Degassing treatment of molten aluminum alloys

Dr. Dmitri Kopeliovich Degassing of molten Aluminum alloys is a foundry operation aimed to remove Hydrogen dissolved in the melt.

Hydrogen in aluminum Degassing by fluxes Rotary degasser

Hydrogen in aluminum Liquid aluminum actively dissolves hydrogen, which forms as a result of chemical reaction with water vapor: 2Al + 3H2O = Al2O3 + 6H Solubility of gaseous hydrogen in liquid aluminum at its melting point (1220.7F/660.4C) is 0.61 in3/lb (2.2 cm3 per 100 g). Solubility of gaseous hydrogen falls sharply when aluminum solidifies: solid aluminum at melting point contains only 0.014 in3/lb (0.05 cm3 per 100 g). Therefore aluminum alloys release excessive amount of hydrogen during Solidification. This results in porosity defects distributed throughout the solid metal. Size of the hydrogen pores and their quantity is determined by the initial content of hydrogen, the alloy composition and the solidification conditions. Sources of hydrogen in molten aluminum:

atmosphere humidity; wet metallic charge; wet furnace lining (crucible, transfer ladles); wet foundry instruments; wet fluxes and other consumables; furnace fuel combustion products containing hydrogen.

Methods of hydrogen content estimation:

Slow solidification. In this method a small portion of liquid aluminum (about 2 in3/33 cm3) is poured into a cavity in a heated refractory brick. The alloy slowly solidifies and the released hydrogen is concentrated in the upper part of the casting in form of frozen

bubbles. Quantity of the hydrogen bubbles at the sample surface is determined by the hydrogen concentration. Vacuum method. This quantitative method uses solidification of a sample portion of the aluminum alloy in a small crucible at low pressure. Hydrogen dissolved in the alloy starts to form a gaseous phase (a bubble) at a certain pressure. When the first bubble is formed both the pressure and the temperature are measured. These parameters are used for determination of the hydrogen content by means of numeric diagrams.

to top Degassing by fluxes Fluxes composed of chlorine and fluorine containing salts are used for degassing molten aluminum alloys. Degassing fluxes are commonly shaped in form of tablets. Degassing operation starts when a flux tablet is plunged by a clean preheated perforated bell to the furnace bottom. The flux components react with aluminum forming gaseous compounds (aluminum chloride, aluminum fluoride). The gas is bubbling and rising through the melt. Partial pressure of hydrogen in the formed bubbles is very low therefore it diffuses from the molten aluminum into the bubbles. The bubbles escape from the melt and the gas is then removed by the exhausting system. The process continues until bubbling ceases. to top Rotary degasser

In the rotary degassing method an inert or chemically inactive gas (Argon, Nitrogen) is purged through a rotating shaft and rotor. Energy of the rotating shaft causes formation of a large number of fine bubbles providing very high surface area-to volume ratio. Large surface area promotes fast and effective diffusion of hydrogen into the gas bubbles resulting in equalizing activity of hydrogen in liquid and gaseous phases. Rotary degasser allows achieve more complete hydrogen removal as compared to the flux degassing. Additionally rotary degasser does not use harmful chlorine and fluorine containing salts. Rotary degasser may also combine the functions of degassing and flux introduction. In this case the inert gas serves as carrier for granulated flux. The method is called flux injection. Advantages of flux injection:

high effectiveness of flux action due to better mixing with the melt; short flux treatment time;

controllable flux introduction; more environmentally friendly method of fluxing.

Fluxes for melting aluminum

Dr. Dmitri Kopeliovich Fluxes for melting aluminum are solid substances (commonly mixtures of chloride and fluoride salts) used in aluminum foundries in order to reduce the melt oxidation, minimize penetration of the atmospheric Hydrogen, absorb non-metallic inclusions suspended in the melt, keep the furnace/ladle wall clean from the built up oxides, decrease the content of aluminum entrapped in the dross, remove hydrogen dissolved in the melt, provide aluminum grain refining during Solidification, modify silicon inclusions in silicon containing alloys, oxidize excessive magnesium. Common practice of flux introduction is manual application. Most of the fluxes are applied on the melt surface and stirred into the melt. Some of the fluxes (degassing, grain refining) are plunged to the bottom by a clean preheated perforated bell. Fluxes may also be introduced into the melt by injection in form of a powder in an inert gas (Argon or Nitrogen) stream. The simplest flux injection technique is a lance immersed into the melt. The most effective flux introduction method is injection by rotary degasser. Classification of fluxes for melting aluminum

Cover fluxes Drossing fluxes Cleaning fluxes Wall cleaning fluxes Degassing fluxes Grain refiners Silicon modifiers Demagging fluxes

to top Cover fluxes Melting point of a cover flux is lower than that of aluminum. Cover flux is applied on the surface of molten aluminum where it melts forming a continuous layer protecting the liquid metal from oxidation and absorption of atmospheric hydrogen. Cover fluxes are composed of a mixture of NaCl and KCl and may also contain some additions of CaCl2, CaF2 or KF. Fluorides (CaF2, KF) provide further decrease of the flux melting point and improve its cleaning ability. The disadvantage of fluoride containing fluxes is harmful fumes released by the flux at work

temperature. Sodium free cover fluxes are used for melting hyper-eutectic aluminum-silicon alloys (alloys containing above 12.6% of Si). Hyper-eutectic alloys are modified by phosphorus, additions of which cause refining of the primary crystals of silicon. Sodium reduce the refining effect of phosphorus in such alloys. to top Drossing fluxes Drossing fluxes promote separation of molten aluminum entrapped in the dross (sometimes up to 80%). Besides chlorides and fluorides drossing fluxes contain oxidizing component (KNO3) reacting exothermically with aluminum when heated. Heat generated by drossing flux improves wettability and fluidity of the entrapped aluminum, drops of which coalescence and flow down to the melt. The dross treated by the drossing flux is powdery and dry. It is easily removed from the furnace. Drossing fluxes helps to reduce losses of aluminum, which makes it very economically effective particularly in remelting aluminum scrap (chips, turnings etc.). to top Cleaning fluxes Cleaning fluxes remove oxides suspended in the melt. Similarly to the Drossing fluxes a cleaning flux is composed of mixture of chlorides, fluorides and an oxidizing agent. Cleaning fluxes generate less heat therefore their aluminum separation effect is lower. However they possess better ability to absorb oxides inclusions from the melt. to top Wall cleaning fluxes Wall cleaning fluxes soften oxides built up on the furnace walls. Wall cleaning fluxes contain double fluorides (Na2SiF6, Na2AlF6) and an oxidizing agent. The oxidizing agent reacts with aluminum generating heat, which promotes penetration of fluorides into the built up oxides softening them. The softened oxides are easily scrapped from the wall by the furnace operator. to top Degassing fluxes Fluxes composed of chlorine and fluorine containing salts are used for degassing molten aluminum alloys. Degassing fluxes are commonly shaped in form of tablets. Degassing operation starts when a flux tablet is plunged by a clean preheated perforated bell to the furnace bottom. The flux components react with aluminum forming gaseous compounds (aluminum chloride, aluminum fluoride). The gas is bubbling and rising through the melt. Partial pressure of hydrogen in the formed bubbles is very low therefore it diffuses from the molten aluminum into the bubbles. The bubbles escape from the melt and the gas is then removed by the exhausting

system. The process continues until bubbling ceases. Degassing flux may also be introduced by an injection method. In this case the inert gas serves as carrier for granulated flux. Besides the degassing effect the degassing treatment allows to remove non-metallic inclusions suspended in the melt (cleaning effect). to top Grain refiners Grain refining fluxes composed of salts containing titanium and boron (K2TiF6 and KBF4). The fluxes cause formation of numerous nuclei of TiAl3 TiB2 when aluminum melt cools down. Aluminum grains start solidification on the nuclei surface. The average solid grain size is determined by the concentration of the nuclei in the melt before solidification. Fine grain structure is characterized by better fluidity during solidification, low Microsegregation of impurities, low shrinkage porosity. Alternative method of aluminum grain refining is introduction of master alloys containing titanium and boron (eg. Al-5%Ti-1%B). to top Silicon modifiers hypo-eutectic and eutectic aluminum-silicon alloys are modified by fluxes containing sodium fluoride. Minor amount of sodium dissolved in the alloys refine the silicon structure resulting in improvement of mechanical properties (Fracture toughness#Toughness, ductility). Hypo-eutectic and eutectic aluminum-silicon alloys are also modified by introduction of metallic sodium or strontium. to top Demagging fluxes Demagging fluxes are used when the melt contains excessive amount of magnesium. The flux helps to reduce the magnesium content by burning (oxidizing) it from the melt. Alternative demagging method is oxidizing the excessive magnesium by gaseous chlorine. Classification of aluminum alloys is established by the International Alloy Designation System (IADS), based on the classification developed by Aluminum Association of the United States. This classification is accepted by most countries.

Classification of wrought aluminum alloys Classification of cast aluminum alloys

Classification of wrought aluminum alloys Each wrought aluminum alloy is designated by a four digit number.

The first digit indicates the alloy group according to the major alloying element: 1xxx Aluminum 99.0% minimum; 2xxx Copper (1.9%...6.8%); 3xxx Manganese (0.3%...1.5%); 4xxx Silicon (3.6%...13.5%); 5xxx Magnesium (0.5%...5.5%); 6xxx Magnesium and Silicon (Mg 0.4%...1.5%, Si 0.2%...1.7%); 7xxx Zinc (1%...8.2%); 8xxx Others. The second digit indicates modification of the alloy or impurity limits. Original (basic) alloy is designated by 0 as the second digit. Numbers 19 indicate various alloy modifications with slight differences in the compositions. In the alloys of the 1xxx series the second digit indicates modifications in impurity limits: 0 means natural impurity limit, 19 indicate special control of one or more impurities or alloying element. The last two digits identify aluminum alloy or indicate the alloy purity. In the alloys of the 1xxx series the last two digits indicate the level of purity of the alloy: 1070 or 1170 mean minimum 99.70% of aluminum in the alloys, 1050 or 1250 mean 99.50% of aluminum in the alloys, 1100 or 1200 mean minimum 99.00% of aluminum in the alloys. In all other groups of aluminum alloys (2xxx through 8xxx) the last two digits signify different alloys in the group. to top Classification of cast aluminum alloys. Each cast aluminum alloy is designated by a four digit number with a decimal point separating the third and the forth digits. The first digit indicates the alloy group according to the major alloying element:

1xx.x Aluminum 99.0% minimum; 2xx.x Copper (4%...4.6%); 3xx.x Silicon (5%...17%) with added copper and/or magnesium; 4xx.x Silicon (5%...12%); 5xx.x Magnesium (4%...10%); 7xx.x Zinc (6.2%...7.5%); 8xx.x Tin; 9xx.x Others. The second two digits identify aluminum alloy or indicate the alloy purity. In the alloys of the 1xx.x series the second two digits indicate the level of purity of the alloy they are the same as the two digits to the right of the decimal point in the minimum concentration of aluminum (in percents): 150.0 means minimum 99.50% of aluminum in the alloy, 120.1 means minimum 99.20% of aluminum in the alloy. In all other groups of aluminum alloys (2xx.x through 9xx.x) the second two digits signify different alloys in the group. The last digit indicates the product form: casting (designated by 0) or ingot (designated by 1 or 2 depending on chemical composition limits.) A modification of the original alloy or impurity limits is indicated by a serial letter before the numerical designation. The serial letters are assigned in alphabetical order starting with A but omitting I, O, Q, and X (the letter X is reserved for experimental alloys).

Effects of alloying elements on properties of aluminum alloys

Dr. Dmitri Kopeliovich Alloying elements when added to Aluminum alloys may produce effects of precipitation hardening (age hardening), solid solution hardening, dispersion strengthening, grain refining, modifying metallic and intermetallic phases, suppression of grain growth at elevated temperatures (e.g. during annealing), wear resistance and other tribological properties.

Silicon, Si (up to 17%)

Improves castability of aluminum alloys due to a better fluidity and lower shrinkage of molten aluminum-silicon alloys. o Increases strength of the alloys. o Improves resistance to abrasive wear. o Silicon in a combination with magnesium allows to strengthen the alloys by precipitation hardening heat treatment (Wrought aluminum-magnesium-silicon alloys (6xxx), Cast aluminum alloy 356.0). Copper, Cu (up to 6.5%) o Increases tensile strength, fatigue strength and hardness of the alloys due to the effect of solid solution hardening. o Allows to strengthen the alloys by precipitation hardening heat treatment (Wrought aluminum-copper alloys (2xxx), Cast aluminum alloy 201.0). o Decreases the ductility of the alloys. o Decreases corrosion resistance. Magnesium, Mg (up to 10%) o Strengthens and hardens the alloys by solid solution hardening mechanism without considerable decrease of ductility (Wrought aluminum-magnesium alloys (5xxx), Cast aluminum alloy 518.0. o In a combination with silicon or zinc allows to strengthen the alloys by precipitation hardening heat treatment (Wrought aluminum-magnesium-silicon alloys (6xxx), Wrought aluminum-zinc-magnesium alloys (7xxx), Cast aluminum alloy 356.0, Cast aluminum alloy 713.0). Manganese, Mn (up to 1.5%) o Strengthens and hardens the alloys (Wrought aluminum-manganese alloys (3xxx)) by solid solution hardening and dispersion hardening mechanisms. o Improves low cycle fatigue resistance. o Increases corrosion resistance. o Improves ductility of aluminum alloys containing iron and silicon due to modification of Al5FeSi intermetallic inclusions from platelet to cubic form Al15(MnFe)3Si2. Zinc, Zn (up to 8%) o In a combination with magnesium or magnesium-copper allows to strengthen the alloys by precipitation hardening heat treatment (Wrought aluminum-zincmagnesium alloys (7xxx), Cast aluminum alloy 713.0). o Increases susceptibility of the alloys to Stress corrosion cracking. Chromium, Cr (up to 0.3%) o Suppresses the grain growth at elevated temperatures (e.g. during heat treatment). o Improves ductility and toughness of aluminum alloys containing iron and silicon due to modification of Al5FeSi intermetallic inclusions from platelet to cubic form (similar to the effect of manganese). o Reduces susceptibility of the alloys to Stress corrosion cracking. Nickel, Ni (up to 2%) o Increases hardness and strength of aluminum-copper (Wrought aluminum-copper alloys (2xxx) and aluminum-silicon (Wrought aluminum-silicon alloy 4032) at elevated temperatures. o Reduces the Coefficient of Thermal Expansion.

Lithium, Li (up to 2.6%) o Increases strength by the precipitation hardening heat treatment. o Increases Modulus of Elasticity. o Reduces density. Titanium, Ti (up to 0.35%) o Refines primary aluminum grains (grains formed during the Solidification) due to formation of fine nuclei Al3Ti. Titanium is commonly added to aluminum alloys together with boron due to their synergistic grain refining effect. Boron, B (up to 0.03%) o Boron in a combination with titanium refines primary aluminum grains (grains formed during the Solidification) due to formation of fine nuclei TiB2. Zirconium, Zr (up to 0.3%); Vanadium, V (up to 0.2%) o Inhibit recovery and recrystallization o Increase the recrystallization temperature. Iron, Fe (up to 1.1%) o Increases strength due to formation of Al-Fe intermetallics. o Decreases ductility. I most aluminum alloys Iron is undesirable impurity. Sodium, Na (up to 0.015%); Antimony, Sb (up to 0.5%); Calcium, Ca (up to 0.015%), Strontium, Sr (up to 0.05%) o Increase ductility of hypoeutectic and eutectic aluminum-silicon alloys (Wrought aluminum-silicon alloys (4xxx), Cast aluminum alloy 443.0) by a modification of the silicon phase from coarse platelet like particles to fine fibrous structure. Tin, Sn (up to 40%) o Reduces coefficient of friction of aluminum alloys (Aluminum based bearing materials). o Increases compatibility of the aluminum bearing alloy. o Improves conformability. o Improves embedability.

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