CN103173663B - 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, relate to a kind of preparation method of high quality Al-Ti-B-Sr master alloy composite refining alterant, specifically, by improving traditional processing technology, utilize " three steps feed in raw material method " and " hot extrusion molding " technique to prepare high quality Al-Ti-B-Sr master alloy composite refining alterant.
Background technology
Al-Si alloy is little owing to having density, the advantage such as specific tenacity is high, good welding performance, thermal expansivity are low and anti-corrosion, heat-resisting and wear resisting property is good, is widely used in high-tech areas such as mechanical industry, automotive industry, aviation and war industrys.Particularly aluminum alloy casting and die casting, almost more than 90% is associated gold manufacture with Al-Si.In castingprocesses, Al-Si alloy is general generates dendritic α-Al phase, and thick faller gill shape eutectic Si and block primary crystal Si phase, and other precipitated phase on a small quantity, 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 declines more.Therefore, generally need to carry out mutually thinning processing to Si in actual applications, by changing form, size and the distribution situation of Si phase, thereby reduce its weakening effect to α-Al matrix, to reach the object that improves 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, interpolation alterant method, ultrasonication, semi-solid casting and Temperature Treatment method etc., wherein, in industrial production, applying maximum also the most simple and effective method is to add alterant method.Conventional alterant element 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 being employed, but Na oxidation in rotten processing, scaling loss fierceness easily corrode crucible, and deteriorating time are short; Sb is subject to the impact of speed of cooling very large in metamorphic process, and can not use together with Na or Sr; Although 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, little to corrosion of crucible, and free from environmental pollution.When add Sr alterant in Al-Si alloy time, except eutectic Si can by thick faller gill shape be transformed into tiny spherical or fibrous, the size of primary crystal Si and quantity also reducing to a certain extent, thereby the mechanical property of having improved greatly alloy, particularly unit elongation is significantly improved.Therefore, 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 to thinning processing and 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 feeding in casting solidification process, improve resistance to air loss and the surface quality etc. of foundry goods.But known according to result of study in the past, although pattern and size that the interpolation of Sr can refinement Si phase but do not affect impact in other words to the dentrite α-Al in tissue little.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, for example: rapid solidification method, mechanical-physical refinement method, physical field refinement method and superalloy method etc.Wherein, the most simple and effective method is in molten aluminium, to add a small amount of grain-refining agent, thereby reaches the object of grain refining.Be mainly as fining agent the forties in 20th century with the salt fusant containing Ti, B, Zr, Nb etc.; The fifties, generally with the salt block agent that contains Ti, B element; The sixties, produce AlTi alloy block ingot (being 5%, 6% and 10% containing Ti per-cent); Develop Al-5Ti-1B silk the seventies; The eighties in 20th century, there is different component content (as Al-5Ti-1B, Al-3Ti-1B, Al-5Ti-0.2B etc.) in Al-Ti-B silk so far.At present, the agent of Al-Ti-B alloy refinement has become the most general in aluminum grain refinement industry and the most effective industrial fining agent, especially best with the effect of Al-5Ti-1B alloy.
Therefore, in actual industrial, in order to put forward heavy alloyed over-all properties, generally all need casting Al-Si alloy to carry out refinement and rotten two kinds for the treatment of process.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-Al crystal grain after these two step process in Al-Si alloy structure and Si have obtained refinement mutually, thereby have promoted the performance of material.But this treatment process mesometamorphism and thinning process separately carry out, extend technical process on the one hand, increase the operating time, promote 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 refinement simultaneously and become very important studying a question with rotten these two processes.At present, there is people to successfully synthesize Al-Ti-B-Sr master alloy by the way of directly adding metal Sr in Al-Ti-B intermediate alloy melt.After Al-Ti-B-Sr master alloy is processed, in Al-Si alloy structure, both there is good thinning effect, the modification effect having had again, and the mechanical property such as intensity, unit elongation of Al-Si alloy is all greatly improved after processing, this research shows that 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 first finished product Al-Ti-B master alloy to be melted, and then metal Sr is directly added to melt.This technique has obvious shortcoming: first, because the temperature of reaction of Sr and Al liquid is high, need to consume a large amount of energy and be used for the melt temperature that raises; Secondly, the activity of metal Sr is very high, directly adds in the reaction of metal Sr scaling loss very large under high temperature, has reduced the interior Al of alloy
4the quantity of Sr phase, increases rotten cost; Again, because Al-Ti-B alloy is 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 steps feed in raw material 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: first in molten aluminium stove, fine aluminium ingot is melted at a certain temperature, then pour into and in medium-frequency induction furnace, prepare alloying; Take K by certain proportion scale afterwards
2tiF
6and KBF
4raw material, mixes, and drops in intermediate frequency furnace and treat among the aluminum melt of alloying by certain speed; Reaction certain hour after again remaining K
2tiF
6and KBF
4compound also drops into molten aluminium, after reaction finishes, outwells grain slag; Through degasification with after slagging-off is processed again, progressively add the Al-20Sr alloy wire of certainweight; Through stirring and slagging-off again, after degassing processing, directly pouring into Al-Ti-B-Sr alloy bar material; Again these alloy bars are delivered on extrusion machine and carried out sectional area gross distortion extrusion process, finally obtaining 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
4sr phase size is also smaller.The Al-Ti-B-Sr master alloy of this microstructure features has well ensured refinement and the modification effect of product, can meet the thinning processing requirement of α-Al phase and Si phase in Al-Si alloy completely.Therefore, this invention is extremely adapted at industrial applying.
Summary of the invention
The present invention seeks to the shortcoming existing in traditional processing technology and problem improvement and bring new ideas in addition, for refinement/alterant industry provides a kind of preparation method of high quality Al-Ti-B-Sr master alloy composite refining alterant, that is: first in molten aluminium stove, fine aluminium ingot is melted at a certain temperature, then pour preparation alloying in medium-frequency induction furnace into; 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 under the intensively stirred effect of aluminium liquid, drops in intermediate frequency furnace by certain speed; Reaction certain hour after again remaining K
2tiF
6and KBF
4compound adds molten aluminium, after finishing etc. total overall reaction by clean grain slag; Then the temperature of aluminum liquid that raises passes into inert nitrogen gas/argon gas simultaneously liquation is carried out to 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 to melt by a certain percentage, and after whole fusings, carry out mechanical stirring and mix, 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; Finally, by the hot extrusion deformation processing at a certain temperature of this bar, make the wire rod of diameter 9.5mm.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: first use special " three steps feed in raw material method " to complete the operating process such as alloying, slagging-off, degasification, then be cast into Al-Ti-B-Sr master alloy bar, finally extrude Al-Ti-B-Sr master alloy wire rod by " hot extrusion molding " technique.
Mainly comprise the following steps:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 DEG C ~ 750 DEG C 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 steps feed in raw material method " is for preparing tiny TiAl
3phase and TiB
2phase, for reaching this target, adopt special KBF
4and K
2tiF
6proportion scale:, require reaction only to generate TiB in the first step alloying process
2phase, does not generate or only generates the seldom TiAl of amount substantially
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
6meter quantity relative ratio relationship show that this occurs in theory completely reacts required K
2tiF
6and KBF
4mass ratio be 0.953:1, but for fear of not exclusively producing superfluous KBF because reacting
4, to such an extent as to there is AlB
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, then by K
2tiF
6+ KBF
4compound adds in aluminum melt by the feed rate of 20 ~ 30kg/min, in reinforced process, wants violent stirring, to guarantee that raw material is evenly distributed on reaction interface, avoids causing the problem such as local superheating, resultant segregation because of the accumulation of villiaumite reactant.After reinforced end, continue to stir 5-15 minute, 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
3be uniformly distributed mutually, prevent that agglomeration from occurring; Can also destroy rich B Huo Fu Ti district, avoid TiB
2and TiAl
3too growing up of phase; In addition, stirring can also promote the carrying out of reaction, promotes the casting yield of the interior Ti of molten aluminium and B.It should be noted that the variation that needs composition in not timing sampling analysis molten aluminium in whipping process, to confirm whether alloying reaction process completes;
3) second step is reinforced: after the first step reaction finishes, by K remaining in required villiaumite
2tiF
6and KBF
4raw material mixes, then add molten aluminium by the feed rate of 20 ~ 30kg/min, also be accompanied by strong stirring action, after the reinforced end of second step, continue to stir 5-15 minute, after sampling analysis composition is qualified, start pouring slag, clean for grain slag being removed, also need to add a certain amount of CaF
2flux come in and grain slag, CaF
2main purpose be the surperficial grain slag layer of neutralization, addition be according to be finished down aluminium liquid top layer residue grain slag amount after grain slag number determine, generally add 5-8kg, after the slag operation that dewaters finishes, finally obtain clean Al-Ti-B liquation.
4) heating, degasification and slagging-off processing: open medium-frequency induction furnace power supply heating molten aluminium to 850 DEG C ~ 900 DEG C and insulation, carbon tube with an about 20mm aperture in heating 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 in melt can continuous emersion surface, ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then aluminum melt is left standstill to 5 ~ 10 minutes.Afterwards, ventilation, slagging-off and standing process are just now repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: in the time that temperature is increased to 850 DEG C ~ 900 DEG C, the Al-20Sr master alloy wire rod of certainweight is progressively added in melt, in the time adding Al-20Sr master alloy wire rod for fear of too much cause melt temperature in induction furnace to decline too many because of feeding quantity, so that melt viscosity is too large, and then have influence on after mass transfer and diffusion process, divide and add aequum 1-3 time, and after adding, there is a time of repose of 10-15 minute at every turn, the temperature so that medium-frequency induction furnace raises if having time again, has also promoted Al simultaneously
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, therefore melt is subject to the stirring action of electromagnetic field all the time, 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
4sr phase.After all Al-20Sr master alloy wire rods interpolations finish, mechanical stirring 5-10 minute, in the time that melt temperature returns to 850 DEG C ~ 900 DEG C, utilizes high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in dynamic measurement melt;
6) cast bar: as hydrogen content in melt (≤0.2ml/100gAl) up to standard, and dispose after surperficial slag blanket simultaneously, Al-Ti-B-Sr alloy melt is poured into diameter 100mm, in the cylindrical iron mould of high 450mm, be cast as Al-Ti-B-Sr bar;
7) hot extrusion molding: the Al-Ti-B-Sr alloy bar material obtaining is heated to 400 DEG C-500 DEG C and carries out sectional area gross distortion hot extrusion, finally obtaining diameter is the Al-Ti-B-Sr master alloy wire rod of 9.5mm.
When the 3rd step is added Al-20Sr master alloy wire rod in the present invention's " three steps feed in raw material method ", be accompanied by strong function composite by electromagnetic stirring.
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.
While feeding in raw material due to the first step in technique of the present invention, adopt 1:1(K
2tiF
6: KBF
4) proportion scale, therefore, in guarantee alloying process, there is not AlB
2under the prerequisite of phase, obtain 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 is constantly exposed to reaction interface and has destroyed rich B region, thereby has affected TiB
2the growth of phase, makes the last TiB generating
2particle size is tiny.In the time that 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 the formation of nucleus becomes very easy, 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 the 3rd step is reinforced, the temperature of reaction while directly there is alloying due to the temperature in stove lower than metal Sr and aluminium liquid on the one hand; Be Al-20Sr alloy wire instead of 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, and therefore the oxidizing reaction degree of Sr element declines, 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, therefore Al
4sr phase size is got back and is further reduced.The Al that these are tiny
4it is fast that Sr has guaranteed to discharge in metamorphic process Sr atomic velocity 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., therefore the present invention produces high quality Al-Ti-B-Sr master alloy composite refining alterant for industry member a kind of extremely important method is provided.
The invention has the advantages that:
1. detailed performance is high.In traditional Al-Ti-B-Sr alloying process, the temperature higher (900 DEG C-1000 DEG C) when 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 DEG C-900 DEG C) of the 3rd step when reinforced, avoid Yin Wendu to raise and the negative impact that brings.Therefore 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 adopted is Al-20Sr master alloy wire rod, and research in the past shows 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, when after the remelting of Al-20Sr master alloy wire rod, Al
4sr also can inherit this shape characteristic, therefore Al in the Al-Ti-B-Sr master alloy wire rod of final production mutually
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 DEG C-1000 DEG C 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 in technique of the present invention, well utilize liberated heat in " villiaumite method " reaction process.Particularly, the initial temperature of aluminum liquid of the present invention is only 700 DEG C-750 DEG C, complete first two steps reinforced after, in reaction, liberated heat can make melt temperature rise to 800 DEG C-900 DEG C, temperature required basic identical or gap is little when this and the 3rd step are reinforced, be raised to default 850 DEG C of-900 DEG C 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 the process that directly adds metal Sr and complete alloying, and therefore the oxidizing reaction of Sr is violent, and scaling loss is very large, and this also makes the content of Sr in the finished product 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 promoting the fusing speed of 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, easy to operate.In the present invention, do not use complicated equipment, also do not occur loaded down with trivial details technical process, therefore for manufacturing enterprise, technique is simple, easy to operate;
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 object 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 meet various clients' needs.
Brief description of the 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
The method of " three steps feed in raw material method " provided by the invention and " heat pressurization " explained hereafter high quality Al-Ti-B-Sr master alloy composite refining alterant is as follows:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 DEG C ~ 750 DEG C in molten aluminium stove, then pours in medium-frequency induction furnace, prepare next step alloying process;
2) the first step is reinforced: 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.Then by K
2tiF
6+ KBF
4compound 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 end, and timing sampling is not analyzed the variation of composition in molten aluminium, to confirm whether alloying reaction process completes;
3) second step is reinforced: after the first step reaction finishes, by K remaining in required villiaumite
2tiF
6and KBF
4raw material mixes, and then adds in molten aluminium by the feed rate of 20 ~ 30kg/min, is also accompanied by strong stirring action, after the reinforced end of second step, continues to stir 5-15 minute, starts pouring slag after sampling analysis composition is qualified.For grain slag being removed totally, also need to add the CaF of 5 ~ 8kg
2flux come in and grain slag.After the slag operation that dewaters finishes, finally obtain clean Al-Ti-B liquation;
4) heating, degasification and slagging-off processing: open medium-frequency induction furnace power supply melt heating to 850 DEG C ~ 900 DEG C, carbon tube with an about 20mm aperture in heating leads to argon gas or nitrogen, air flow with allow aluminium liquid from bottom to up continuously rolling boiling be advisable, the residue in melt can continuous emersion surface; Ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then aluminum melt is left standstill to 5 ~ 10 minutes.Afterwards, ventilation, slagging-off and standing process are just now repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: in the time that temperature is increased to 850 DEG C ~ 900 DEG C, the Al-20Sr master alloy wire rod of certainweight is progressively added in melt; Wherein, Al-20Sr master alloy wire rod divides and adds aequum 1-3 time, has the time of repose of 10-15 minute after adding at every turn, after all Al-20Sr master alloy wire rods add and finish, and mechanical stirring 5-10 minute.In the time that melt temperature returns to 850 DEG C ~ 900 DEG C, utilize high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in dynamic measurement melt;
6) cast bar: as hydrogen content in melt (≤0.2ml/100gAl) up to standard, and dispose after surperficial slag blanket simultaneously, Al-Ti-B-Sr alloy melt is poured into diameter 100mm, in the cylindrical iron mould of high 450mm, be cast as Al-Ti-B-Sr bar;
7) hot extrusion molding: the Al-Ti-B-Sr alloy bar material obtaining is heated to 400 DEG C-500 DEG C and 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.Do not departing under the prerequisite of 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 of request protection of the present invention, has all been documented in claims.
Embodiment 1: the manufacture 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 DEG C, 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
4total amount 80%) KBF of purity 98%
4raw material, mixes.The K just now weighing 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 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, is also accompanied by strong stirring action simultaneously.After the reinforced end of second step, continue to stir, until 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 the slag that this process is produced is also removed clean together.Afterwards, open medium-frequency induction furnace power supply melt heating to 870 DEG C, in middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to 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 3 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then aluminum melt is left standstill to 10 minutes, afterwards, then ventilate 3 minutes, after removing residue, leave standstill 10 minutes, ventilate for the third time 3 minutes and remove residue.In the time that temperature reaches default 870 DEG C, the Al-20Sr master alloy wire rod of 200kg is progressively added to melt, then leave standstill 15 minutes, again the Al-20Sr master alloy wire rod of 200kg is progressively added to melt, leave standstill 15 minutes more afterwards, finally again the Al-20Sr master alloy wire rod of 193 kg is progressively added to melt.After all Al-20Sr master alloy wire rod fusings, mechanical stirring 10 minutes.In the time that melt temperature returns to 870 DEG C, utilize high speed rotating getter, logical argon gas carries out degas operation 15 minutes to melt, and the content of hydrogen in dynamic measurement melt.As hydrogen content in melt (≤0.2ml/100gAl) up to standard, and dispose after surperficial slag blanket simultaneously, Al-5Ti-1B-10Sr alloy melt is poured into diameter 100mm, in the cylindrical iron mould of high 450mm, be cast as bar (Φ 100mm).Finally these Al-5Ti-1B-10Sr alloy bar materials are placed on extrusion machine, in the time of 450 DEG C, carry out sectional area gross distortion hot extrusion processing treatment, 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 and in tissue, have the bulk of a lot of whites and particulate state and tiny black particle, according to research in the past, we know, wherein to have the white cake mass of a lot of holes, finedraw be Al on size slightly large and inner or surface
4sr 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 pattern, size and the distribution situation of phase and Al-5Ti-1B-10Sr master alloy wire rod are closely related.Wherein, TiAl
3and TiB
2the size of particle is less, it is more even to distribute, 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.From Fig. 2, see Al
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, after Image-Pro Plus 6.0 image analysis software statistical measurements, gained diameter Distribution situation is as shown in table 1, 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
2in scope, not occurring size, king-sized (>50 μ m) 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 manufacture 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 DEG C, 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
4total amount 80%) KBF of purity 98%
4raw material, mixes.The K just now weighing 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 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, is also accompanied by strong stirring action simultaneously.After the reinforced end of second step, continue to stir, until 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 the slag that this process is produced is also removed clean together.Afterwards, open medium-frequency induction furnace power supply melt heating to 870 DEG C, in middle frequency furnace heating, the carbon tube in an about 20mm aperture is inserted to 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 3 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then aluminum melt is left standstill to 10 minutes, afterwards, then ventilate 3 minutes, after removing residue, leave standstill 10 minutes, ventilate for the third time 3 minutes and remove residue.In the time that temperature reaches default 870 DEG C, the Al-20Sr master alloy wire rod of 195kg is progressively added to melt.After all Al-20Sr master alloy wire rod fusings, mechanical stirring 10 minutes.In the time that melt temperature returns to 870 DEG C, utilize high speed rotating getter, logical argon gas carries out degas operation 12 minutes to melt, and the content of hydrogen in dynamic measurement melt.As hydrogen content in melt (≤0.2ml/100gAl) up to standard, and dispose after surperficial slag blanket simultaneously, Al-5Ti-1B-10Sr alloy melt is poured into diameter 100mm, in the cylindrical iron mould of high 450mm, be cast as bar (Φ 100mm).Finally these Al-5Ti-1B-10Sr alloy bar materials are placed on extrusion machine, in the time of 450 DEG C, carry out sectional area gross distortion hot extrusion processing treatment, 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.From Fig. 7, see Al
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, after Image-Pro Plus 6.0 image analysis software statistical measurements, gained diameter Distribution situation is as shown in table 3, 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
2in scope, not occurring size, king-sized (>50 μ m) 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. a preparation method for high quality Al-Ti-B-Sr master alloy composite refining alterant is first melting fine aluminium ingot in molten aluminium stove, then pours preparation alloying in medium-frequency induction furnace into; Then take K
2tiF
6and KBF
4raw material, mixes, and drops among the aluminum melt for the treatment of alloying in intermediate frequency furnace; Reaction certain hour after again remaining K
2tiF
6and KBF
4compound drops into molten aluminium, after reaction finishes, outwells grain slag; Through degasification with after slagging-off is processed again, progressively add the Al-20Sr alloy wire of certainweight; Through stirring and slagging-off again, after degassing processing, directly pouring into Al-Ti-B-Sr alloy bar material; Afterwards these alloy bars are delivered to and on extrusion machine, carried 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, it is characterized in that the preparation method that " three steps feed in raw material method " and " hot extrusion molding " technique combine, specifically comprise the steps:
1) fine aluminium fusing: the aluminium ingot of required weight is heated to 700 DEG C ~ 750 DEG C in molten aluminium stove, then pours in medium-frequency induction furnace, prepare next step alloying process;
2) the first step is reinforced: 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; Then by K
2tiF
6+ KBF
4compound 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 end, and timing sampling is not analyzed the variation of composition in molten aluminium, to confirm whether alloying reaction process completes;
3) second step is reinforced: after the first step reaction finishes, by K remaining in required villiaumite
2tiF
6and KBF
4raw material mixes, and then adds in molten aluminium by the feed rate of 20 ~ 30kg/min, is also accompanied by strong stirring action; After the reinforced end of second step, continue to stir 5-15 minute, after sampling analysis composition is qualified, start down surperficial grain slag; Add CaF
2during flux comes and the grain slag of remained on surface, and the slag that this process is produced also removes totally together, after the slag operation that dewaters finishes, finally obtains clean Al-Ti-B liquation;
4) heating, degasification and slagging-off processing: open medium-frequency induction furnace power supply melt heating to 850 DEG C ~ 900 DEG C, carbon tube with a 20mm aperture in heating 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 in melt can continuous emersion surface, ventilate after 3 ~ 5 minutes, remove carbon tube, close source of the gas, the residue of surperficial emersion is disposed, then aluminum melt is left standstill to 5 ~ 10 minutes; Afterwards, aforesaid ventilation, slagging-off and standing process are repeated 1 ~ 3 time again;
5) the 3rd step is reinforced: in the time that temperature is increased to 850 DEG C ~ 900 DEG C, the Al-20Sr master alloy wire rod of certainweight is progressively added in melt; Wherein, Al-20Sr master alloy wire rod divides and adds aequum 1-3 time, has the time of repose of 10-15 minute after adding at every turn, after all Al-20Sr master alloy wire rods add and finish, and mechanical stirring 5-10 minute; In the time that melt temperature returns to 850 DEG C ~ 900 DEG C, utilize high speed rotating getter, logical argon gas carries out degas operation 10-20 minute to melt, and the content of hydrogen in dynamic measurement melt;
6) cast bar: as hydrogen content≤0.2ml/100gAl in melt, and dispose after surperficial slag blanket simultaneously, Al-Ti-B-Sr alloy melt is poured into diameter 100mm, be cast as 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 obtaining is heated to 400 DEG C-500 DEG C and 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: when the 3rd step is added Al-20Sr master alloy wire rod in " three steps feed in raw material method ", be accompanied by strong function composite by electromagnetic stirring.
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 be according to be finished down aluminium liquid top layer residue grain slag amount after grain slag number determine, be 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 is to adopt machine mixer, rotating speed is 100-120 rev/min.
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| CN104131201B (en) * | 2014-08-18 | 2016-03-30 | 河南誉金技术服务有限公司 | A kind of Mg-Al base alloy refinement alterant and its preparation method and application |
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| CN110804704A (en) * | 2019-10-12 | 2020-02-18 | 浙江今飞汽摩配技术研究院有限公司 | Preparation method of Al-Ti-B-Sr intermediate alloy and Al-Ti-B-Sr intermediate alloy |
| CN111349822B (en) * | 2020-03-20 | 2021-08-13 | 永城金联星铝合金有限公司 | Aluminum-titanium-boron-strontium-rare earth alloy wire and preparation method thereof |
| CN112048589A (en) * | 2020-09-03 | 2020-12-08 | 遵义金业机械铸造有限公司 | Aluminum-based composite deoxidizing modifier alloy |
| CN114294950B (en) * | 2021-12-27 | 2024-02-13 | 福建省漳平市九鼎氟化工有限公司 | Setting and method for preparing aluminum-titanium-boron alloy refiner |
| CN115505777A (en) * | 2022-10-08 | 2022-12-23 | 秦皇岛峰越科技有限公司 | Preparation method of aluminum-lanthanum-boron-titanium grain refiner |
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