The manufacture method of a kind of high-cleanness, high Al-Ti-B alloy refinement
Technical field
The present invention relates to the manufacturing process of Al-Ti-B alloy material, refer in particular to the manufacture method of a kind of high-cleanness, high Al-Ti-B alloy refinement.
Background technology
The development of aluminum grain refiner roughly is divided into following several stages: in the 40's of 20th century, use to contain the salt fusant matter of Ti, B, Zr, Nb etc. as fining agent; In the 50's, generally use the salt block agent that contains Ti, B element; In the 60's, AlTi alloy block ingot (containing Ti5%, 6%, 10%) is as the fining agent that generally uses; The 70's were developed AlTiB silk (AlTi5%B1%), and the fining agent of this titaniferous, boron has extremely strong thinning effect than the independent fining agent that contains titanium elements (AlTi); The 80's of 20th century, different component content (as AlTi5%B1%, AlTi3%B1%, AlTi5%B0.2% etc.) appearred in aluminium titanium boron wire so far.At present, become the processing method of the most general and effective employing of aluminum grain refinement with al-ti-b refiner.At present, al-ti-b refiner become aluminium and alloy refinement thereof handle the most efficient, stablize fining agent.
In preparing the method for aluminum grain refiner, be divided into conventional ceramic technique, villiaumite method, pure titanium particle method etc. by raw material; Be divided into by preparation technology: thermit reduction, electrolytic process, self propagating high temperature synthesis method etc.Up till now, it is the villiaumite method that the whole world prepares the most extensive and effective means of Al-Ti-B intermediate alloy, promptly utilizes potassium fluotitanate and potassium fluoborate to produce Al-Ti-B alloy by thermite reaction.Its thinning effect of Al-Ti-B alloy that this method is produced by force and very stable.But its shortcoming is because the inclusion that metallic compound impurity that by product hydrofluoaluminic acid sylvite that produces in alloying process and reaction are brought into and fused salt are brought into the corrosion of refractory materials is difficult to effectively thoroughly remove from Al-Ti-B alloy.Cause these impurity to be brought into by in the middle of the alloy of refinement with fining agent.Weakened the aluminium alloy thinning effect greatly.The existence of low melting point salt impurity simultaneously causes being worsened by the hot workability of refinement alloy and welding property.Can not satisfy the high-accuracy of continuous development, the demand that grain refining is handled in the high-quality aluminum alloy material castingprocesses.
The present thin alloying agents of aluminium titanium boron, owing in the alloying process of its manufacturing, need to add a large amount of potassium fluotitanates and fluoroboric acid sylvite, thermite reaction produces a large amount of hydrofluoaluminic acid sylvite by product, villiaumite impurities and brings the corrosion to furnace lining of aluminium liquid and fluoride salt into, and bring the inclusion of a large amount of iron content, silicon, magnesium, calcium etc. into, these low-melting fluorine chloric acid sylvite are difficult to separate with alloy liquid with compound impurity, and part is present in the fining agent, its thinning effect is weakened greatly, simultaneously also for to be brought into new impurity component by the refinement aluminum alloy melt.Particularly the inclusion of salt such as low-melting potassium fluoroaluminate is present in the fining agent, and is brought into by in the refinement aluminium alloy, will worsen by performances such as the hot-work of refinement aluminium alloy, welding, makes it produce hot tearing.Can not satisfy the requirement of the thinning processing of growing and high-grade, precision and advanced, the high-quality aluminum alloy material of constantly bringing forth new ideas.
Summary of the invention
The objective of the invention is to be improved and innovate, a kind of manufacture method that can satisfy the high-cleanness, high Al-Ti-B alloy refinement of high-grade, precision and advanced, high-end aluminium alloy thinning processing is provided at the shortcoming that exists in the background technology and problem.
The present invention is 11-12:2-3:1-2 with the weight ratio of starting material fine aluminium, potassium fluotitanate, potassium fluoborate.Alloying under the electromagnetic force effect; with in the aluminum oxide powder and surperficial low melting point scum silica frost; take the residue that wraps up in the aluminium liquid with the logical argon gas of graphite (or other is not by aluminium corrosion material) pipe out of by the boiling of rolling of aluminium liquid; utilize rare gas element argon gas and rotation getter that Al-Ti-B alloy liquid is made degassing processing; relief is under a kind of protection of formulated covering flux; aluminium liquid is warming up to overheated condition; and, be cast into magnificent husband's ingot or produce aluminium titanium boron wire by continuous casting and continuous rolling mill by behind the aluminum oxide foam ceramic filter.Specifically may further comprise the steps:
1,, adds potassium fluotitanate and potassium fluoborate compound, alloying under intermediate frequency (200-2500 hertz) electromagnetic field stirring action with the fusing of the aluminium ingot of required weight and be heated to 700-740 ℃.
2, treat that thermite reaction finishes, composition qualified after, topple over the byproduct of reaction that to float on the aluminium surface, and with in the aluminum oxide powder and skimming behind the remaining raffinate.Subsequently the alloy liquid temp is promoted to 740-780 ° of C and induction furnace heat tracing, and sprinkles the aluminum oxide bisque of about 5-10mm in aluminium liquid surface.
3, the carbon tube (or other pipe of the corrosive of anti-aluminium) with about 20mm aperture leads to argon gas (or nitrogen), allow the boiling of rolling continuously from bottom to up of aluminium liquid, residue liquid emersion is constantly arranged, and by the aluminum oxide powder on aluminium liquid surface absorption neutralization, process continues about 20-30 minute.
4, when aluminium liquid at 740-780 ℃, utilize small bubbles rotation degasification refining techniques, at temperature of aluminum liquid 740-780 ℃, with the logical argon gas degasification refining in the graphite rotator of 300-400rpm of rotation getter, gas flow is controlled at about 10-30ml/min. according to varying in weight of aluminium liquid, and measures its hydrogen content.When reaching 0.2ml/100gAl, hydrogen content stops degassing processing when following.
5, when aluminium liquid under superheat state more than 800 °, need aluminium liquid surface to sprinkle Repone K, Sodium Fluoride and the aluminum oxide powder special lid agent layer formed of 3:1:1 by weight, the tectum of this special composition will at high temperature be avoided alloy liquid oxidation and air-breathing.
6, the temperature of aluminum liquid under the above-mentioned special high temperature covering agent layer is risen to 900-950 ° of C, simultaneously with aluminium liquid under the protection of this special insulating covering agent layer, import the filter box that the alumina-ceramic strainer is housed, alloy liquid is filtered.
7, filtered alloy liquid is passed through temperature drop to 720-760 ° of C, the skim surface scum is cast into magnificent husband's ingot and continuous casting and rolling and makes slick aluminium titanium boron wire wire rod.
Advantage of the present invention and beneficial effect:
The present invention produces the Al-Ti-B alloy fining agent of high-cleanness, high by a kind of new manufacturing process.This technology can effectively be isolated fluoride salt in the Al-Ti-B alloy liquid and other inclusion, makes that impurities reduces in the Al-Ti-B alloy fining agent, cleanliness factor increases substantially.By metallographicinspection, 1 square centimeter of possibility that the above inclusion of 0.1 mm size occurs is between 6-8%; Every square centimeter of possibility that inclusion more than 0.2 millimeter occurs is between 2-3%; Every square centimeter of possibility that 0.5 millimeter impurity occurs is 0.5-1.0%.Its hydrogen content of while can be controlled in 0.3-0.3ml/100gAl. and satisfies requirement high-grade, precision and advanced, the high-quality aluminum alloy thinning processing better.
The material cleanliness factor height that the inventive method is produced, the compound impurity of contained byproduct of reaction hydrofluoaluminic acid sylvite and iron, silicon, magnesium, calcium is very low.Reduced greatly aluminium alloy in the melting and casting process owing to add the compound impurity of iron content that the refinement material brought, silicon, magnesium, calcium, and the harm that aluminum alloy materials is brought of salt contaminating impurity such as potassium fluoroaluminate, have stronger thinning effect and seldom bring rubbish pollution into being gone up substantially by the refinement aluminium alloy.
Embodiment
Embodiment 1: the manufacturing of high clean aluminium titanium boron wire (AlTi5B1)
The al-ti-b refiner of the composition of titaniferous 5% and boracic 1% is a kind of wrought aluminium alloy that is widely used in most, particularly the refinement material of manufacturing such as aluminium alloy extrusions and plate, band.
To melt in the 1050kg99.7% aluminium ingot adding Medium frequency induction aluminium, and be heated to 720 ° of C, the potassium fluoborate compound that adds the potassium fluotitanate of 230kg purity 98% and 120kg purity 98% down in intermediate frequency electromagnetic force (1000 hertz of frequencies) effect is in aluminium melt surface, and the maintenance temperature of aluminum liquid.Continue intermediate frequency induction stirring and insulation 30 minutes, question response finishes, the qualified back of sampling composition (titanium content 4.5-5.5%, boron content 0.8-1.2%), topple over the byproduct of reaction that to float on the aluminium surface, and be sprinkling upon skimming behind the remaining raffinate of aluminium liquid surface neutralization with 5 kilograms of aluminum oxide powders.The alloy liquid temp is promoted to intermediate frequency induction stirring under 750 ° of C and induction furnace heat tracing and 1000 hertz frequencies, and sprinkles about 5 kilograms aluminum oxide bisque in aluminium liquid surface aluminium liquid is covered.Utilize the logical argon gas of carbon tube in about 20mm aperture, allow the boiling of rolling continuously from bottom to up of aluminium liquid, residue liquid emersion is constantly arranged, and floated on the surface oxidation aluminium powder and adsorb, handle after 30 minutes always and stop skimming.Then, utilize small bubbles rotation degasification refining techniques, aluminium liquid is carried out degassing processing with the rotation getter.At 750 ℃, use the rotation getter, with the logical argon gas degasification refining of graphite rotator of 300rpm rotating speed, gas flow is controlled at 15ml/min.And constantly measure hydrogen richness, and about 30 minutes, as H≤0.2ml/100gAl, stop degassing processing, and with aluminum oxide powder neutralizing treatment surface low melting point residue.Aluminium liquid surface is sprinkled 5 kilograms by Repone K, Sodium Fluoride and the aluminum oxide powder special insulating covering agent layer formed of 3:1:1 by weight; utilize medium-frequency induction furnace to heat up; after temperature of aluminum liquid risen to 920 ° of C; under the protection of special insulating covering agent, the importing of superheated aluminum alloy melt is equipped with in the filter box of alumina-ceramic strainer; alloy liquid is carried out on-line filtration to be handled; the aperture of porcelain filter is 20ppi, is of a size of 200mm X 200mm X 50mm.Aluminium liquid after filtering is cooled to 750 ° of C, is cast into the magnificent husband's ingot of AlTi5B1 or the aluminium titanium boron wire that continuous casting and rolling becomes AlTi5B1.It is qualified to obtain composition, the low Al-Ti-B alloy of gassiness dregginess in the alloy.Be specially: show 1 square centimeter of possibility 6.6% that the above inclusion of 0.1 mm size occurs by the metallographicinspection statistics; Every square centimeter of possibility 2.5% that inclusion more than 0.2 millimeter occurs; Every square centimeter of possibility that 0.5 millimeter impurity occurs is 0.9%.While its hydrogen content 0.27ml/100gAl.
Embodiment 2:The manufacturing of high clean Al-Ti-B alloy AlTi5B0.2
The al-ti-b refiner of the composition of titaniferous 5% and boracic 0.2% is a kind of aluminium alloy extrusions that is widely used in, and uses the part foundry returns to do the thinning processing material of the aluminium alloy extrusions founding of raw material especially.
To melt in the 1050kg99.7% aluminium ingot adding Medium frequency induction aluminium, and be heated to 700-740 ° of C, the potassium fluoborate compound that adds the potassium fluotitanate of 230kg purity 98% and 25kg purity 98% down in intermediate frequency electromagnetic force (1000 hertz of frequencies) effect is in aluminium melt surface, and the maintenance temperature of aluminum liquid.Continue intermediate frequency induction stirring and insulation 30 minutes, question response finishes, the qualified back of sampling composition (titanium content 4.5-5.5%, boron content 0.18-0.24%), topple over the byproduct of reaction that to float on the aluminium surface, and be sprinkling upon skimming behind the remaining raffinate of aluminium liquid surface neutralization with 3 kilograms of aluminum oxide powders.The alloy liquid temp is promoted to intermediate frequency induction stirring under 750 ° of C and induction furnace heat tracing and 1000 hertz frequencies, and sprinkles about 3 kilograms aluminum oxide bisque in aluminium liquid surface aluminium liquid is covered.Utilize the logical argon gas of carbon tube in about 20mm aperture, allow the boiling of rolling continuously from bottom to up of aluminium liquid, residue liquid emersion is constantly arranged, and floated on the surface oxidation aluminium powder and adsorb, handle after 20 minutes always and stop skimming.Then, utilize small bubbles rotation degasification refining techniques, aluminium liquid is carried out degassing processing with the rotation getter.At 750 ℃, use the rotation getter, with the logical argon gas degasification refining of graphite rotator of 300rpm rotating speed, gas flow is controlled at 15ml/min.And constantly measure hydrogen richness, as H≤0.2ml/100gAl, stop degassing processing, and with aluminum oxide powder neutralizing treatment surface low melting point residue.Aluminium liquid surface sprinkles Repone K, Sodium Fluoride and the aluminum oxide powder special high-temp antioxidizing and the air-breathing insulating covering agent layer of 3:1:1 composition by weight; utilize medium-frequency induction furnace to heat up; after temperature of aluminum liquid is superheated to 920 ° of C; with aluminium liquid under the protection of this special insulating covering agent layer; importing is equipped with in the filter box of alumina-ceramic strainer; alloy liquid is carried out filtration treatment, and the aperture of porcelain filter is 30ppi, is of a size of 200mm X 200mm X 50mm.Aluminium liquid after filtering is cooled to 750 ° of C, is cast into magnificent husband's ingot of AlTi5B0.2 and makes the aluminium titanium boron wire of AlTi5B0.2 by continuous casting and rolling production line by foudry line.It is qualified to obtain composition, the low Al-Ti-B alloy of gassiness dregginess in the alloy.Be specially: show 1 square centimeter of possibility 6.2% that the above inclusion of 0.1 mm size occurs by the metallographicinspection statistics; Every square centimeter of possibility 2.5% that inclusion more than 0.2 millimeter occurs; Every square centimeter of possibility that 0.5 millimeter impurity occurs is 0.8%.While its hydrogen content 0.25ml/100gAl.
Embodiment of the present invention only is the description that preferred implementation of the present invention is carried out; be not that design of the present invention and scope are limited; under the prerequisite that does not break away from design philosophy of the present invention; engineering technical personnel make technical scheme of the present invention in this area various modification and improvement; 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.