air flow with aluminum melt from bottom to up continuously rolling boiling be advisable, the residue of melt inside can continuous emersion the surface.Ventilate after 3 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then with standing 10 minutes of aluminum melt, afterwards, then ventilated 3 minutes, removed after residue standing 10 minutes, ventilated for the third time 3 minutes and removed residue.When temperature reaches default 870 ℃, the Al-20Sr master alloy wire rod of 200kg is progressively added melt, then standing 15 minutes, again the Al-20Sr master alloy wire rod of 200kg is progressively added melt, again standing 15 minutes afterwards, again the Al-20Sr master alloy wire rod of 193 kg is progressively added melt at last.After all Al-20Sr master alloy wire rod fusings, mechanical stirring 10 minutes.When melt temperature returns to 870 ℃, utilize the high speed rotating getter, logical argon gas carried out degas operation 15 minutes to melt, and the content of hydrogen in the dynamic measurement melt.In melt hydrogen content up to standard (≤0.2ml/100gAl), and after disposing simultaneously surperficial slag blanket, the Al-5Ti-1B-10Sr alloy melt is poured into diameter 100mm, be cast as bar (Φ 100mm) in the cylindrical iron mould of high 450mm.At last these Al-5Ti-1B-10Sr alloy bar materials are placed on extrusion machine, carry out sectional area gross distortion hot extrusion processing treatment in the time of 450 ℃, finally obtain Al-5Ti-1B-10Sr master alloy wire product (Φ 9.5mm), as shown in Figure 1.
The metallographic structure of the Al-5Ti-1B-10Sr master alloy wire rod that embodiment 1 produces as shown in Figure 2.Can see bulk and particulate state and tiny black particle that a lot of whites are arranged in tissue, we know according in the past research, and wherein the white cake mass of a lot of holes, finedraw is arranged is Al on size slightly large and inner or surface
4The Sr phase, and size is slightly little, surface and inside all flawless white granular material are TiAl
3Phase, in addition, those very tiny black particles are TiB
2Phase.As everyone knows, Al
4Sr, TiAl
3And TiB
2Refinement and the modification effect of the pattern of phase, size and distribution situation and Al-5Ti-1B-10Sr master alloy wire rod are closely related.Wherein, TiAl
3And TiB
2The size of particle is less, distribution is more even, and the dissolution rate of its Ti is faster, and final thinning effect is better; And Al
4Sr is more tiny mutually, and the speed that its Sr atom discharges is faster, and deterioration latency stage is shorter, and modification effect is better.Therefore from Al
4Sr, TiAl
3And TiB
2The pattern of phase and size just can judge refinement and the rotten ability of this Al-5Ti-1B-10Sr master alloy wire rod.See Al from Fig. 2
4Sr presents bulk mutually, and inside exists many holes and finedraw, is evenly distributed, and size is less.Its length of gained and width distribution figure (Fig. 3) after Image-Pro Plus 6.0 image analysis software statistical measurements.Wherein, Al
4Sr phase average length is 43.2 μ m, and width is 26.8 μ m.TiAl
3Present mutually particulate state, distribute very even, and size is tiny, gained diameter Distribution situation is as shown in table 1 after Image-Pro Plus 6.0 image analysis software statistical measurements, and obtains diameter Distribution figure (Fig. 4) according to data in table.Wherein, TiAl
3Phase average diameter 14.4 μ m, the per-cent of diameter≤36 μ m reaches 92.58%, and maximum diameter is 43.55 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
2Even particle distribution does not have agglomeration to occur.Gained TiB after laser particle analyzer detects analysis
2The distribution of sizes situation of particle is as shown in table 2, and obtains size distribution plot (Fig. 5) according to data in table.Wherein, the TiB of size≤1.97 μ m
2The per-cent of particle is 95.77%, and overall dimension is 2.89 μ m.
TiB in Al-5Ti-1B-10Sr 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 | 0.96 | 100.00 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.40 | 0.40 | 3.50 | 0.00 | 100.00 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.43 | 0.83 | 4.24 | 0.00 | 100.00 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.82 | 1.65 | 5.13 | 0.00 | 100.00 | 74.2 | 0.00 | 100.00 |
| 0.43 | 1.79 | 3.44 | 6.21 | 0.00 | 100.00 | 89.8 | 0.00 | 100.00 |
| 0.52 | 3.19 | 6.63 | 7.51 | 0.00 | 100.00 | 108.6 | 0.00 | 100.00 |
| 0.63 | 7.79 | 14.42 | 9.09 | 0.00 | 100.00 | 131.5 | 0.00 | 100.00 |
| 0.76 | 12.89 | 27.31 | 11.00 | 0.00 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 16.98 | 44.29 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 18.20 | 62.49 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 16.42 | 78.91 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 10.39 | 89.30 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 6.47 | 95.77 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 3.27 | 99.04 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
Embodiment 2: the manufacturing of high quality Al-5Ti-1B-5Sr alloy wire
The aluminium ingot of 505kg purity 99.7% is melted in molten aluminium stove, and be heated to 736 ℃, then pour in medium-frequency induction furnace, prepare alloying process after disposing the impurity on aluminium liquid surface and oxide film.Take the K of 65kg purity 98%
2TiF
6With 65kg(be required KBF
4 Total amount 80%) KBF of purity 98%
4Raw material mixes.The K that just now weighed up
2TiF
6+ KBF
4Compound adds aluminium liquid with the speed of 24kg/min, the stirring action that simultaneous is strong.The first step is reinforced finish after, continue to stir, until the sampling analysis composition qualified after again the K that takes for the second time 104kg purity 98%
2TiF
6KBF with 16kg purity 98%
4Mixing raw material adds aluminum melt with the speed of 22kg/min, also is accompanied by strong stirring action simultaneously.After the reinforced end of second step, continue to stir, until the sampling analysis composition is qualified.Afterwards the grain slag on aluminium liquid surface is outwelled, added the CaF of 5kg left and right
2In powder and the grain slag of remained on surface, and also remove the slag that this process produces together clean.Afterwards, open medium-frequency induction furnace power supply and melt heating to 870 ℃, in the middle frequency furnace heating, one approximately the carbon tube in 20mm aperture insert the aluminum melt bottom, and begin to pass into nitrogen, air flow with aluminum melt from bottom to up continuously rolling boiling be advisable, the residue of melt inside can continuous emersion the surface.Ventilate after 3 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then with standing 10 minutes of aluminum melt, afterwards, then ventilated 3 minutes, removed after residue standing 10 minutes, ventilated for the third time 3 minutes and removed residue.When temperature reaches default 870 ℃, the Al-20Sr master alloy wire rod of 195kg is progressively added melt.After all Al-20Sr master alloy wire rod fusings, mechanical stirring 10 minutes.When melt temperature returns to 870 ℃, utilize the high speed rotating getter, logical argon gas carried out degas operation 12 minutes to melt, and the content of hydrogen in the dynamic measurement melt.In melt hydrogen content up to standard (≤0.2ml/100gAl), and after disposing simultaneously surperficial slag blanket, the Al-5Ti-1B-10Sr alloy melt is poured into diameter 100mm, be cast as bar (Φ 100mm) in the cylindrical iron mould of high 450mm.At last these Al-5Ti-1B-10Sr alloy bar materials are placed on extrusion machine, carry out sectional area gross distortion hot extrusion processing treatment in the time of 450 ℃, finally obtain Al-5Ti-1B-10Sr master alloy wire product (Φ 9.5mm), as shown in Figure 6.
The metallographic structure of the Al-5Ti-1B-5Sr master alloy wire rod that embodiment 2 produces as shown in Figure 7.See Al from Fig. 7
4Sr presents bulk mutually, and inside exists many holes and finedraw, is evenly distributed, and size is less.Its length of gained and width distribution figure (Fig. 8) after Image-Pro Plus 6.0 image analysis software statistical measurements.Wherein, Al
4Sr phase average length is 47.7 μ m, and width is 30.3 μ m.TiAl
3Present mutually particulate state, distribute very even, and size is tiny, gained diameter Distribution situation is as shown in table 3 after Image-Pro Plus 6.0 image analysis software statistical measurements, and obtains diameter Distribution figure (Fig. 9) according to data in table.Wherein, TiAl
3Phase average diameter 12.6 μ m, the per-cent of diameter≤30 μ m reaches 92.83%, and maximum diameter is 39.57 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
2Even particle distribution does not have agglomeration to occur.Gained TiB after laser particle analyzer detects analysis
2The distribution of sizes situation of particle is as shown in table 4, and obtains size distribution plot (Figure 10) according to data in table.Wherein, the TiB of size≤1.97 μ m
2The per-cent of particle is 97.41%, and overall dimension is only 2.89 μ m.
TiAl in Al-5Ti-1B-5Sr master alloy wire rod in table 3 example 2
3The diameter statistic data of phase
TiB in Al-5Ti-1B-5Sr 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 | 0.22 | 100.00 | 41.8 | 0.00 | 100.00 |
| 0.24 | 0.33 | 0.33 | 3.50 | 0.00 | 100.00 | 50.6 | 0.00 | 100.00 |
| 0.29 | 0.41 | 0.74 | 4.24 | 0.00 | 100.00 | 61.3 | 0.00 | 100.00 |
| 0.35 | 0.78 | 1.52 | 5.13 | 0.00 | 100.00 | 74.2 | 0.00 | 100.00 |
| 0.43 | 1.64 | 3.16 | 6.21 | 0.00 | 100.00 | 89.8 | 0.00 | 100.00 |
| 0.52 | 2.86 | 6.02 | 7.51 | 0.00 | 100.00 | 108.6 | 0.00 | 100.00 |
| 0.63 | 6.03 | 12.05 | 9.09 | 0.00 | 100.00 | 131.5 | 0.00 | 100.00 |
| 0.76 | 10.07 | 22.12 | 11.00 | 0.00 | 100.00 | 159.1 | 0.00 | 100.00 |
| 0.92 | 15.02 | 37.14 | 13.31 | 0.00 | 100.00 | 192.6 | 0.00 | 100.00 |
| 1.11 | 18.86 | 56.00 | 16.11 | 0.00 | 100.00 | 233.1 | 0.00 | 100.00 |
| 1.35 | 21.07 | 77.07 | 19.50 | 0.00 | 100.00 | 282.1 | 0.00 | 100.00 |
| 1.63 | 13.48 | 90.55 | 23.60 | 0.00 | 100.00 | 341.4 | 0.00 | 100.00 |
| 1.97 | 6.85 | 97.41 | 28.56 | 0.00 | 100.00 | 413.1 | 0.00 | 100.00 |
| 2.39 | 2.38 | 99.78 | 34.57 | 0.00 | 100.00 | 500.00 | 0.00 | 100.00 |
Claims (6)
1. the preparation method of a high quality Al-Ti-B-Sr master alloy composite refining alterant, at first melting the fine aluminium ingot in molten aluminium stove, then pours into and prepare alloying in medium-frequency induction furnace; Then take K
2TiF
6And KBF
4Raw material mixes, and drops in intermediate frequency furnace and treat among the aluminum melt of alloying; After the reaction certain hour again remaining K
2TiF
6And KBF
4Compound drops into molten aluminium, and reaction is outwelled grain slag after finishing; Through degasification with after slagging-off is processed again, progressively add the Al-20Sr alloy wire of certainweight; Through stirring and again after slagging-off, degassing processing, directly pouring into the Al-Ti-B-Sr alloy bar material; Afterwards these alloy bars are delivered to and carried out sectional area gross distortion hot extrusion on extrusion machine, obtaining at last diameter is the Al-Ti-B-Sr master alloy composite refining alterant wire rod of 9.5mm, it is characterized in that the preparation method that " three reinforced methods of step " and " hot extrusion molding " technique combine, specifically comprise the steps:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 ℃ ~ 750 ℃ in molten aluminium stove, then pours in medium-frequency induction furnace, prepare next step alloying process;
2) the first step is reinforced: the mass ratio by 1:1 takes respectively a certain amount of K
2TiF
6And KBF
4Raw material mixes, wherein, and KBF during the first step is reinforced
4Weight be required KBF
460% ~ 90% of total amount; Then with K
2TiF
6+ KBF
4Whether compound adds in aluminum melt by the feed rate of 20 ~ 30kg/min, and is accompanied by strong stirring action, continues to stir 5-15 minute after reinforced the end, and timing sampling is not analyzed the variation of composition in molten aluminium, complete to confirm the alloying reaction process;
3) second step is reinforced: after the first step reaction finishes, with K remaining in required villiaumite
2TiF
6And KBF
4Raw material mixes, and then the feed rate by 20 ~ 30kg/min adds in molten aluminium, also is accompanied by strong stirring action; After the reinforced end of second step, continue to stir 5-15 minute, begin down surperficial grain slag after the sampling analysis composition is qualified; Add CaF
2During flux comes and the grain slag of remained on surface, and the slag that this process produces is also removed together clean, the slag operation that dewaters obtains clean Al-Ti-B liquation after finishing at last;
4) heating, degasification and slagging-off are processed: open medium-frequency induction furnace power supply and melt heating to 850 ℃ ~ 900 ℃, in heating with one approximately the carbon tube in 20mm aperture lead to argon gas or nitrogen, air flow is advisable to allow aluminium liquid roll continuously to seethe with excitement from bottom to up, the continuous emersion of residue meeting surface in melt, ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then with standing 5 ~ 10 minutes of aluminum melt; Afterwards, aforesaid ventilation, slagging-off and standing process are repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: when temperature is increased to 850 ℃ ~ 900 ℃, progressively add the Al-20Sr master alloy wire rod of certainweight in melt; Wherein, Al-20Sr master alloy wire rod divides and adds aequum 1-3 time, and the time of repose of 10-15 minute is arranged after adding at every turn, until all Al-20Sr master alloy wire rods add finish after, mechanical stirring 5-10 minute; When melt temperature returns to 850 ℃ ~ 900 ℃, utilize the high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in the dynamic measurement melt;
6) cast bar: hydrogen content≤0.2ml/100gAl in melt, and after disposing simultaneously surperficial slag blanket, the Al-Ti-B-Sr alloy melt is poured into diameter 100mm, be cast as the Al-Ti-B-Sr bar in the cylindrical iron mould of high 450mm;
7) hot extrusion molding: the Al-Ti-B-Sr alloy bar material that obtains is heated to 400 ℃-500 ℃ carries out sectional area gross distortion hot extrusion, finally obtaining diameter is the Al-Ti-B-Sr master alloy composite refining alterant wire rod of 9.5mm.
2. preparation method as claimed in claim 1, is characterized in that: be accompanied by strong function composite by electromagnetic stirring when in " three reinforced methods of step ", the 3rd step was added Al-20Sr master alloy wire rod.
3. preparation method as claimed in claim 1, is characterized in that described Al-Ti-B-Sr master alloy composite refining alterant comprises Al-5Ti-1B-10Sr, Al-5Ti-1B-5Sr, Al-3Ti-1B-10Sr, Al-3Ti-1B-5Sr, Al-5Ti-0.5B-10Sr master alloy.
4. preparation method as claimed in claim 1, is characterized in that described K
2TiF
6And KBF
4Add-on is to calculate to determine according to the ratio of Ti and B in prepared Al-Ti-B-Sr master alloy.
5. preparation method as claimed in claim 1, is characterized in that described CaF
2Addition is to determine according to what that are finished down aluminium liquid top layer residue grain slag amount after grain slag, is generally 5-8kg.
6. preparation method as claimed in claim 1, the violent stirring that it is characterized in that the first step and second step adopt machine mixer, and rotating speed is 100-120 rev/min.
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