Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/02—Making non-ferrous alloys by melting
  • C22C1/026—Alloys based on aluminium

Definitions

• the aluminum-titanium-boron ternary system is commonly used as grain refiners in aluminum melts in order to obtain a small, equiaxed grain size during solidification. This is important in order to increase the resistance to ingot cracking and in order to improve the mechanical properties and the surface quality of the aluminum alloys produced.
• preparation of such alloys results in the formation of titanium diboride particles and clusters of said particles which are insoluble in the aluminum matrix.
• titanium diboride particles are desirable, it is desirable to minimize growth of the titanium diboride particles and clusters since they reduce the effectiveness of the alloy.
• preparation of such alloys results in the formation of TiAl 3 particles and large titanium aluminide particles may cause processing problems.
• KBF 4 is commonly used as a commercial source of boron in obtaining these alloys; however, this material has a high cost which adds greatly to the raw material costs in producing these alloys.
• U.S. Patent 3,961,995 describes a process for producing certain aluminum-titanium-boron alloys including the formation of titanium diboride by reacting liquid aluminum with titanium oxide and boron oxide in solution in molten cryolite and quenching the alloy rapidly to cool and solubilize the reaction product.
• this reference is limited to boron contents of 0.2 to 0.8% and requires high operating temperatures generally in excess of 1000°C.
• the method of the present invention forms an aluminum base alloy containing titanium and boron, including the steps of: providing a bath of molten aluminum; adding to the melt (1) a boron containing material consisting essentially of borax, but which may also contain boron oxide, boric acid and mixtures thereof, and a titanium containing material consisting essentially of K 2 TiF 6 and stirring the molten bath to intimately admix the boron containing material, the K 2 TiF 6 and the molten aluminum and to form an aluminum base alloy containing titanium and boron.
• the boron containing material should desirably be mixed with or added to the melt before the K 2 TiF 6 .
• the preferred boron containing material is calcined borax and it is preferred to use a ratio of at least 5 parts titanium to 1 part boron.
• an inert salt cover is provided over the bath of molten aluminum (preferably at least in part consisting of potassium-aluminum-fluoride), the mixture of boron containing material and K 2 TiF 6 (potassium salt) are added to the molten aluminum to form a molten mixture and the molten mixture stirred for at least 10 minutes.
• the resultant aluminum-titanium-boron alloy is characterized by improved properties and consists essentially of boron from 0.1 to 3.0%, generally from 0.1 to 1.0%, titanium from 1 to 10%, generally from 2 to 5% and the balance essentially aluminum.
• the alloy produces an average grain size of below 300 microns when added to aluminum and generally below 250 microns. All percentages herein are percentages by weight.
• the aluminum-titanium-boron alloy contains TiB 2 particles dispersed throughout said matrix having an average particle size of less than 1 micron. Still further, the matrix contains fewer of the undesirable clusters of said TiB 2 particles, with said clusters being defined as greater than 10 microns in size and with said matrix containing an average of less than 4 of said clusters per 2 cm 2 , generally less than 3 of said clusters per 2 cm 2 .
• the aluminum-titanium-boron alloy contains TiAl 3 particles having a desirably small particle size with the average titanium aluminide diameter being less than 25 microns and generally less than 20 microns.
• aluminum alloys are formed containing titanium and boron.
• the alloys prepared include from 0.1 to 3.0% boron, generally from 0.1 to 1.0%, and from 1 to 10% titanium, generally from 2 to 5%, with the balance essentially aluminum.
• other alloying additions may readily be utilized in accordance with the present invention and conventional impurities are contemplated.
• the process of the present invention adds the boron and titanium containing materials to a bath of molten aluminum, maintained at a temperature in excess of 1220°F.
• the present invention adds a boron containing material consisting essentially of borax, but which may also contain such other boron-containing materials as boron oxide and boric acid and mixtures thereof, plus K 2 TiF 6 . It is preferred to employ the borax, Na 2 B 4 O 7 , as a calcined material, and one generally employs calcined borax. It is also preferred to premix the boron and titanium containing materials and it is also preferred to use a ratio of at least 5 parts titanium to 1 part boron provided by the borax.
• the reaction of calcined borax with the aluminum produces aluminum oxide.
• concentration of oxide present in the spent salt is around 18%, the apparent maximum in solution, while keeping the spent salt relatively fluid at the standard operating temperature. The reason for the high ratio is so that the spent salt remains fluid and can be readily separated from the aluminum. If the spent salt is too viscous, it will be partially entrained in the product which is undesirable. If the ratio is low, a preferred practice would be to use an inert salt cover. The lowest titanium to boron ratio contemplated would be 2.2:1. In this case, the oxide concentration is 32% in the spent salt. Therefore, an inert salt should be added such that the oxide concentration is no more than 18% in the spent salt.
• a portion of the boron may be provided by KBF 4 , preferably as a separate addition, especially for low titanium content alloys.
• An inert salt cover may be used over the molten aluminum and can act as an oxide absorber. This facilitates the use of a lower titanium-boron ratio. Experimentation has shown that an inert salt cover will not affect the recoveries of the boron or titanium. Fluoride salts are preferred for the inert salt cover, and one can combine fluorides and chlorides. Potassium-aluminum-fluoride or potassium cryolite is a preferred material for the salt cover. Lower melting point salts are preferred for the salt cover with the melting point naturally being in excess of the 1220°F melting point of the aluminum bath, and it is preferred to employ inert salts with melting points below about 1850°F. It is preferred to employ a sufficient amount of salt cover to absorb the aluminum oxide which is a product of the reaction, and generally an inert salt cover of at least 6 inches is employed in order to prevent additional aluminum oxidation due to aluminum exposure while stirring vigorously.
• the molten bath contains a fairly large volume fraction of spent salt during the process, which is actually reduced in terms of total volume using the process of the present invention. Moreover, the throughput is improved in the process of the present invention and thus is an advantage of the present invention.
• borax contains 21.5% boron and KBF 4 contains 8.6% boron, which means that a larger volume of KBF 4 is added when using this material.
• the reaction mixture should be thoroughly stirred.
• the reaction time is not especially critical. If one employs a mixture of the boron and titanium containing materials, an instantaneous reaction occurs. If a mixture of the boron and titanium containing materials is not employed, a higher reaction temperature should be employed, as for example, between 1600 and 1800°F. The reaction is exothermic so that the temperature will rise during the reaction. The temperature will tend to rise fairly rapidly with a blend of boron and titanium containing materials and fairly slowly if the components are added individually. Reaction times of at least 10 minutes are preferred and generally less than 2 hours. The reaction is complete when the temperature tends to level off. More rapid reaction times occur using the premixed boron and titanium containing materials than without.
• the salt is decanted off.
• KBF 4 is employed as the commercial source of boron, and sources of titanium include titanium sponge, titanium turnings and K 2 TiF 6 . It is a disadvantage of KBF 4 that it has a high cost.
• hard TiB 2 particles form in the aluminum matrix. It is desirable to obtain a small particle size for the TiB 2 particles. Further, these particles, which include TiB 2 complexes, tend to cluster together in the aluminum matrix with clusters over 10 microns in size. The TiB 2 and the clusters of TiB 2 may cause defects in use, especially in rolling or in the formation of thin gauge products. It is desirable, therefore, to obtain a small particle size for the TiB 2 particles and a small number of clusters of same so that when the grain refiner alloy is added to promote grain refining, a smaller number of these particles are present in the final grain refined product.
• the aluminum grain refiner alloy be effective to produce a relatively small average grain size in the grain refined product so that a smaller proportion is required to be added.
• the aluminum matrix of the grain refined product has an average grain size below 300 microns and generally below 250 microns at an addition level of 0.01% titanium when using a 5% Ti/1% B alloy.
• the matrix contains TiB 2 particles, including complexes thereof, dispersed throughout the matrix which have an average particle size of less than 1 micron, with many particles approaching 0.1 micron in size. This is a significant advantage in view of the small particle size.
• the material of the present invention forms fewer clusters of said TiB 2 particles.
• the matrix of the present invention contains clusters of the TiB 2 particles, with the clusters being greater than 10 microns in size, and with the matrix containing an average of less than 4 said clusters per 2 cm 2 , and generally less than 3 of said clusters per 2 cm 2 . This represents a significant advantage in view of the small number of TiB 2 clusters formed. Conventional materials have substantially greater numbers of these.
• the aluminum-titanium-boron alloy of the present invention contains TiAl 3 particles having a desirably small particle size.
• the average titanium aluminide diameter is less than 25 microns and generally less than 20 microns. This represents a considerable advantage and indicates that the titanium alumindes in accordance with the present invention are desirably much smaller and therefore more numerous for a given titanium concentration.
• An aluminum melt was formed at a temperature of 1300°F and using approximately 2000 pounds of aluminum.
• a blend of K 2 TiF 6 and borax was prepared using 30 pounds of borax and 300 pounds of K 2 TiF 6 powder. No salt cover was employed and the blend was added to the melt while stirring.
• a salt layer formed over the melt during the reaction and the temperature was monitored. The temperature of the melt rose rapidly to about 1500°F in about 10 minutes, whereupon the temperature levelled off and the reaction was complete.
• a second flux was added containing about 253 pounds of K 2 TiF 6 and 180 pounds of KBF 4 .
• the salt was then decanted.
• the resulting alloy contained about 5% titanium and 1% boron. The results were evaluated using an average of 10 heats.
• Titanium and boron recoveries were virtually 100%.
• the average grain size of a grain refined product at an addition level of 0.01% Ti was less than 250 microns.
• the average TiB 2 particle size in the Al-Ti-B alloy prepared was less than 1 micron.
• the average number of clusters of TiB 2 greater than 10 microns in size per 2 cm 2 was about 2.5 in the alloy produced.
• Example II essentially repeated the procedure of Example I utilizing KBF 4 instead of the borax.
• the amounts employed were calculated to give a final alloy containing 5% titanium and 1% boron.
• the mixture was added to the melt while continuously stirring whereupon the temperature rose to 1600 to 1650°F in from about 30 minutes to 1 hour, and levelled off indicating that the reaction was complete.
• the results were evaluated based on an average of 10 heats.
• the average titanium and boron recoveries were less than in Example I.
• the average grain size of a grain refined product at an addition level of 0.01% Ti was about 350 microns.
• the particle size of the TiB 2 averaged about 2 microns in the Al-Ti-B alloy produced. Substantially more clusters of TiB 2 particles greater than 10 microns in size were found per 2 cm 2 with an average of 5.3 of said clusters being found per 2 cm 2 sample in the alloy produced.
• Example II essentially repeated the procedure of Example I blending 100 pounds of borax with 536 pounds of K 2 TiF 6 . This blend was added to molten aluminum such that the final concentration was 5% Ti and 1% B. A sample of the resultant alloy was examined and it was found that there were three small TiB 2 clusters greater than 10 microns in size in a 2 cm 2 area. Also, the average TiAl 3 diameter was less than 20 microns based on image analysis. High titanium and boron recoveries were obtained. The temperature rise due to the exothermic reaction was about 260°F.

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Citations (7)

• 1995
  • 1995-03-17 EP EP95103920A patent/EP0732414A1/fr not_active Ceased

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