Silicon

Atomic number Density, Atomic weight Melting point Boiling point

GENERAL Silicon, the second most abundant element in the Earth's crust (25.7%), is present in virtually all steels, either as a residual from ore, scrap or deoxidants, or as an intentional addition. Silicon products used in steelmaking are produced from quartzite, silica sand or by a variety of processes, almost all of which currently use submerged arc electric furnaces as reaction vessels. Low grade ferrosilicon was once made in blast furnaces, but the practice has now been completely discontinued in the U.S. Ultrahigh purity silicon, not intended for steelmaking, may be produced by reducing intermediate silicon compounds with hydrogen. AVAILABLE FORMS Because of its many uses, silicon is contained in a wide variety of addition agents. Some of these are simply used to add silicon and have general application; in others, the silicon serves as a carrier for other elements. Ferrosilicon is by far the most common addition agent. It is available in several standard grades containing from 15 to 95% Si. Of these, the 75% grade is the most widely used. The 75% FeSi grade is exothermic while 50% FeSi is endothermic. Significant impurities in ferrosilicon include carbon (up to 0.25%, but generally less than 0.10%) and aluminum (generally 1-1.5%, but lower, 0.10%, or higher, to 2%, in certain

14 20 C (68 F) 2.34 g/cm3 28.09 1412 C (2573 F) 2355 C (4270 F)

grades). Manganese will usually be present as well, but not over 0.40% unless specified. In all cases, phosphorus and sulfur contents are restricted to low residual levels: in general they will not exceed 0.025 and 0.040%, respectively. Standard foundry grades of ferrosilicon specify aluminum and calcium (0.501.50%). Silicon contents parallel those for steelmaking ferrosilicon. Ductile iron foundries also use magnesium ferrosilicon in both 5 and 9% magnesium grade with or without cerium, calcium and/or aluminum. Silicon-bearing deoxidizers on the market include: calcium silicon, calcium barium silicon, calcium barium silicon aluminum (Hypercal), calcium manganese silicon, silicon carbide and ferrosilicon zirconium. Silicon metal (97.5%) is used for superalloys, silicones, and nonferrous applications. Ferrosilicon and related alloys are generally sold in lump or granular form. Standard sizes range from 8 in. x D to as fine as 8 mesh x D. Coarser lumps are used for better slag penetration during deoxidation; finer sizes insure rapid dissolution when used as an alloying addition. Ferrosilicon is fairly friable and excessive handling will generate unwanted fines. Calcium silicon is exceedingly friable and must be handled carefully. Silicon carbide (SiC) is usually in a granular form. Sizing is 3/8 in. x D, 3/8 in. x 100 mesh, or 3/8 in. x 65 mesh depending on the need to control fines. Larger sizes are available up to 3 in. x 1 in., but only from producers using "big furnace" technology. Inerts are primarily silica and alumina. Petroleum coke and charcoal based silicon carbide usually runs 4-6% SiO2 and less than 1% Al2O3. Coal based SiC has 2-4% SiO2 and 25% Al2O3. The higher alumina in coal based SiC has proven to be a problem in continuous cast silicon killed steels. ADDITION PRACTICE The way in which silicon is used in steelmaking depends on the intended purpose of the addition, the practice involved, the condition of the steel, the aim residual silicon level, and the experience and preference of the individual operator. All these factors are implicitly related to the strong deoxidizing power of silicon which, at 1600 C (2910 F), ranks between manganese and titanium, but well below calcium. The deoxidizing power of silicon relative to that of carbon depends on pressure, i.e., on the partial pressure of CO above the melt. At one atmosphere, as in the furnace or an open ladle, silicon is slightly

stronger than carbon; at low pressures (0.10 atm or less), as in a vacuum degasser, the deoxidizing power of carbon is greater than silicon, especially at higher carbon concentrations. Silicon is the first major element removed from hot metal during melt down and is a major source of heat. If the silicon from the blast furnace iron is too low, the steelmaker may add ferrosilicon or silicon carbide for additional heat. Residual silicon levels will not exceed about 0.02% after melt down. In stainless steel melting, silicon additions may be made to the furnace to maintain silicon levels above 0.3% to maximize chromium recovery. Two points should be emphasized here: 1. Although silicon is a stronger deoxidizer than manganese, when the two elements are used together (either separately or as silicomanganese) they leave a much lower oxygen level in the steel. This is because their joint deoxidation product will be a manganese silicate, in which the activity of silicon is considerably less than it would be if silica were the only product formed. It should be noted that the effectiveness of manganese in increasing silicon's deoxidizing power decreases with increasing silicon content: the increase caused by 0.8% Mn is about ten times greater at 0.05% Si than at 0.2% Si. 2. Preliminary furnace deoxidation with ferrosilicon should be done with care since silicon has the power to reduce P2O5 in the slag. Thus, if slag phosphorus content is high and the slag is not flushed, it may remain insufficiently basic after the ferrosilicon addition. These conditions can lead to phosphorus reversion in the heat, especially if the slag is hot, and the bath analysis after block exceeds about 0.10% Si and 0.40% Mn at carbon levels over 0.15%. Modern practice aims to keep expensive furnace time as short as possible, tapping the heat "open" and relying mostly on ladle deoxidation. Ferrosilicon and silicomanganese become the primary deoxidizers. The amount of silicon added will depend on tap temperature and oxygen content and the residual silicon level needed after solidification.

Fully killed steels usually contain silicon in the range 0.15-0.30% Si. Exceptions are steels in which silicon is also an alloying agent, in which case silicon content will be somewhat higher, or aluminum killed steels such as AKDQ, where it is not needed at all. As a general rule, alloy steels and most medium carbon steels will be fully killed with ferrosilicon, even if only as a protection against reoxidation. Steels to which the elements titanium, zirconium, and rare earth metals are added (for inclusion shape control, or as nitrogen scavengers to protect subsequent or concurrent boron additions) will be deoxidized first with ferrosilicon for reasons of economy. These elements combine readily with oxygen and will be lost to the slag or remain trapped as oxide inclusions if the steel has been inadequately deoxidized. An inexpensive prior deoxidation therefore raises their ultimate recovery or improves their efficiency as nitrogen scavengers, as the case may be. Silicon carbide is added in three areas. As a ladle addition for silicon killed steel, granular SiC is added to the stream or directly into the ladle after at least 10% filled. Silicon recovery will be similar to that of 75% FeSi, while carbon recovery will be near 100%. In furnace applications (slag reduction), SiC is injected into the slag at the end of the oxygen blow. Moderate foaming occurs, which aids arc energy transfer to final temperature. One pound SiC will reduce 5.8 lbs. of FeO, 5.6 lbs. MnO, or 3.8 lbs. Cr2O3. It will react first with whichever of these oxides is present in the highest concentration. As a BOF fuel, SiC is added as briquettes or 96% Lump product into the BOF after scrap melt down and preliminary oxygen blow. SiC fuel component may be added into the stream during the blow as the need for additional temperature becomes apparent or is predetermined for the computer program. Additional lime is not required when using cement based SiC briquettes, but may be needed to offset the SiO2 produced when using the 96% Lump material. SiC can be used for chemical heating in the BOF, where hot metal is short or where there is an economic advantage to using a higher percentage of scrap. SiC is added to the foundry cupola charge as cement bonded bricks typically containing 36% SiC with 20 - 30% free carbon, to 75% SiC with almost no free carbon. Si recovery is usually 70 - 85%. In induction melting, 90% metallurgical grain is added for Si and C pickup and to deoxidize the bath. In heel melt applications, SiC is added

before the charge metal. In batch melt furnaces, SiC is added after, between 1/4 and 1/2 the charge is in. Sprue is added first when batch melting and steel added first in heel melt operations. ROLLING/FORGING Silicon strengthens ferrite and, to a lesser degree, austenite by solid solution hardening. Mill loads will therefore increase nominally with increasing silicon content. Strengthening is accompanied by a reduction in ductility, although this has little effect on workability at the silicon levels found in ordinary alloy steels. High silicon steels such as the electrical grades (see below) are quite brittle and require special care during cold rolling to the extent that hand mills are still sometimes used on special high-quality grades. Silicon steels have a reduced tendency to scale at elevated temperatures, but such scale as does form will be more difficult to remove during pickling. Silicon has a mild hardenability effect. Its multiplying factor is between that of chromium (higher) and nickel (lower). Silicon is therefore not added to steels for deep hardening, its function in heat treated steels being primarily to strengthen the ferrite in which carbides appear. Silicon is a graphitizer and, like nickel, has limited application in tool steels. It is used, however, in a class of oil hardening graphitic tool steels, AISI 06, as well as an air hardening graphitic tool steel, AISI A10, and two shock resisting tool steels, AISI S2 and S5. Silicon lowers the eutectoid carbon content but raises the eutectoid temperature. It is a ferrite former and when present in sufficient concentration, closes the g-loop completely. The effect is strongly dependent on carbon content: 2.25% Si will close the g-loop at <0.02% C, but some austenite will remain when carbon increases beyond 0.05%. Silicon may increase the tendency to 260 C (500 F) embrittlement and will have a slight, though detrimental, effect on temper embrittlement. It raises the impact transition temperature (ITT) but does contribute to solid solution strengthening. APPLICATIONS The solid solution strengthening properties of silicon are exploited in several classes of steels including HSLA grades and such ultrahigh strength steels as 300-M (1.6% Si). Silicon is present in AISI/SAE heat treatable alloy steels because these

products are always produced in the fully killed condition. Additionally, however, silicon confers a modest resistance to tempering (it does not produce secondary hardening). Silicon improves high temperature oxidation resistance and is therefore intentionally added to heat resisting Cr-Mo and Cr-Mo-V steels. It is also present in high temperature valve and spring steels for automotive engine applications. Both ferritic and austenitic stainless steels will contain about 1% silicon for oxidation resistance: Type 314 contains 2% silicon for this purpose. Silicon is the principal alloying element in a unique class of electrical steels used in transformers, electric motor laminations, generators and relays. Silicon confers a relatively high permeability, raises electrical resistivity and lowers hysteresis (core) loss, all beneficial trends in these materials. Generally, core losses decrease (quality is raised) as silicon level increases. Electrical steels will contain between 0.5 and 5.0% silicon, but there are two overlapping classifications: oriented sheet is heat treated to produce a particularly favorable crystallographic texture for ease of magnetization: non-oriented sheet has a random texture but may contain as much or more silicon. Electrical steels must be very clean (free from inclusions) and often require such special processing as pack rolling, frequent intermediate anneals plus, in the case of oriented grades, a final recrystallization anneal in dry hydrogen. Top of Page Copyright 2002. Shieldalloy Metallurgical Corporation. All rights reserved.